The effects of the SnO 2 pore size and metal oxide promoters on the sensing properties of SnO 2-based thick film gas sensors were investigated to improve the detection of very low H 2S concentrations (<1 ppm). SnO 2 sensors and SnO 2-based thick-film gas sensors promoted with NiO, ZnO, MoO 3, CuO or Fe 2O 3 were prepared, and their sensing properties were examined in a flow system. The SnO 2 materials were prepared by calcining SnO 2 at 600, 800, 1,000 and 1,200 °C to give materials identified as SnO 2(600), SnO 2(800), SnO 2(1000), and SnO 2(1200), respectively. The Sn(12)Mo5Ni3 sensor, which was prepared by physically mixing 5 wt% MoO 3 (Mo5), 3 wt% NiO (Ni3) and SnO 2(1200) with a large pore size of 312 nm, exhibited a high sensor response of approximately 75% for the detection of 1 ppm H 2S at 350 °C with excellent recovery properties. Unlike the SnO 2 sensors, its response was maintained during multiple cycles without deactivation. This was attributed to the promoter effect of MoO 3. In particular, the Sn(12)Mo5Ni3 sensor developed in this study showed twice the response of the Sn(6)Mo5Ni3 sensor, which was prepared by SnO 2(600) with the smaller pore size than SnO 2(1200). The excellent sensor response and recovery properties of Sn(12)Mo5Ni3 are believed to be due to the combined promoter effects of MoO 3 and NiO and the diffusion effect of H 2S as a result of the large pore size of SnO 2.
References
[1]
Hwang, I.S.; Choi, J.K.; Kim, S.J.; Dong, K.Y.; Kwon, J.H.; Ju, B.K.; Lee, J.H. Enhanced H2S sensing characteristics of SnO2 nanowires functionalized with CuO. Sens. Actuators B 2009, 142, 105–110.
[2]
Kim, S.Y.; Lee, S.C.; Hwang, B.W.; Lee, W.S.; Jung, S.Y.; Lee, D.D.; Kim, J.C. New SnO2-based thick film gas sensor promoted with molybdenum and nickel oxides for H2S detection. J. Nanoelectron. Optoelectron. 2011, 6, 293–296.
[3]
Jain, G.H.; Patil, L.A.; Wagh, M.S.; Patil, D.R.; Patil, S.A.; Amalnerkar, D.P. Surface modified BaTiO3 thick film resistors as H2S gas sensors. Sens. Actuators B 2006, 117, 159–165.
[4]
Yamazoe, N.; Matsushima, S.; Maekawa, T.; Tamaki, J.; Miura, N. Control of Pd-dispersion in SnO2 based sensors. Meas. Sci. Technol. 1991, 1, 201–205.
[5]
Gong, J.; Chen, Q.; Lian, M.; Liu, N.; Stevenson, R.G.; Adamic, F. Micromachined nanocrystalline silver doped SnO2 H2S Sensor. Sens. Actuators B 2006, 114, 32149.
[6]
Lantto, V.; Romppainen, P. Response of some SnO2 gas sensors to H2S after quick cooling. J. Electrochem. Soc. 1988, 135, 255055556.
Chowdhuri, A.; Gupta, V.; Sreenivas, K. Fast response H2S gas sensing characteristics with ultra-thin CuO islands on sputtered SnO2. Sens. Actuator B 2003, 93, 572–579.
[9]
Chowdhuri, A.; Gupta, V.; Sreenivas, K. Response speed of SnO2-based H2S gas sensors with CuO nanoparticles. Appl. Phys. Lett. 2004, 84, 1180–1182.
[10]
Kumar, R.; Khanna, A.; Tripathi, P.; Nandedkar, R.V.; Potdar, S.R.; Chaudhari, S.M.; Bhattti, S.S. CuO.tha2 element as hydrogen sulfide gas sensor prepared by a sequential electron beam evaporation technique. J. Appl. Phys. 2003, 36, 237737381.
[11]
Katti, V.R.; Debnath, A.K.; Muthe, K.P.; Kaur, M.; Dua, A.K.; Gadkari, S.C.; Gupta, S.K.; Sahni, V.C. Mechanism of drifts in H2S sensing properties of SnO2:CuO composite thin film sensors prepared by thermal evaporation. Sens. Actuators B 2003, 96, 2454052.
[12]
Yuanda, W.; Maosong, T.; Xiuli, H.; Yushu, Z.; Guorui, D. Thin film sensors of SnO2–nOsors,2 sandwich structure to H2S. Sens. Actuators B 2001, 79, 1878091.
[13]
Patil, L.A.; Patil, D.R. Heterocontact type CuO-modified SnO2 sensor for the detection of a ppm level H2S gas at room temperature. Sens. Actuators B 2006, 120, 316–323.
[14]
Wagh, M.S.; Patil, L.A.; Seth, T.; Amalnerkar, D.P. Surface cupricated SnO2–ZnO thick film as a H2S gas sensor. Mater. Chem. Phys. 2004, 84, 228–233.
[15]
Tsai, S.W.; Chiou, J.C. Improved crystalline structure and H2S sensing performance of CuO-Au-SnO2 thin film using SiO2 additive concentration. Sens. Actuators B 2011, 152, 176–182.
[16]
Park, H.D.; Lee, D.D.; Lee, W.I.; Kim, J.M.; Kim, J.M. Sensitivity of SnO2-based thick-film devices to CH3CN. Sensor. Meter. 1994, 5, 209–220.
[17]
Liu, H.; Gong, S.P.; Hu, Y.X.; Liu, J.Q.; Zhou, D.X. Properties and mechanism study of SnO2 nanocrystals for H2S thick-film sensors. Sens. Actuator B 2009, 140, 190–195.
[18]
Brunol, E.; Berger, F.; Fromm, M.; Planade, R. Detection of dimethyl methylphosphonate (DMMP) by tin dioxide-based gas sensor: Response curve and understanding of the reactional mechanism. Sens. Actuator B 2006, 120, 35–41.
[19]
Berger, F.; Brunol, E.; Planade, R.; Chambaudet, A. Detection of DEMP vapors using SnO2-based gas sensors: Understanding of the chemical reactional mechanism. Thin Solid Films 2003, 436, 136.
[20]
Choi, N J.; Lee, Y.S.; Kwak, J.H.; Park, J.S.; Park, K.B.; Shin, K.S.; Park, H.D.; Kim, J.C.; Huh, J.S.; Lee, D.D. Classification of chemical warfare agents using thick film gas sensor array. Sens. Actuators B 2005, 108, 298–304.
[21]
Kim, J.C.; Jun, H.K.; Huh, J.S.; Lee, D.D. Tin oxide-based methane gas sensor promoted by alumina-supported Pd catalyst. Sens. Actuators B 1997, 45, 271–277.
[22]
Lee, W.S.; Lee, S.C.; Lee, S.J.; Lee, D.D.; Huh, J.S.; Jun, H.K.; Kim, J.C. The sensing behavior of SnO2-based thick-film gas sensors at a low concentration of chemical agent simulants. Sens. Actuators B. Chem. 2005, 108, 148–153.
[23]
Lee, W.S.; Choi, H.Y.; Lee, S.C.; Lee, S.J.; Lee, D.D.; Huh, J.J.; Kim, J.C. Recoverable SnO2-based sensors promoted with MoO3 and Sb2O3 for the detection of DMMP. Rare Met. Mater. Eng. 2006, 35, 155–156.
[24]
Lee, S.C.; Hwang, B.W.; Lee, S.J.; Choi, H.Y.; Kim, S.Y.; Jung, S.Y.; Ragupathy, D.; Lee, D.D.; Kim, J.C. A novel tin oxide-based recoverable thick film SO2 gas sensor promoted with magnesium and vanadium oxides. Sens. Actuators B 2011, 160, 1328–1334.
[25]
Lee, S.C.; Kim, S.Y.; Lee, W.S.; Jung, S.Y.; Hwang, B.W.; Ragupathy, D.; Lee, D.D.; Lee, S.Y.; Kim, J.C. Effects of textural properties on the response of a SnO2-based gas sensor for the detection of chemical warfare agents. Sensors 2011, 11, 6893–6904.
[26]
Lee, S.C.; Choi, H.Y.; Lee, S.J.; Lee, W.S.; Huh, J.S.; Lee, D.D.; Kim, J.C. The development of SnO2-based recoverable gas sensors for the detection of DMMP. Sens. Actuators B 2009, 137, 239–245.
[27]
Lee, S.C.; Choi, H.Y.; Lee, S.J.; Lee, W.S.; Huh, J.S.; Lee, D.D.; Kim, J.C. Novel SnO2-based gas sensors promoted with metal oxides for the detection of dichloromethane. Sens. Actuators B 2009, 138, 446–452.
[28]
Lee, S.C.; Choi, H.Y.; Lee, W.S.; Lee, S.J.; Ragupathy, D.; Lee, D.D.; Kim, J.C. Improvement of recovery of SnO2-based thick film gas sensors for dimethyl methylphosphonate (DMMP) detection. Sens. Lett. 2011, 9, 101–105.
[29]
Lu, C,H.; Yeh, C.H. Influence of hydrothermal conditions on the morphology and particle size of zinc oxide powder. Ceram. Int. 2000, 26, 351–357.
[30]
Chena, Y.F.; Lee, C.Y.; Yeng, M.Y.; Chiu, H.T. The effect of calcination temperature on the crystallinity of TiO2 nanopowders. J. Cryst. Growth 2003, 247, 363–370.