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Tai-Jin Kim, Si-Dong Kim*, Nam-Ki Min
Department of Control and Instrumentation Engineering Korea University Jochiwon, Korea * Auto Electronic Corp email@example.com
Abstract—We present a micromachined NH3 chemiresistor sensor based on O2 plasma functionalized multiwall carbon nanotube (MWCNT)/ conducting polymer (CP) composites, and discuss its gas sensing mechanism. The FTIR spectra of plasma-treated MWCNTs indicate that oxygenated groups are created on the surface of CNTs after the plasma treatment. The plasma-functionalized MWCNT/PANI sensor exhibits a linear response of 3.34% per ppm NH3 for concentrations ranging from 10 to 100 ppm, and a sensitivity of about 7 times higher than that from a corresponding pristine MWCNT sensor. This dramatic change in resistance is attributed to the fact that the binding of the functional group with the defective CNT is stronger than that with the perfect one.
James Jungho Pak, Cheol-Jin Lee,Soo-Won Kim
School of Electrical Engineering Korea University Seoul, Korea
Ammonia (NH3) occurs naturally and is produced by human activity. It is an important source of nitrogen which is needed by plants and animals. No health effects have been found in humans exposed to typical environmental concentrations of ammonia. However, exposure to high levels of ammonia can cause irritation and serious burns on the skin and in the mouth, throat, lungs, and eyes. At very high levels, ammonia can even cause death. Ammonia is also flammable at concentrations of approximately 15% to 28% by volume in air. The United States Occupational Safety and Health Administration has set an acceptable 8h exposure limit at 25 ppm and a short-term (15 min) exposure level at 35 ppm by volume . Thus many efforts have been made towards the development of gas sensors for the proper control and detection of ammonia in the range of 0.1-100 ppm levels. There are many principles for measuring ammonia: metal-oxide gas sensors, catalytic ammonia detectors, and conducting polymer sensors. Although metal oxide sensors are highly sensitive, they require high operating temperature (>200 °C) in order to maintain high sensitivity levels [2,3]. Conducting polymer-based sensors have been observed to offer short response time [4,5];
however these devices suffer from limited sensitivity [2,5]. Recently, it was reported [6,7] that carbon nanotubes could be potentially used in a wide variety of chemical, gas, and biosensors. Carbon nanotube-based sensors offer significant advantages over traditional gas sensors such as semiconducting metal oxide- and polymer-based gas sensors. They can be operated at room temperature, offer greater conductivities, and are smaller than conventional gas sensors. Most CNT-based chemiresistors uses the mixture of CNTs with traditional bulk materials, typically polymer. For these nanocomposite devices, the matrix materials detects the analyte of interest, and the CNTs embedded in the matrix act as electrical conduction pathways from the matrix to the metal electrodes. NH3 gas sensors with various device architectures and matrix materials have been fabricated using CNT itself [6,8,9] and CNT/polymer nanocomposite materials[10,11]. In this paper, we demonstrate a micromachined NH3 chemiresistor sensor based on plasma-functionalized multiwall carbon nanotubes (p-MWCNT)/conducting polymer(CP) to enhance the sensitivity and impart the selectivity to sensors. Plasma-treatment of carbon nanotubes has been performed to facilitate the CNT-PC bond in the nanocomposite materials and to promote conduction between the CNTs and the CP. II. SENSOR FABRICATION
Fig. 1 shows a NH3 sensor based on plasma functionalized MWCNT/conducting polymer(CP) composite. MWCNTs were synthesized by the catalytic decomposition of C2H4 over Fe/Mo/Al2O3 catalyst at 923 K in an Ar/H2 atmosphere. The procedure is like that described in the previous paper . A mixture of Fe(NO3)3•9H2O and Mo was dissolved in ethanol, and this solution was added to aluminum isopropoxide dissolved in ethanol. The catalyst was calcined at 923 K in O2 for 2h, followed by a
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IEEE SENSORS 2008 Conference
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mechanical grinding for several hours. For comparative purposes. Then. 30W/90s or 100W/30s. PANI films were prepared by direct deposition from PANI solution onto the electrode set. Si3N4 membrane Pt heater Si Fig. Thus.5m). washed to neutral pH. resulting 209 Authorized licensed use limited to: Korea University.5-mm-thick CVD Si3N4 /SiO2 layers to isolate a 200 nm thick Cr electrodes from the heater. They show adsorption peaks corresponding to stretching vibrations of C=O and C-O. and H2 were introduced into the quartz tube at flow rates of 300. If a vacancy is functionalized with O2. and dried at 393 K for 12 h. the oxygen plasma treatment was carried out at a power of 30 W.5mm x 1. and sonicated for 5 hours. After the acid treatment. resulting in one C=O and C-O-C functional group [13. Electrodes Pt heater RTD Cr electrode MWCNT/PANI composite Fig. 1 (a) Micrograph of a microhotplate.5mm Si3N4 membrane. A backside silicon etching with KOH at 80℃ was used to form a 1. RESULTS AND DISCUSSION The FTIR absorption spectra of plasma-treated MWCNTs are showed in Fig. dissociation is observed. the CNT surface was etched chemically. Fig. The MWCNTs were purified by the treatment with 3 N nitric acid. 2 FTIR absorption spectra of plasma-treated MWCNTs for different plasma treatment time. The fabrication process starts with the LPCVD deposition of low-stress silicon nitride layers (8000 Å) to be used as a supporting membrane for the devices. and 500 sccm. The MWCNTs (1g) and 3 N nitric acid (400 mL) were added into a glass flask. O2 plasma treatment is expected to create defects such as vacancies in the sidewalls of CNTs.2. 500. The concentration of oxygen evaluated by FTIR and XPS was found to increase with increasing plasma treatment time up to 60s and then gradually decrease for treatment time beyond 60s. When a strong plasma treatment. and (b) schematic representation of the structure of micromachined MWCNT/CP NH3 sensors. C2H4. respectively.14]. For the production of MWCNTs. 3 XPS spectra of plasma-treated MWCNTs for different plasma treatment time. This caused CNT to be thinner or bent. III. in a polymer:solvent weight ratio of 3:100. followed by heating at 333 K for 12 h with continuously stirring. followed by air drying. The patterned heater and RTD were covered with 0. The microhotplate consists of the following stacked layers: a low-stress Si3N4 layer. treatment with oxygen plasma gives rise to carbonyl groups rather than hydroxyl groups. 2009 at 02:55 from IEEE Xplore. The dispersed MWCNT solution was accurately drop deposited across Cr electrodes by a micromanipulator. although OH groups have higher interaction energy with a perfect CNT wall as compared to other types of oxygen-containing groups . a pristine CNT and MWCNT/Nafion composites. . two NH3 sensors were also formed using different sensing materials. Fig. The temperature of the microheaters was controlled by external current. Si3N4 /SiO2 layers to insulate the heater from the electrodes. Polyaniline powder was dissolved in methylpyrrolidone. Pt/Ta layers for microheater and thermometer(RTD). and Pt electrodes. The oxygenated surface groups are suggested to be the anchoring sites for functional groups or gas molecules . Downloaded on June 16. For microheater and RTD 2000Å/200Å thick Pt/Ta layers were deposited on the device center by lift-off with optical lithography using negative photoresist. This indicates that oxygenated groups were created on the surface of CNTs after the plasma treatment. 3 shows the XPS survey spectra after the oxygen plasma treatment. Restrictions apply. The sample was heated up to 100℃ using microheater to enhance the adhesion of CNT film. was used. Ar. A 20 ml of 3wt% PANI solution in a 1 M HCl was stirred for 5 h and dried for 24 h at room temperature. These spectra reveal the presence of carbon and oxygen on the MWCNT samples. and the MWCNTs/ acid mixture was then subject to sonication for 30 min. the product was filtered on a membrane filter (PTFE 0. as well as at the open ends.
Fig. 6 Variation of △R/R0 of the plasma-functionalized MWCNT exposed to different NH3 concentrations.012 MWCNT/PANI P-MWCNT/PANI ΔR/R0 Fig. thus forming energetically more favorable ammonium ions (NH4+).002 0 20 40 60 80 100 These doped states can be controlled by acid/base reactions. Downloaded on June 16. N2 R/R0 1. After the first exposure to NH3.010 1. So positively charged local centers placed at nitrogen are formed.015 1. 210 Authorized licensed use limited to: Korea University.in the decrease of oxygen concentration on the sample.002 0. The sensitivity of the plasma-functionalized MWCNTPANI sensor was also compared to those of pristine MWCNT and MWCNT/nafion sensors. Restrictions apply. while the plasma-functionalized MWCNT/PANI sensor exhibits a linear response of 3. .025 1. For nanocomposite chemiresistor devices. Generally.004 0. A plasma-functionalized MWCNT/nafion sensor shows better sensitivity and better accuracy than a pristine MWCNT sensor. 4 Repetitive response of the plasma-functionalized MWCNT/PANI gas sensor to NH3 gas.000 0 20 40 60 80 100 Concentration (ppm) Fig.020 form . the matrix material detects the analyte of interest. This process is reversible. and the MWCNTs embedded in the matrix act as conduction pathways from the matrix to the metal electrodes. 5 NH3 gas detection mechanism of the plasma.014 0. the response of pristine MWCNT-based sensors are non-linear.5.6). This high sensitivity may be due to a presence of oxygen at the surface of O2 plasma-functionalized MWCNTs. while PANI itself turns into its base Concentration (ppm) Fig.001 0. replacement of the analyte with N2 decreases the resistance to a level that is maintained in subsequent recoveries from exposure to NH3.005 1. and when ammonia atmosphere is removed. forming N+-H chemical bonds (protonation).005 Pristine MWCNT P-MWCNT ΔR : R-R0 R0 : Initial resistance ΔR/R0 0. 2 and 3.006 0. 0. 7 Variation of △R/R0 of the plasma-functionalized MWCNT/PANI gas sensor at 0-100ppm NH3 concentration. When PANI is exposed in ammonia gas. an ammonia molecule takes up protons from PANA and then the protons on –NH– groups are transferred to NH3 molecules.006 0.008 0. and a sensitivity of about 7 times higher than that from a corresponding pristine MWCNT sensor. 0.007 0. neutral PANI molecules gains protons. compared to plasma-treated MWCNT/PANI devices.34% per ppm NH3 for concentrations ranging from 10 ppm to 100 ppm. providing the anchoring sites for functional groups. As shown in Figs. 2009 at 02:55 from IEEE Xplore. This is the PANI dedoping by deprotonation (Fig. as shown Fig. the ammonium ion can be decomposed to ammonia gas and proton. 6 and 7. as shown in Fig. The deprotonation reaction causes the electrical resistance of the PANI layer to increase [15-17]. This dramatic change in resistance is attributed to the fact that the binding of the functional group with the defective carbon nanotube is stronger than that with the perfect one. During doping.004 0. 0. 1. but with a much lower sensitivity and a higher low limit (detection limit) around 20 ppm. the MWCNTs are primarily used to increase the conductivity of the materials. 4 shows the response curves of plasmafunctionalized MWCNT/PANI sensor for four consecutive exposures to 100 ppm of NH3.000 0 NH3 1000 2000 Time (s) 3000 4000 5000 6000 Fig.010 0.functionalized MWCNT-PANI gas sensor.003 0.016 0.
573–590. M.1996. as evident from Figs. B. Ponchin-Epaillard. E. Q. pp. C. Actuators B. and C.18. “Persistence Length of Multiwalled Carbone Nanotubes with static Bending.” Science. Leanne Beer. D. 475. J. ΔR/R0 0. Actuators B. indicating linear increase in sensitivity with treatment time up to 60s. N. Itkis. W.. pp.C. pp. The sensitivity of MWCNTs/PANI composite sensor to NH3 gas was affected significantly by oxygen plasma treatment. Elena Bekyarova.  IV.012 0.009  0. Yeow.Y. A. K. Phys. 2006.000 0 20 40 60 80 100  Plasma treatment time (s) Fig. E.a review. Chapline. 2005.0.”Gas sensing characteristics of multi-wall carbon nanotubes. Itkis. CONCLUSION In summary. Van Lier. pp.36-46. vol. S. pp. Piletsky. Phys. vol. Shirshov. H. A. B. Yanga.  A. B. O.” Multi-walled carbon nanotube-based gas sensors for NH3 detection. vol. 2004. P. E. Diamond and Related Materials.  A. Lei. H. Han. Actuators B. 9 depicts the variation of △R/R0 with plasma treatment. Vol. 2007.074308.98.666-677. S. Charlier. Kong. A. C.D. Cinke.”Nanotube Molecular Wires as Chemical Sensors. Jing Li.37. Wanga. E. p. pp.018 MWCNT/Nafion P-MWCNT/Nafion ACKNOWLEDGMENT This work was supported by grant No. Bittencourt. H. K. X. Espinosa. 8 Variation of △R/R0 of the plasma-functionalized MWCNT/Nafion gas sensor at 0-100ppm NH3 concentration. R. Downloaded on June 16.014 0. Restrictions apply. Felten. vol. C.107. 2006. Sotter. Cho. 2005. K2060100000207E0100-00210 from Korea Foundation for International Cooperation of Science ＆ Technology. C. N. Peng.” Analytica Chimica Acta.129. Yun. . M. 2004.32-41.” Electroanalysis.” J. Ionescu. “Polyaniline as a new sensitive layer for gas sensors.J. vol.H. V. and CF4 treatments. Pireaux.022 0. P. “Fabrication and Properties of Conducting Polypyrrole/SWNT-PABS Composite Films and Nanotubes.C. vol. pp.” J. Lu. vol. C. M. Sunshine.024 0.” J. Grimes. pp. J. Charlier.020 0. Haddon. NH3. Zhongc. Bai and G. van den Berg.34% per ppm NH3 for concentrations ranging from 0 to 100 ppm. Olthuis. we have demonstrated a new O2 plasma functionalized multiwall carbon nanotube/ conducting polymer composite chemiresistor sensor. Shi. R. G. Mikhail E. AM.K Varghese. Zhao. pp. Franklin. vol. N. Pireaux .A. B. 2000. 2007. Zhang M.. D.008 20 40 60 80 100  Concentration (ppm) Fig. Ma. S. Kim. “Ammonia sensors and their applications .M.” Sensors.108. “Oxygen functionalisation of MWNT and their use as gas sensitive thick-film layers. Sinha. pp. 2001. Phys.003  Plasma treatment power : 30W 0. Kukla.” Electroanalysis. Chem. Gong." Sens. M. M. Ong. Dai1. The plasmafunctionalized MWCNT/PANI sensor exhibited a linear response of 3. J. Chen. W.L.135-140. Vol. REFERENCES   Toxic FAQ Sheet for Ammonia published by the Agency for Toxic Substances and Disease Registry (ATSDR). Nix. and J. Zhou. Haddon. R. Bekyarova.“Chemically functionalized single. S.” NANO LETTERS. D. 2003. These results suggest that nanocomposites of MWCNTs and conducting polymers offer great promise for the practical realization of high sensitivity NH3 gas sensors. Nelson Cabrera.walled carbon nanotubes as a Ammonia sensors. E. C. M. pp. A.-C. J.2 and 3. J.1327–1332. Wanekaya. 2006.   Fig. Llobet. Correig. The presence of oxygen on the surface of plasma functionalized MWCNT was found to increase the sensitivity to NH3.18882-18887. Vol.111. Sellinb. E.” Sens. T.“Ammonia sensors based on sensitive polyaniline films. Actuators B. Vilanova. which may be due to the decreased number of defects on the MWCNT surface available for interaction with PANI and NH3 molecules. 2006.10700-10706. vol.” Carbon Nanotube-Based Sensors. “RF-plasma functionalisation of carbon nanotubes surface: O2.1-15. Nanoscience and Nanotechnology.13. Van Lier.006 0. and R.” Sens. Y. Vol. Ye.622-625. X. Q. Lee.6. J. K.287. Burch.012  ΔR/R0 0.J.7. Nicolas-Debarnot and F. Chem.3. Bekyarova.010 0.    211 Authorized licensed use limited to: Korea University.Timmer. Meyyappan.015 0. H.” J. and M. G.81.H. J.” Sens.G.929-933. Deshusses. E. Davis. CHEM. pp.J. “Carbon Nanotube Sensors for Gas and Organic Vapor Detection. 2007. vol. Y.016 0.G.18.A. “Mechanism of Ammonia Detection by Chemically Functionalized Single-Walled Carbon Nanotubes: In Situ Electrical and Optical Study of Gas Analyte Detection. Vol.“Gas Sensors Based on Conducting Polymers.19719-19720. Dickey. Irina Kalinina. pp.1153-1158. September 2004.B. 9 Variation of △R/R0 of the plasma-functionalized MWCNT/PANI gas sensor at 100ppm NH3 concentration. and then decrease for treatment time beyond 60s.113. Yoo.     0. Lee. and Robert C. Haddon. Appl. G. 2009 at 02:55 from IEEE Xplore. J. 2003. Zhanga.10471054.J.Kichambre. pp. T. G. Bittencourt. S. vol. Felten. Myung “Electrochemically Functionalized Single-Walled Carbon Nanotube Gas Sensor.F.267-307.” J. pp. Yu. C. SOC.
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