Sensors and Actuators B 77 (2001) 463467

A study on thin lm gas sensor based on SnO2 prepared by pulsed laser deposition method
C.K. Kima,*, S.M. Choia, I.H. Noha, J.H. Leea, C. Hongb, H.B. Chaeb, G.E. Jangc, H.D. Parkd
a

School of Information Technology Engineering, Soonchunhyang University, Asan, Choongnam 336-745, South Korea b Department of Information and Physics, Soonchunhyang University, Asan, Choongnam 336-745, South Korea c Department of Materials Engineering, Chungbuk National University, Cheongju, Chungbuk 361-763, South Korea d MEMS Research Team, Korea Electronics Technology Institute, 455-6 Masan, Jinwi, Pyungtaek, Kyonggi-do 451-860, South Korea

Abstract SnO2 thin lms were fabricated by pulsed laser deposition (PLD) technique using Sn metallic target under ambient O2 gas. X-ray diffraction (XRD) and atomic force microscopy (AFM) were used to investigate the morphology and structure of the lms. From a study of the gas sensing characteristics of SnO2 lms, it was evident that if the shorter wavelength of the laser beam was used for lm deposition, the better sample was obtained. The sample, heated to 3758C during ablation and post-annealed at 5008C for 4 h, showed higher sensitivity compared to sample which was not heated. It can be explained, that the substrate heating is needed to compensate the kinetic energy of particles in laser plasma decreased due to loose-focusing. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: PLD; SnO2; Microsensor; Nd:YAG laser; MEMS

1. Introduction SnO2 is a typical n-type oxide semiconductor and is mostly used as reducing gas sensors [1]. The SnO2 thin lms are generally prepared by evaporation, sputtering, chemical vapor deposition, or solgel processes. In this study, SnO2 thin lms were also prepared by pulsed laser deposition (PLD) method using SnO2 target [2,3]. However, gas sensor using lms deposited by PLD method has not been actively studied yet. The last two decades have been considerable interest in PLD lms because of simple experimental set-up for deposition and possibility to prepare a wide variety of materials in thin lm form. The properties of the lms prepared by PLD method depend on the following process variables: substrate temperature, target composition, mutual arrangement of the substrate and the target, conditions in the chamber, and lasing parameters, such as power density, wavelength, and pulse repetition rate. If the sample is fabricated using tight-focusing method of laser beam, the droplet on the lm can be formed. To reduce the droplet, loose-focusing method was used in this

study. If loose-focusing to form thin lm is used, kinetic energies of ions ejected from the target decreases. Therefore, if the loose-focusing method to form thin lm with good quality are used, we need to heat the substrate at moderate temperature for compensating the kinetic energy [4,5]. In this work, we used two wavelengths, 532 and 355 nm, of Q-switched Nd:YAG laser to deposit the SnO2 lms to investigate the effect on the wavelength of the laser beam. The effect of substrate temperature during the deposition of the thin lm was also investigated. We fabricated the SnO2 microsensor using MEMS technology, which was composed of membrane, Pt thin lm on low stress Si3N4 membrane as heater and temperature sensor and SnO2 thin lm prepared by PLD method as a sensing layer. 2. Experimental The sensors were fabricated by using conventional silicon IC technology. The tin oxide microsensors were using three metal masks for photolithogray process and a shadow mask. A three-metal mask process was carried out for the fabrication of the tin oxide microsensor. The major processing steps are shown in Fig. 1. The microsensor device was fabricated on a silicon wafer.

* Corresponding author. Tel.: 82-41-530-1339; fax: 82-41-530-1373. E-mail address: ckkim1@sch.ac.kr (C.K. Kim).

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 2 6 - 2

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layer using mask I. An 0.5 mm thick SiO2 layer was deposited by plasma enhanced chemical vapor deposition (PECVD) method to passivate and insulate the sensing material. The SiO2 layer was subsequently subjected to a photolithography process to dene contact holes and sensing layer using mask II. The SnO2 sensing layer was then deposited onto the electrode using a shadow mask by PLD method. The Si3N4 layer on the backside of the silicon wafer to be used as a window for backside-etching was etched out by the reactive ion etching (RIE) process using mask III. The backside of silicon substrate was anisotropically etched by tetramethyl ammonium hydroxde (TMAH) solution, thereby, leaving behind the thin layers of sensing element, heater, electrode, and membrane. The mechanical stability of the membrane, especially its behavior at high temperature, was examined by subjecting the sensor to the temperaure cycles between room temperature and 3508C for 15 days. The SnO2 sensing lms were deposited by PLD method with the use of a Nd:YAG laser. The beam of the Nd:YAG laser (532 and 355 nm) was focused on purity (99.75%) tin target in spot size of 3 mm 3 mm with a plane-convex lens (focal length of 28 cm). The uences for 355 and 532 nm wavelengths were 250 and 400 mJ/pulse, respectively. The target was 10 mm in diameter. The base pressure in chamber was maintained about 5 106 Torr and then working pressure, when oxygen gas was introduced, was 8 104 Torr. The target was then ablated to produce tin plasma and oxygen was ionized in the form of O or O2 due to the interaction of laser beam and oxygen molecule. The substrate was heated to 3758C to compensate the kinetic energy during the deposition. The measurement of gas sensing properties was carried out in a system fully controlled by a personal computer. The crystallographic structures of SnO2 thin lms deposited by PLD method were studied using X-ray diffraction (XRD) analysis and surface microstructure was also investigated using atomic force microscopy (AFM).
Fig. 1. Schematic diagram for the fabrication process of microsensor.

3. Results and discussion Fig. 2 shows the XRD diffraction pattern of the SnO2 lm fabricated using a beam with wavelength of 355 nm of Nd:YAG laser where the substrate was heated to 3758C during laser ablation and post-annealed at 5008C for 4 h in air environment. It can be seen from Fig. 2 that the SnO2 phase was obtained. Fig. 3 shows the AFM image of a SnO2 lm, after the gas sensing, whose surface roughness is 0.139 mm, which is a typical characteristic shown in lms fabricated by PLD method. The nodule is formed since the laser plasma was periodically maintained for several tens of ms. It is because laser beam was applied periodically for several tens of ms. Up to now the effect on gas-sensing characteristics of the nodule was not investigated.

The detailed fabrication processes are as follows. The base material is a p-type (1 0 0) oriented 4 in. silicon wafer. The 2 mm Si3N4 layers on both sides of silicon wafer were deposited by low pressure chemical vapor deposition (LPCVD) method. The heater was made of the platinum deposited on a tantalum layer which works as a buffer layer not only to improve the adhesion of platinum onto the under layer but also to reduce inter diffusion at the processing and working temperature. Tantalum and platinum were depos , respectively, by ited to the thickness of 400 and 2000 A dc sputtering under standard conditions. The Pt/Ta doublelayer was then annealed at 5508C for 30 min. A lift-off process was used to make the heater and temperature sensor

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Fig. 2. XRD diffraction pattern of the SnO2 thin film.

Fig. 4 shows the hydrogen sensitivities of the samples fabricated by PLD technique where the used wavelengths of Nd:YAG laser beams were 355 and 532 nm. Then the substrate was not heated. Gas sensitivity is dened here as Rgas/Rair where Rgas is the resistance of SnO2 thin lm in hydrogen gas and Rair is the clean resistance under the ambient air atmosphere. The sensitivity of the sample using wavelength of 355 nm was higher than that of 532 nm. This could be explained, that if the wavelength of the laser beam is shorter, the kinetic energy of the ions ejected from the target is higher and the quality of sample.

The hydrogen sensitivity of SnO2 lm deposited by PLD technique is signicantly changed with substrate temperature during deposition and post-annealing as shown in Fig. 5. As shown in Fig. 5, the sample heated to 3758C during ablation and post-annealed at 5008C for 4 h showed higher sensitivity compared to sample which was not heated. In this experiments, the loose-focusing of the laser beam was used to reduce the droplet, where the laser beam size on the target was 3 mm 3 mm. If loose-focusing was used, the kinetic energy of the ions ejected from the target decreased. Therefore, the substrate heating is needed to compensate the kinetic energy decreased due to loose-focusing.

Fig. 3. AFM image of SnO2 film prepared by PLD.

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appeared on the surface of the sample. The sensitivity of the sample using wavelength of 355 nm was higher than that of 532 nm. This could be explained that if the wavelength of the laser beam is shorter, the kinetic energy of the ions ejected from the target is higher and the tin cluster ejected from the target is smaller, resulting in forming better surface quality of SnO2 lm. The sample heated to 3758C during the ablation and post-annealed at 5008C for 4 h showed higher sensitivity compared to sample which was not heated. If loose-focusing was used, the kinetic energy of the ions ejected from the target decreased. Therefore, the substrate heating is needed to compensate the kinetic energy decreased due to loose-focusing. References
[1] M.J. Madou, S.R Morrison, Chemical Sensing with Solid State Devices, Academic Press, Boston, 1989. [2] G. Williams, G.S.V. Coles, Gas sensing properties of nanocrystalline metal oxide powders produced by a laser evaporation technique, J. Mater. Chem. 8 (1998) 16571664. [3] W.S. Hu, Z.G. Liu, J.G. Zheng, X.B. Hu, X.L. Guo, Preparation of nanocrystalline SnO2 thin films used in chemisorption sensors by pulsed laser reactive ablation, J. Mater. Sci.: Mater. Electron. 8 (1997) 155158. [4] Y. Lifshitz, G.D. Lempert, E. Grossman, H.J. Scheibe, S. Voelinar, B. Schultrich, A. Breskin, R. Cehchik, E. Shefer, D. Bason, R. Kalish, A. Hoffman, Optical and photomission studies of DLC films prepared with a systematic variation of the sp3 composition, Diamond Relat. Mater. 6 (1997) 687693. [5] Y. Lifshitz, Hydrogen-free amorphous carbon films: correlation between growth conditions and properties, Diamond Relat. Mater. 5 (1996) 388400.

Fig. 4. Hydrogen sensitivities of the samples prepared by PLD method with wavelength of 355 and 532 nm.

Biographies
C.K. Kim received his BS and MS degrees in Electrical Engineering from Yonsei University in 1981 and 1983, respectively, and his PhD degree in Electrical Engineering from Vanderbilt University, 1992. Since 1993, he has been an Associate Professor at Soonchunhyang University in Korea. His research interests include semiconductor gas sensor, FED, and high power devices. S.M. Choi was born in Korea on 30 August 1973. He received his BS degree in Electrical Engineering from Soonchunhyang University in 1999. He is currently an MS candidate in Electrical Engineering at Soonchunhyang University. His research interests include micro gas sensor and biosensor. I.H. Noh was born in South Korea on 20 July 1974. He received his BS degree in Electrical Engineering from Soonchunhyang University in 2000. He is currently an MS candidate in Electrical Engineering at Soonchunhyang University. His research interests include micro gas sensor and FED. J.H. Lee was born in South Korea in 1969. He received his BS and MS degrees in Electrical Engineering from Soonchunhyang University in 1996 and 1998. He is currently a PhD candidate in Electrical Engineering at Soonchunhyang University. His research interests include micro gas sensor and FED.

Fig. 5. Hydrogen sensitivity of SnO2 film deposited by PLD method with substrate heating during deposition and post-annealing and without substrate heating and post-annealing.

4. Conclusions The gas sensor using thin lms deposited by PLD method was prepared on the microsensor fabricated by MEMS technology and its hydrogen sensitivity and microstructure were investigated. The nodule with the size of 2 mm was

C.K. Kim et al. / Sensors and Actuators B 77 (2001) 463467 C. Hong received his BS and MS degrees in Physics from Yonsei University, Seoul, South Korea and his PhD degree in Physics from the University of Texas at Dallas, TX, USA. After receiving a PhD in 1994, he is currently a Associate Professor in the Department of Information Technology and Physics at the Soonchunhyang University, Korea. His research interests lie in studying the growth of the pulsed-laser deposited carbon films with a preferred crystalline axis and diagnosing the laser plasma consisting of carbon atoms with the ionic and optical probes. Also he is interested in developing the organic EL devices using the PLD technique. H.B. Chae is currently a professor in the Department of Physics and Information Technology at Soonchunhyang University, Republic of Korea. After receiving a PhD in Physics from the University of Michigan, Ann Arbor, MI, in 1987, he spent 2 years as a Post-Doc at the Division of Thermophysical Properties in NIST, Gaithersburg, MD. His research interests lie in studying the thermophysical properties of CVD diamond, thin solid films, and the physical processes of PLD.

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G.E. Jang was born in 1956. He received the BS degree in Inorganic Materials Engineering from Han Yang University in 1983. He received his MS degree in Material Science & Engineering from University of Utah, USA, in 1987. He received his PhD degree in Material Science and Engineering from Michigan State University, USA in 1992. He joined the Korea Atomic Energy Research Institute as a senior researcher in 1993, where he remained until September 1995. He is currently an Associate Professor at the Department of Materials Engineering, Chungbuk National University, South Korea. H.D. Park received his BS, MS and PhD degrees in Electronic Engineering from Kyungpook National University, Taegu, Korea, in 1984, 1986 and 1993, respectively. He joined the Micromachine research center of Korea Electronics Technology Institute (KETI) in 1993. His research interests include the micro electro mechanical systems (MEMS) based sensors and optical devices. Currently, he is a principal researcher at KETI micromachine team.