# Surface Modification of Carbon Nanotube  Networked Films with Au Nanoclusters for  EnhancedNO2 Gas Sensing Applications

Authors: M. Penza; R. Rossi; M. Alvisi; G. Cassano; M. A. Signore; E. Serra; R. Giorgi
Journal: Journal of Sensors
 (2008)

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## Abstract

Multiwalled carbon nanotube (MWCNT) films have been deposited by using plasma-enhanced chemical vapor deposition (PECVD) system onto alumina substrates, provided with 6 nm thick cobalt (Co) growth catalyst for remarkably improvedNO2 gas sensing, at working temperature in the range of 100–250∘C. Functionalization of the MWCNTs with nanoclusters of gold (Au) sputtering has been performed to modify the surface of carbon nanotube networked films for enhanced and specific NO2 gas detection up to sub-ppm level. It is demonstrated that the NO2 gas sensitivity of the MWCNT-based sensors depends on Au-loading used as surface-catalyst. The gas response of MWCNT-based chemiresistor is attributed to p-type conductivity in the Au-modified semiconducting MWCNTs with a very good short-term repeatability and faster recovery. The sensor temperature of maximum NO2 sensitivity of the Au-functionalized MWCNTs is found to decrease with increasing Au-loading on their surface, and continuous gas monitoring at ppb level of NO2 is effectively performed with Au-modified MWCNT chemiresistors.


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## Body

## 1. Introduction

Carbon nanotubes [1] (CNTs)  are quasi-one-dimensional
nanostructures that exhibit very attractive structural, electrical, optical, and
mechanical properties for emerging nanotechnology devices [2]. In particular,
the CNTs are considered promising  nanomaterials for gas sensing due to their
large surface-to-volume ratio and hollow structure. CNTs have been used for
detecting small concentrations of gases [3–7] with high sensitivity upon
ambient conditions with different types and geometries of transducers
[6, 8–13]. The adsorption of electron-withdrawing (e.g., NO2) or electron-donating (e.g., NH3) molecules onto the surface of CNTs causes a charge transfer
between CNTs and the gas molecules with a typical p-type electrical behavior of semiconducting carbon nanotubes. Hole
carriers are increased in the CNTs when exposed to NO2 gas, causing an increase in their conductance. The interaction with
the NH3 gas produced an opposite effect.The need for air-quality monitoring demands the development of highly sensitive sensors that are selective for the detection of individual pollutant gases, especially NO2 gas which is a very toxic air-pollutant to be detected at sub-ppm level with high sensitivity and selectivity. Gas sensors based on CNTs are commonly cross-sensitive to many target gases with low specificity. Different strategies involving their surface modifications have been used to enhance sensitivity
and/or selectivity toward various gases: wrapped polymer coatings
[14], molecular engineering of purified CNT-based nanocomposites [15], polymer functionalization of carbon nanotubes for fabricating nanocomposite [16], surface-functionalizations with specific functional groups [17], and chemical and
physical modifications with metal nanoclusters [18]. The limitations of the low selectivity and slow recovery at room temperature of the CNT chemiresistors have
been investigated with successful attempts by means of functionalizations with
metal catalyst nanoclusters and operations at sensor temperatures above room
temperature up to 200–300°C. Recently,
our work [19] demonstrated that nanoclusters of
gold (Au) and platinum (Pt) enhance the gas sensitivity of CNT-based chemiresistors for NO2 and NH3 gas, respectively, with a working temperature in the range of 100–250°C achieving faster recovery than room-temperature operation.In this study, we investigate the effects of the tailored loading of Au-nanoclusters, which were deposited onto the surface of the modified CNTs, on the electrical properties of the CNTs gas sensors for selective NO2 gas environmental monitoring, at sensor temperature in the range of
100–250°C.


## 2. Experimental

### 2.1. Growth of Carbon Nanotubes and Sensor Fabrication

Multiwalled carbon nanotube (MWCNT) layers were prepared by a radiofrequency
plasma-enhanced chemical vapor deposition (RF-PECVD) system, at a reasonably low
growth-temperature of 450°C, onto low-cost alumina substrates (10 mm width × 10 mm length × 0.6 mm thickness). A schematic view of the fabricated chemiresistor
utilized is shown in Figure 1. A film
of cobalt (Co) nanoclusters with a nominal thickness of 6 nm was sputtering
deposited at 10-1 mbar onto room-temperature substrates for MWCNTs growth. The
catalysed-substrates were heated to 450°C with a heating rate of
10°C/min in H2 atmosphere, with an H2 flow of
100 sccm at a total pressure of 1.5 Torr. After the process temperature of 450°C is reached, an H2 plasma pretreatment was performed at an rf power (13.56 MHz) of 100 Watts for 10 minutes to obtain the metallic nanoclusters necessary for the nanotubes growth. Then, acetylene (C2H2), as carbon precursor, was introduced into the chamber. The gas flow rate ratio
between C2H2 and H2 was kept constant at
20/80 sccm, respectively. The MWCNTs PECVD-deposition was performed with constant rf power,
pressure, and temperature of 100 Watts, 1.5 Torr, and 450°C, respectively, for 30 minutes by depositing a carbon nanotube networked film that was estimated as about 250–300 nm thick.
Modification of the MWCNTs involved DC-sputtering of tailored loading of Au
nanoclusters with a nominal thickness of 2.5, 5, and 10 nm over the entire
substrate coated by MWCNTs. Two metal strips (2 mm width × 10 mm length) of Cr(20 nm)/Au(350 nm) were vacuum evaporated onto MWCNT
films for electrical contacts in the two-pole geometry. The electrical resistance, at room temperature, of unfunctionalized and Au-modified MWCNTs with increasing loading was measured
as 9.2 (0 nm Au), 8.1 (2.5 nm Au), 7.2 (5 nm Au), and 6.8
(10 nm Au) kΩ, respectively. Thus, the surface modification of MWCNTs with increasing
loading of Au-catalyst is found to decrease the resistance of the carbon
nanotube networked films, as expected. Before gas sensing exposure, the unfunctionalized
MWCNTs and Au-modified MWCNTs were thermally annealed at 300°C upon dry air
flow for 2 hours to purify the MWCNTs removing amorphous carbon and to stabilize
the sensing properties of catalyst nanoclusters improving their adhesion onto
MWCNTs.Figure 1
Cross-sectional view of the two-pole chemiresistor based
on Au-modified carbon nanotubes, grown with Co-catalyst by means of RF-PECVD
technology.


### 2.2. Measurements Setup

The experimental setup used for gas sensing measurements of the multiple chemiresistors upon
multiplexed readout and controlled gas flow system is shown in Figure2. The so-fabricated MWCNT sensors have been located in a test cell (500 mL volume) for gas exposure measurements. The cell case is able to host up to four chemiresitive sensors. The sensors were at thermal contact with a hot-plate, powered by a dc power supply (Agilent, 6644A) for controlling the desired working temperature. Dry air was
used as reference gas and diluting gas to air-conditioning the sensors. The gas
flow rate was controlled by different mass flowmeters (MFC) with various full
scale. These digital MFCs (MKS 1179A) were regulated and driven by a
controller-unit (MKS, GGK DMFC-5), equipped with a multiplexing/conversion
system communicating with a desktop-host via standard RS-485/RS-232 serial bus.
The total flow rate per exposure was kept constant at 1500 mL/min. The gas
sensing experiments have been performed by measuring the electrical conductance
of MWCNT thin films in the two-pole format upon controlled ambient of NO2
oxidizing gas and NH3 reducing gas in the range of 100 ppb–10 ppm and 5–1000 ppm, respectively, at sensor temperature ranging from 100 to 250°C. The sensor temperature was measured by a J-type thermocouple, whose output dc voltage was
measured by a multimeter (Agilent, 34401A).Figure 2
Experimental setup for gas sensing measurements of the
multiple chemiresistors in multiplexed read-out.The dc electrical conductance of the MWCNT sensors has been measured by the volt-amperometric
technique in the two-pole format by a multimeter (Agilent, 34401A). The sensors
were scanned by a switch system (Keithley, 7001) equipped by a low-current
scanner card (Keithley, 7158) with a multiplexed read-out. All acquired data
were stored in a PC-based workstation, interfaced with instrumentation by USB-GPIB
card (Agilent, 82357A), in software ambient compiled in Agilent-VEE.


## 2.1. Growth of Carbon Nanotubes and Sensor Fabrication

Multiwalled carbon nanotube (MWCNT) layers were prepared by a radiofrequency
plasma-enhanced chemical vapor deposition (RF-PECVD) system, at a reasonably low
growth-temperature of 450°C, onto low-cost alumina substrates (10 mm width × 10 mm length × 0.6 mm thickness). A schematic view of the fabricated chemiresistor
utilized is shown in Figure 1. A film
of cobalt (Co) nanoclusters with a nominal thickness of 6 nm was sputtering
deposited at 10-1 mbar onto room-temperature substrates for MWCNTs growth. The
catalysed-substrates were heated to 450°C with a heating rate of
10°C/min in H2 atmosphere, with an H2 flow of
100 sccm at a total pressure of 1.5 Torr. After the process temperature of 450°C is reached, an H2 plasma pretreatment was performed at an rf power (13.56 MHz) of 100 Watts for 10 minutes to obtain the metallic nanoclusters necessary for the nanotubes growth. Then, acetylene (C2H2), as carbon precursor, was introduced into the chamber. The gas flow rate ratio
between C2H2 and H2 was kept constant at
20/80 sccm, respectively. The MWCNTs PECVD-deposition was performed with constant rf power,
pressure, and temperature of 100 Watts, 1.5 Torr, and 450°C, respectively, for 30 minutes by depositing a carbon nanotube networked film that was estimated as about 250–300 nm thick.
Modification of the MWCNTs involved DC-sputtering of tailored loading of Au
nanoclusters with a nominal thickness of 2.5, 5, and 10 nm over the entire
substrate coated by MWCNTs. Two metal strips (2 mm width × 10 mm length) of Cr(20 nm)/Au(350 nm) were vacuum evaporated onto MWCNT
films for electrical contacts in the two-pole geometry. The electrical resistance, at room temperature, of unfunctionalized and Au-modified MWCNTs with increasing loading was measured
as 9.2 (0 nm Au), 8.1 (2.5 nm Au), 7.2 (5 nm Au), and 6.8
(10 nm Au) kΩ, respectively. Thus, the surface modification of MWCNTs with increasing
loading of Au-catalyst is found to decrease the resistance of the carbon
nanotube networked films, as expected. Before gas sensing exposure, the unfunctionalized
MWCNTs and Au-modified MWCNTs were thermally annealed at 300°C upon dry air
flow for 2 hours to purify the MWCNTs removing amorphous carbon and to stabilize
the sensing properties of catalyst nanoclusters improving their adhesion onto
MWCNTs.Figure 1
Cross-sectional view of the two-pole chemiresistor based
on Au-modified carbon nanotubes, grown with Co-catalyst by means of RF-PECVD
technology.


## 2.2. Measurements Setup

The experimental setup used for gas sensing measurements of the multiple chemiresistors upon
multiplexed readout and controlled gas flow system is shown in Figure2. The so-fabricated MWCNT sensors have been located in a test cell (500 mL volume) for gas exposure measurements. The cell case is able to host up to four chemiresitive sensors. The sensors were at thermal contact with a hot-plate, powered by a dc power supply (Agilent, 6644A) for controlling the desired working temperature. Dry air was
used as reference gas and diluting gas to air-conditioning the sensors. The gas
flow rate was controlled by different mass flowmeters (MFC) with various full
scale. These digital MFCs (MKS 1179A) were regulated and driven by a
controller-unit (MKS, GGK DMFC-5), equipped with a multiplexing/conversion
system communicating with a desktop-host via standard RS-485/RS-232 serial bus.
The total flow rate per exposure was kept constant at 1500 mL/min. The gas
sensing experiments have been performed by measuring the electrical conductance
of MWCNT thin films in the two-pole format upon controlled ambient of NO2
oxidizing gas and NH3 reducing gas in the range of 100 ppb–10 ppm and 5–1000 ppm, respectively, at sensor temperature ranging from 100 to 250°C. The sensor temperature was measured by a J-type thermocouple, whose output dc voltage was
measured by a multimeter (Agilent, 34401A).Figure 2
Experimental setup for gas sensing measurements of the
multiple chemiresistors in multiplexed read-out.The dc electrical conductance of the MWCNT sensors has been measured by the volt-amperometric
technique in the two-pole format by a multimeter (Agilent, 34401A). The sensors
were scanned by a switch system (Keithley, 7001) equipped by a low-current
scanner card (Keithley, 7158) with a multiplexed read-out. All acquired data
were stored in a PC-based workstation, interfaced with instrumentation by USB-GPIB
card (Agilent, 82357A), in software ambient compiled in Agilent-VEE.


## 3. Results and Discussion

Figure3 displays field
emission gun-scanning electron microscopy (FEG-SEM) images of unfunctionalized
MWCNT films and surface-modified with the increasing of Au-loading of 2.5, 5,
and 10 nm. The nanostructures show a pronounced tubular structure forming a
tangled net of bundled nanotubular chains densely distributed in mats. Some
amount of amorphous carbon is still present in the samples, even after the purification
procedure mentioned. A complete removal of amorphous carbon should require
higher temperature and/or longer annealing time although structural damage
should be avoided in the nanotube carbon-based material. However, the average
diameter of the MWCNTs seems to be varied in the range of 10–30 nm. The Au
particles partially decorating MWCNT sidewalls form isolated nanoclusters with
increasing size in the range of 5–15 nm, 5–30 nm, and 5–60 nm, respectively, with the increasing Au-loading deposited onto CNTs due to
migration and coalescence of the Au atoms induced by the temperature. The rational
modification of the CNTs surface with Au nanoclusters enables nanotubes with
tunable surface properties for the fabrication of selective gas sensors. The catalytic
covering of nanotubes strongly affects their properties of gas adsorption, hence,
the tailoring of gas sensitivity.FEG-SEM image at high magnification of RF-PECVD MWCNT
films, using a 6 nm thick Co growth catalyst onto alumina substrate, (a)
without Au-nanoclusters and with (b) 2.5 nm Au loading,
(c) 5 nm Au loading, (d) 10 nm Au loading.
(a)(b)(c)(d)Figure4 reports the time
response of the MWCNT chemiresistors, unfunctionalized and surface-modified
with different nanoclustered Au-loading of 2.5, 5, and 10 nm, exposed to 10-minute
pulses of decreasing spot concentrations of NO2 gas in the low range from 4 to 0.5 ppm. The working sensor temperature
was 200°C with the relative humidity in test cell of about 20%. The electrical
resistance of Au-loaded and unloaded MWCNT devices decreases rapidly when
exposed to NO2 gas, thus the p-type characteristic is maintained also after functionalization of the MWCNTs with Au
nanoclusters. The p-type character of
the semiconducting CNTs in the unfunctionalized format has been found by
several theoretical studies and experimental investigations reported in
[3, 4, 6, 7, 19]. Also, the functionalizing material of the CNTs could change from p-type to n-type the electrical behavior of the functionalized CNTs, as in the case of polyethyleneimine functional layer [7]. At this operating temperature
of 200°C, all MWCNT sensors show a fast recovery upon dry air of the baseline.
The MWCNTs functionalized with various Au-loadings exhibit a faster recovery
with respect to unloaded MWCNTs. A first rapid recovery step is followed by a
slower second step in the functionalized MWCNT-based sensors. This could be
attributed to the rapid desorption of the NO2 molecules in the first
recovery step, and a slower desorption of NO3 molecules, formed by
dissociation of two NO2 molecules onto CNTs surface [20]. The slower desorption of NO3 molecules from CNTs is explained by their higher
binding energy, ranging from −1.0 to −1.2 eV, with respect to NO2 molecules with lower binding energy, ranging from −0.34 to −0.79 eV. Thus,
the NO3 molecules are the most likely long-lived species on CNTs [20]. Different strategies for speeding the recovery phenomena are the degassing by heating of the sensor at a temperature above operating temperature [21], the
increased flux of the carrier gas during the recovery step [21], and ultraviolet illumination during the photoinduced recovery [22].(a) Time response of the NO2 gas chemiresistor
based on Co grown RF-PECVD MWCNT films, functionalized with Au-loading of 2.5,
5, and 10 nm, at working temperature of 200°C. The MWCNTs thickness is about 250–300 nm. The inset
plots the calibration curves for four CNT sensors toward NO2 gas at
200°C. (b) Time response of the NO2 gas chemiresistor based on Co grown
RF-PECVD 250–300 nm-thick
MWCNT films, functionalized with Au-loading of 5 nm at working temperature of
250°C.
(a)(b)In our experiments, the sensor response has been calculated as the percentage relative resistance
change ΔR/Ri (%) = [(Ri−Rf)/Ri] (%), where
Ri and Rf are the electrical resistance steady-state values of the MWCNT films
upon exposure to dry air and test gas, respectively. The inset of Figure 4(a)
shows the calibration curves of the MWCNT sensors, unmodified and
functionalized with various Au-loading nanoclusters, exposed to a wide range of
NO2 low concentrations, at sensor temperature of 200°C. The comparison
of NO2 gas sensitivity demonstrates that all Au-modified MWCNTs
have higher sensitivity than unfunctionalized MWCNT sensor up to two times more; and the highest sensitivity
to NO2 has been achieved by the MWCNTs with Au-loading of 5 nm. This
enhanced NO2 gas sensitivity of Au-loaded MWCNT sensors mainly depends on the
catalytic activity of the Au nanoclusters improving their sensing performance.
The chemical activity of Au may change with nanocluster size [23, 24]: the fraction of low-coordinated Au atoms allocated at the perimeter in the nanoclusters scales approximately with the catalytic activity, suggesting that
this fraction of most catalytically active Au sites changes with the size of
the nanoclusters with an optimal size related to the Au loading of 5 nm, as measured
as the highest NO2 gas sensitivity for MWCNTs surface loaded with 5 nm of Au.A typical NO2 gas detection  at ppb level of interest for environmental monitoring
is shown in Figure 4(b) by an MWCNT sensor loaded with 5 nm of Au at the operating temperature of 250°C. A minimum detection of 200 ppb NO2
has been clearly measured. This threshold is considered as alarm level in the Italian
regulations for air pollution. This very low detection level is attributed to a
very high gas sensitivity of Au-modified gas sensors. In fact, our device operating
at 250°C exhibits a gas response in terms of electrical change of 410 Ω to 200 ppb NO2 that is comparable with the response of 450 Ω to 100 ppb NO2 of high-sensitive thermally treated CNTs chemiresistors operating at 165°C [4]. This detection limit of 200 ppb NO2 is also comparable with the detection limit of 44 ppb NO2 measured at room temperature by casting single-walled CNTs sensors reported in literature [5]. However, multiple single-walled carbon nanotube n-type devices functionalized with
polyethyleneimine coating are capable of detecting NO2 at less than 1 ppb concentration [7]. These very low levels of sub-ppb
detection typically require high-resolution spectroscopy techniques. Finally,
the detection limit of a few hundreds of ppb for our device could be further improved
by an optimal choice of the Au clusters size and sensor working temperature.Moreover, the baseline of the Au-loaded MWCNT sensor is found to drift due to the high mobility of Au atoms on CNTs sidewalls [25]. Generally, the mobility increases with the temperature, thus it was extremely difficult to obtain stable conditions of the
baseline of the sensor at elevated temperatures. However, also the size of the
Au-nanoclusters should be optimal to reduce the thermal drift effects on sensor
baseline.The cross-sensitivity of four MWCNT sensors, unmodified and Au-loaded, has been measured in terms of mean sensitivity (%/ppm), expressed as percentage relative resistance change ΔR/Ri (%) weighted by exposed gas concentration (ppm) toward NO2 and NH3. Figure 5 reports the comparison of the chemical patterns obtained
at working temperature of 200°C. The experimental results indicate excellent selectivity
of all MWCNT sensors to NO2 with respect to NH3 with an NO2 mean sensitivity higher up to more than an order of magnitude for MWCNTs
loaded with 5 nm of Au. This property of the CNT sensors based on surface functionalization
with Au nanoclusters is very promising for environmental NO2 air-monitoring applications.Figure 5
Comparison of mean sensitivity of the MWCNT chemiresistor,
unmodified and Au-loaded of 2.5, 5, and 10 nm, toward NO2 and NH3 gas at working temperature of 200°C. The MWCNTs thickness is 250–300 nm and the
nominal thickness of Co growth-catalyst is 6 nm. The exposure time is 10
minutes.The effects of the temperature on the NO2 mean sensitivity of the MWCNTs, unloaded and Au-modified with 5 and 10 nm, are reported in Figure
6. At a given operating temperature, the mean sensitivity of the Au-loaded MWCNT sensors results to be higher than unfunctionalized sensors; and the temperature of maximum NO2 sensitivity of the Au-loaded MWCNT sensors decreases with
Au-loading: sensor temperature of 200°C for MWCNT sensor loaded with 5 nm of
Au, and 150°C for MWCNT sensor loaded with 10 nm of Au. Probably, the catalytic
activity of bigger Au nanoclusters degrades with the increasing temperature in
the range examined. In fact, the loss of low-coordinated Au atoms, present at
the extended nanoclusters perimeter, is highly probable occurring upon thermal
annealing at higher temperature considered resulting in a smoother and compact
nanoclusters shape, as observed in Figure 3.Figure 6
Comparison of NO2 mean sensitivity of the MWCNT chemiresistor, unmodified and
Au-loaded of 5 and 10 nm, as a function of sensor temperature in the range of
100–200°C. The MWCNTs
thickness is about 250–300 nm and the
nominal thickness of Co growth-catalyst is 6 nm. The exposure time is 10
minutes.Figure7 reports the short-term
repeatability of the response of the unfunctionalized and Au-modified
MWCNT-based sensors, at working temperature of 200°C to 10-minute five pulses
of the individual gases of 10 and 1 ppm NO2 and of 1000 and 100 ppm
NH3. The experimental results indicate very good short-term repeatability
in the real-time gas detection with better rate for the Au-modified MWCNT
sensor. To evaluate the short-term repeatability of the gas response of the
sensors, a figure of merit has been defined as the coefficient of variation,
D (%), expressed by the percentage ratio of the standard deviation (SD) over mean (M) for n gas concentration exposures repeated. The coefficient of variation, D, is given by
(1)D(%)=SDM×100.
The lower the coefficient of variation, D, the better is the short-term repeatability of the sensor to a given gas concentration repeated. The results achieved by calculating the
coefficient of variation for three CNT-based sensors have been reported in
Table 1. From data analysis, generally, the lowest D has been measured for the CNT sensor modified with an Au-loading
of 5 nm, excluding the gas concentration of 1 ppm NO2. However, both
Au-modified CNT sensors exhibit a coefficient of variation lower than that
related to unfunctionalized CNT sensor; thus the Au-modified CNT sensors show a
better short-term repeatability and the best repeatability has been found for
the CNT sensor modified with an Au-loading of 5 nm. These Au-modified CNT chemiresistors
show a better short-term repeatability compared to the commercial TGS Taguchi
gas sensors based on SnO2 thick films
[26] used to detect volatile organic compounds (VOCs) in the range
of gas concentration ranging from 25 to 100 ppm. In fact, the
coefficient of variation, D, of our
Au-modified CNT sensor results to be lower, up to about an order of magnitude,
than that of the commercial TGS VOCs SnO2-sensors, reported in literature [26].Table 1
Comparison of the coefficient of variation,D (%) for three MWCNT-based gas sensors: (i) CNTs unfunctionalized, (ii)
CNTs modified with Au loading of 5 nm, (iii)
CNTs modified with Au loading of 10 nm, toward five gas exposures of individual
gas of 1 and 10 ppm NO2, 100 and 1000 ppm NH3. The sensor
temperature for all sensors is 200°C. The thickness of MWCNTs is about
250–300 nm.
Gas concentrationCoefficient of variation,D (%)Sensor CNTsSensor CNTs_Au-5 mSensor CNTs_Au-10 m1
ppm NO23.43.12.910
ppm NO214.11.23.0100
ppm NH35.12.93.51000
ppm NH313.15.011.2Repeatability of the response of the unfunctionalized and
Au-5 nm modified MWCNT-based sensors toward 10-minute five pulses of (a) 10 and
1 ppm NO2 gas and (b) 1000 and 100 ppm NH3 gas at working
temperature of 200°C. The CNTs thickness is about 250–300 nm and the
nominal thickness of the growth-catalyst of Co is 6 nm.
(a)(b)Figure8 shows the continuous detection at sub-ppm level ranging from 100 to 600 ppb NO2 in the 30 minute step-pulse format using two CNT chemiresistors, at operating temperature of 200°C. As observed, the CNT sensor functionalized with Au-10 nm loading is
of higher sensitivity and higher resolution than unmodified CNT sensor, and the Au-modified CNT sensor is able to detect more efficiently also 100 ppb NO2 although being with a time-delayed response. This limit represents the NO2 attention level for environmental monitoring in the Italian
regulations. Finally, the comparison shows that the continuous
gas monitoring at ppb level of NO2 is effectively performed with
Au-modified MWCNT chemiresistors.Figure 8
Time online responses of two chemiresistors based on
unmodified CNTs and 10-nm loaded Au-modified CNTs (CNTs_Au-10 nm), exposed to
30-minute pulses of NO2 gas ranging from 100 to 600 ppb, at sensor temperature of 200°C. The thickness of CNTs films is about 250–300 nm.


## 4. Conclusions

In conclusion, CNT-based
chemiresistors have been successfully fabricated onto low-cost alumina
substrates using RF-PECVD technology for NO2 gas detection at operating
temperature in the range of 100–250°C. The
surface modification of the CNT networked films with size-controlled Au nanoclusters
enhances the NO2 gas sensitivity up to detection of sub-ppm level of great interest
for selective environmental NO2 air monitoring.
The effects of tailored Au-loading onto CNTs surface on NO2 gas sensitivity depend on nanoclusters size and sensor working temperature. An excellent short-term repeatability of the response to the selected targeted gases has been also measured for the Au-modified CNT-based sensors. A
continuous gas monitoring at ppb level of NO2 has been effectively
performed with CNT chemiresistors modified with a loading of Au-10 nm, at
sensor temperature of 200°C. The p-type character of the Au-modified CNT sensors has been also measured. Future work on different metal surface modifications of carbon nanotube networked films is planned for specific gas detection in sensor arrays concerning environmental monitoring applications.



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*Source: 107057-2008-11-16.xml*