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2010 International Conference on Nanotechnology and Biosensors IPCBEE vol.

2 (2011) (2011) IACSIT Press, Singapore

Synthesis of Carbon Nanotubes by Chemical Vapor Deposition and their Application for CO2 and CH4 Detection
Amin Firouzi, Shafreeza Sobri, Faizah Mohd Yasin, Fakhrul-razi b. Ahmadun
Department of Chemical and Environmental Engineering Universiti Putra Malaysia Serdang, Malaysia Firouzi.amin@gamil.com, eeza@eng.upm.edu.my, fmy@eng.upm.edu.my, fakhrul@eng.upm.edu.my
AbstractIn this letter, we demonstrate synthesis of Carbon Nanotubes (CNTs) and also, fabrication and testing of CNTsbased gas sensors. CNTs were synthesized by Floating Catalyst Chemical Vapor Deposition (FC-CVD) at 950C under methane gas flow rate of 150 Standard Cubic Centimeters per minute (SCCM) on quartz substrate. Then, the electrical resistance of CNTs was measured by exposing the sensor to CO2 and CH4 concentrations operating at room temperature. The sensors were highly responsive to the gaseous molecules. In the same experimental conditions, the recovery of the sensors was different for CO2 and CH4. The fabrication process was relatively simple and did not require special techniques. Keywords-carbon nanotubes; chemical vapor deposition; electrical resistance; gas exposure; quartz substrate

In this work, we present the synthesis of CNTs and employing them to fabricate gas sensors. In addition, the possible sensing mechanism is discussed. II. EXPERIMENTAL DETAILS

I.

INTRODUCTION

Since their discovery in 1991 by Iijima [1] Carbon nanotubes (CNTs) has attracted attention of scientific and researchers all over the world due to their extraordinary mechanical and unique electronic properties that make them useful for many applications such as conductive and high strength composites [2, 3], chemical [4] and gas [5] sensors and etc. For most applications, massive production of CNTs is required. Chemical Vapor Deposition (CVD) appears as a promising technique for production high quality nanotubes at large scales that is achieved by pyrolytic decomposition of hydrocarbon gases at elevated temperatures in the range of 600-1200C [6, 7]. Using methane as carbon source, reaction temperature in the range of 850-1000C, suitable catalyst materials and flow conditions, it is possible to grow high quality CNTs by a simple CVD process [8, 9, 10]. As a gas sensor, CNTs offer several competing advantages over the metal-oxide-based sensors, such as room temperature operating, low power consumption, small size and high sensitivity [4]. CNTs based sensors for detection of gases, such as H2, NH3, CO2 or CH4 have already been successfully demonstrated [11, 12, 13]. As we know, CO2 and CH4 are most abundant greenhouse gases and they can contribute to global warming so, detection of them is essential for environmental monitoring.

A. Nanotubes Growth In a typical process, the synthesis of CNTs was carried out in a ceramic tube reactor placed in a horizontal furnace. The ceramic reactor has 40 mm of internal diameter and 100 cm of length. The reactant gases employed were high purity methane and hydrogen and also ferrocene (C10H10Fe) was used as catalyst. A quartz substrate (1 cm 1 cm) was placed inside the ceramic tube. At first, argon flow was passed through the ceramic tube to remove the air inside the chamber, whereas the furnace was heating to reach 950C. Then, argon gas was pumped out of the chamber and mixture of methane (150 SCCM) and H2 (350 SCCM) were introduced to the reactor after sublimation of ferrocene [14]. The following reaction occurs with addition of ferrocene vapors [6]: CH4 (g) + H2 (g) 600-1200C Ferrocene C (s) + 3H2 (g)

In which (s) and (g) designate solid and gaseous phases, respectively. The reaction time is over after 30 minutes. Furnace was subsequently cooled to room temperature by argon gas. Fig. 1 shows the schematic of the synthesis process [7].

Figure 1. Schematic of the synthesis process.

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B. Gas Sensing Procedure Gas sensing experiments were carried out by placing CNTs synthesized on a quartz substrate in a sealed plexiglas test chamber of 0.027 m3 volume with electrical feedthrough. At first, chamber was purged continuously with pure argon gas about 1 hour. Then, diluted CO2 or CH4 in the argon as a carrier gas with concentration of 369 ppm was injected into the chamber at room temperature of 25C. Sensors resistance was measured at interval of one second with a digital multimeter connected to a computer using a RS232 interface that was fully automated and logged by a program. We repeated each test for three times to obtain the exact results. A schematic for the apparatus used for gas detection is shown in Fig. 2. III. RESULTS AND DISCUSSION

A. Structure Characterization The samples were characterized by using Scanning Electron Microscopy (SEM) and Transmission Electron Microscope (TEM). Fig. 3a shows the SEM image of CNTs obtained on quartz substrate after the catalytic decomposition of methane at high temperature of 950C. Dense and relatively aligned forests of CNTs are visible on SEM micrographs (Fig. 3a). Also, SEM image shows that the grown CNTs are uniform and meadow-like. From TEM image (Fig. 3b) we observed CNTs with fairly thin diameters of about 18-35 nm. It seems to be linked to the effect of starting catalyst particles size on nanotube diameter [15, 16]. As we used a relatively high flow rate of hydrogen (350 ml/min), some iron nanoparticles were driven away from the furnace, decreasing the number of catalyst particles inside the furnace, resulting in low collisions between the particles, which leads to the formation of smaller clusters and formation of CNTs with rather narrow diameter.

Figure 3. Synthesized CNTs on quartz (a) SEM image (b) TEM image.

Figure 2. Schematic of gas sensing system.

B. Gas Sensing Characterization After purging with argon gas, the sensors were employed to detect CO2 and CH4 gases. Fig. 4 shows the electrical resistance variations of CNTs-based sensor to CH4 gas. We obtained our sensor are highly sensitive with a fast response time of 45 seconds. It also indicates that the recovery of the sensors is relatively fast and complete. This can be due to the fact that methane is a saturated hydrocarbon, resulting in the weak interaction between tested gas and CNTs molecules.

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Fig. 5 depicts the variations of the sensors resistance to CO2 exposure with two ohm increments per injection. The recovery of the sensors is slow and incomplete at room temperature compared to that of the methane gas within the same time frame. This can be ascribed to the higher adsorption energy and rather strong interaction between CO2 molecules and CNTs molecules resulting in the incomplete CO2 desorption in the short time.

S (%) = (( Rg R0 )/R0 )*100

(1)

Where, Rg and R0 are the resistance values of the sensor with and without gas exposure, respectively. Table 1 summarizes the Sensitivity of sensors to gas exposure. IV. CONCLUSION In conclusion, we synthesized dense and high quality CNTs on quartz substrate by CVD of methane at 950C. The grown CNTs have been utilized to detect CO2 and CH4 as gas sensors. Our sensors showed good responses to the same concentration of these gases at room temperature. We observed that the electrical resistance of sensors increased after gas exposure in all experiments, due to the hole depletion of p-type semiconductor CNTs. Therefore, CNTs should be promising to fabricate novel miniaturized chemical sensors and it is expected that many applications of CNT-based sensors will be explored in the future. ACKNOWLEDGMENT This work was supported by the research grant provided by the Malaysian Ministry of Science, Technology and Innovation.
TABLE I. SENSITIVITY, S (%), OF SENSORS TO CH4 AND CO2 EXPOSURE

Figure 4. Electrical resistance variations of CNTs-based sensor upon injection of CH4 gas.

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We observed that the resistance of CNTs increased for both exposures. This increase can be described as follows: Since it is known that CO2 and CH4 are electron donor gases [17]. When the sensor is exposed to these gases, they donate electrons to the valence band of CNTs thereby, increasing the separation between the Fermi level and the valence band, resulting in hole depletion in the p-type semiconductor CNTs and increasing the electrical resistance [4]. The sensor sensitivity (S) is calculated using (1) [18]:

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