A carbon nanotube based ammonia sensor on

cellulose paper
Jin-Woo Han, Beomseok Kim, Jing Li and M. Meyyappan
A single-wall carbon nanotube (CNT) based ammonia sensor was implemented on cellulose paper. Two
types of devices were fabricated and compared: CNT-on-paper and a CNTcellulose composite. The
resistance shift of the CNT network upon ammonia exposure was monitored in the chemiresistor
approach. The CNT-on-paper showed faster response/recovery and higher sensitivity than the CNT
cellulose composite due to the larger reaction surface. Compared to the control sensor made on a glass
substrate, the paper based sensor characteristics exhibited superior uniformity and repeatability. The
present approach can be utilized for smart paper featuring low-cost disposable applications.
1 Introduction
Electronic devices built on cellulose paper substrates have
attracted much attention due to their exible, foldable, biode-
gradable, and disposable properties. The paper as a substrate is
much cheaper than others including plastic, glass, and silicon
wafer. These features create smart papers with new applications
such as biomedical sensors, intelligent packages, and e-books.
Several studies have implemented various components on
paper including lab-on-paper,
1
thin-lm transistors,
2
nonvola-
tile memory devices,
3
RFID tags,
4
electroluminescence devices,
5
dye-sensitized solar cells,
6
batteries,
7
supercapacitors,
8
printed
circuit boards,
9
and humidity sensors.
10
The CNT based chem-
ical sensor on paper substrate was reported previously
11
where a
pencil lead composed of CNT served as a source of sensing
material, thus oering an attractive approach for the fast
fabrication of sensors. Likewise, the present work utilizing CNT
ink is also suitable for rapid prototyping as the fabrication
process mainly consists of drawing the needed device struc-
tures. Herein, we present an ammonia (NH
3
) gas sensor on
paper substrate as a new building block for the smart paper.
NH
3
is a toxic gas that can be present at higher than allow-
able concentrations near farms, chemical industries, and
refrigeration systems. An increase in NH
3
concentration in
human breath is found in patients with kidney disorders and
ulcer. Therefore, NH
3
sensors are needed in many applications
such as air quality control, leak detection and clinical diag-
nostics. Oxide thin lms such as titanium oxide (TiO
2
), zinc
oxide (ZnO) and tin oxide (SnO
2
) have been used widely in
chemical sensors. Recently, the nanowire form of these oxides
has also been considered for gas and vapor sensing.
12
Unfor-
tunately, metal-oxide semiconductors work only at
temperatures above 150

C, which is not suitable for ordinary
paper. In contrast, room temperature operation is possible with
CNT sensors.
13
Furthermore, the dispersion and deposition of
CNTs can be done by solution processing without the need for
any high temperature procedures. In this work, CNT-on-paper
and CNTcellulose composite were fabricated and their prop-
erties were characterized and compared. Based on the require-
ment of USOSHA (US Occupational Safety and Health
Administration) for the acceptable exposure of NH
3
(e.g.,
25 ppm for 8 hours and 35 ppm for 15 min. exposure), a test
range of 10100 ppm was considered.
2 Experimental work
The CNTcellulose paper structure can be prepared by two
approaches: (i) the CNT network directly on the surface of the
paper, namely a layer-by-layer structure and (ii) a composite of
the nanoscale CNTs and the microscale cellulose bers. These
structures can be produced by various methods including
ltration, LangmuirBlodgett deposition, electro-spinning and
spin coating of dispersed CNT solutions. However, since rapid
and inexpensive processing are the desirable features for paper
electronics, the simple drop-coating method for the layer-by-
layer structure and papermaking ltration approach for the
CNTcellulose composite lm were selected in the present
work. Fig. 1 shows the schematic and scanning electron
microscopy (SEM) images of the paper sensors. The cellulose
lter paper and single wall CNTs were the starting materials.
The bare lter paper was used as a paper substrate and its
disentangled bers were used for composite matrix. For the
CNT-on-paper, CNTs in a dispersion solution were drop cast on
a 10 cmlter paper, followed by ambient drying. The composite
paper was prepared by ordinary paper making process with
minor modications. The chopped lter paper immersed in
deionized water was subjected to magnet agitation for 24 hours.
Center for Nanotechnology, NASA Ames Research Center, Moett Field, California
94035, USA. E-mail: jin-woo.han@nasa.gov
Cite this: RSC Adv., 2014, 4, 549
Received 14th August 2013
Accepted 7th November 2013
DOI: 10.1039/c3ra46347h
www.rsc.org/advances
This journal is The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 549553 | 549
RSC Advances
PAPER
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Next, the SWCNTs were mixed with the cellulose suspension
and the ber composites were further dispersed by ultra-
sonication for 1 hour. The single wall CNTcellulose mixture
solution was vacuum ltered and the aqueous at paper was
completely dried under vacuum ambient. The paper based
sensors can be simply cut into custom geometry as shown in
Fig. 1(c). A test clip with gold-plated copper pad was used for
electrodes and the custom-cut paper sensors were mounted on
the pins with 0.1 inch spacing. The stainless steel spring
assured the connection to the sample.
Fig. 2 shows the experimental setup for real-time measure-
ment for the fabricated sensors. The gas sensing experiments
were carried out using Environix variable air volume system
with Agilent digital multimeter. The sensor was placed in a
chamber with electrical feed-through. A DC current of 10 mA was
applied and then the induced DC voltage was measured for
calculating the resistance. For example, the measured voltage of
10 V deduces a resistance of 1 MU. 99.99% NH
3
was used as gas
source and a mixture of compressed dry air and water vapor was
used as carrier gas. The dry air was mixed with pure NH
3
and
then the relative humidity was controlled by varying the volu-
metric moisture content until it reached the pre-specied value.
Prior to rst NH
3
exposure, the carrier gas with no NH
3
was
own for 5 min to ush out the pre-adsorbed species such as
moisture and stabilize the sensor. Such sensor conditioning is
routine in practical sensor operation. The adsorption and
desorption periods were xed for 3 min and 5 min, respectively.
Unless otherwise specied, the relative humidity and tempera-
ture of all gases were controlled to 30% and 25

C respectively in
the sensor evaluation runs.
3 Results and discussion
The CNTs oer plenty of reaction sites and when NH
3
molecules
are adsorbed on the surface, they donate electrons to CNTs.
Under ambient conditions, the CNTs tend to be a p-type semi-
conductor with holes as majority carriers. Hence, the reduction
of hole concentration due to electron supply upon NH
3
adsorption increases the resistance. Fig. 3 shows the responses
of the two dierent types of paper sensors. The response and
recovery behaviors are repeatable. The response (R) is dened as
R 100 [(R
t
R
0
)/R
0
], where R
0
and R
t
represent the resis-
tances before and aer exposure to NH
3
. The positive R values
upon exposure to ammonia imply an increase in resistance. The
ambient humidity was approximately 60% before measurement
but the baseline humidity during measurement was kept 30%.
Moisture aects the resistance of CNTs; the current of the p-type
CNTs decreases as humidity increases up to 65% and then,
starts to increase again with increasing humidity aer this
point.
14
Therefore, during the sensor conditioning step, the
resistance decreased as the humidity was decreased from 60%
to 30%. The moisture molecules absorbed on the CNT surface
serve as charge traps; in other words, desorption of surface
moisture during the initial conditioning step can mitigate the
charge trapping and consequently decrease the resistance as
shown in Fig. 3(a).
Fig. 1 Paper based sensors, (a) schematics of CNT on cellulose paper
(layer-by-layer), (b) CNTcellulose composite, (c) photo image of the
paper based sensor, (d) SEM image of the CNTs on cellulose paper, (e)
higher magnication of the image in (d).
Fig. 2 Experimental setup for real-time measurement for the gas
sensors.
Fig. 3 (a) The sensor response of layer-by-layer (blue lines) and
composite sensors (red lines). The layer-by-layer structure shows
faster and higher response/recovery than the composite structure. (b)
The sensor calibration curves for the layer-by-layer (blue squares) and
composite sensor (red circles). The layer-by-layer sensor shows a
better minimum detection limit.
550 | RSC Adv., 2014, 4, 549553 This journal is The Royal Society of Chemistry 2014
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Doping and introducing defects have been known to
increase the sensitivity. Here, no eorts were made to dope the
CNTs. Only the celluloseCNT composite could have had
defects introduced along the sidewall of the CNTs during the
ultrasonication process. Nevertheless, the celluloseCNT
composite shows smaller sensitivity than the layer-by-layer
structure. A substantial fraction of the CNTs is enclosed inside
the cellulose matrix, whereas the CNTs lying on the paper
surface have a larger surface reaction area. Thus, the active
surface area of the CNTcellulose composite tends to be smaller
than that of the layer-by-layer structure. As the volume density
of CNTs in composite becomes small, the tube-to-tube charge
transport can be hindered. Therefore, the conductivity change
of the CNT network upon reaction with NH
3
can be smaller for
the composite than for the lm. Fig. 3(b) shows the calibration
curves for both sensors showing response versus ammonia
concentration. The composite sensor shows a linear behavior in
the 10100 ppm range whereas the layer-by-layer structure
shows a tendency to saturate at high concentrations.
For some gases and vapors, a slow sensor recovery has oen
been reported.
15,16
Heating,
17
high vacuum operation,
18
and
ultraviolet light illumination
16
have been attempted to eec-
tively accelerate desorption of molecules. But the same methods
may not be suitable in paper electronics, which feature high
portability and mobility and low operation power and temper-
ature. In any case, our sensors here show reasonable recovery
characteristics with no additional eorts. The recovery proper-
ties may be explained by the ventilation eect. Since the
substrate surfaces of glass and Teon are closed, the desorbed
gas molecules must bounce back against the air inow in the
test chamber, which may hinder the desorption causing a slow
recovery. In contrast, the cellulose paper or the composite is
porous, enabling the sensors to breathe. The desorbed mole-
cules can be shuttled and evacuated by the gas ow through the
pores. Therefore, the residual gas molecules are quickly taken
away, leading to relatively rapid sensor recovery. The layer-by-
layer structure shows faster recovery than the composite; this
can be expected because the CNTs on paper are more favorably
exposed to the ambient whereas the CNTs in composites are
embedded within the matrix.
The cellulose bers can also be involved in chemical reac-
tions because the CNTs are entwined with not only the adjacent
CNTs but also with the cellulose bers. The cellulose is a
straight chain polymer with multiple hydroxyl groups on its
surface. Some surface hydroxyl groups form hydrogen bonding
with neighboring celluloses or adjacent CNTs. But a fraction of
the surface hydroxyl groups that remain unconnected can be
reaction sites with ambient chemicals. Therefore, the hydroxyl
group and ammonia together can result in a chemical reaction
such as OH + NH
3
/ NH
2
+ H
2
O. Nevertheless, it should be
noted that such reactions do not change the resistance of
cellulose as the backbone of cellulose ber is intrinsically an
insulator. Though the cellulose bers are intrinsically insu-
lating, the localized cellulose bers segmented by CNTs can
contribute to the intertube charge transport. Since CNT network
is closely and densely entwined in cellulose matrix, the cellulose
ber can bridge adjacent CNTs in nanoscopic dimension. The
percolating network of water molecules absorbed to OH

units
on the cellulose chain allows the conduction process.
19,20
When
the distance between the OH

sites becomes narrow, the

tunneling transport mechanism can be involved so that the
charge conduction between nanotubenanotube in nanoscale
distance can be assisted by the cellulose matrix. Therefore, the
carrier hopping or tunneling can take place through the surface
states of cellulose, which can enhance the charge conduction.
The current conduction pathways are therefore formed across
CNTs as well as bridging via cellulose on the paper substrate.
More specically, the localized cellulose bers segmented by
CNTs can contribute to the intertube charge transport. Thus, not
only the physical morphology but also the chemical properties of
cellulose can aect the sensitivity. The cellulose is a straight chain
polymer with multiple hydroxyl groups (OH

). These end-groups
form hydrogen bonds within and between cellulose molecules
and adjacent CNTs. Most of the hydroxyl groups remain on the
surface, which can react with the analyte molecules. Therefore,
the cellulose boosts the charge transport of CNT network upon
NH
3
exposure. It is noted that the present sensor uses non-
functionalized CNTs in a preliminary demonstration and
improvement of sensitivity can be attempted by using strategies
previously reported in the literature such as surface functionali-
zation, selective doping or metal loading to elicit stronger
response for the chosen target vapor of interest.
2123
Statistical variations in sensor performance can be an issue
since solution-processed devices tend to suer performance
uctuations. The paper substrate here showed noticeably little
variation. To understand the mechanism of uctuation, control
sensors were fabricated on at and uniformsubstrates such as a
glass and Teon using identical processing approach (including
the same amount of CNTs) described earlier. Ten sensors were
repeatedly characterized for establishing the statistical varia-
tions. Fig. 4(a) shows the sensor response characteristics of the
control sensors with both devices showing high device-to-device
uctuation. Note that the fair comparison between the glass
substrate and the paper substrate is almost impossible as the
standard deviation of response at the glass substrate is
extremely large. Fig. 4(b) compares the mean and standard
deviation of various substrates. As seen here, the paper based
sensors show signicantly less variation. Referring to the de-
nition, the response depends not only on the resistance shi
(DR R
t
R
0
), but also the initial resistance (R
0
). It implies that
the deviation can come from the resistance shi and/or the
initial resistance. To clarify the source of deviation, statistical
analysis was carried out for DR and R
0
. Fig. 4(c) and (d) show the
DR with respect to 50 ppm of NH
3
for the respective R
0
collected
from a number of sensors. The slopes of each line represent the
responses of respective samples. All sensors show a scatter in
R
0
, but when DR is normalized by R
0
, the responses of the paper
substrate appear to converge into a single line but those of the
glass and Teon substrates are still scattered. While drying the
suspension uid on the hydrophobic surface of the glass and
Teon substrates, the CNTs agglomerate and then get clustered.
Therefore, the distribution of CNTs on the solid substrates can
be less uniform than on the paper substrate, which leads to the
statistical variation of the initial resistance. In contrast, when
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the suspension uid wets the hydrophilic surface of the cellu-
lose paper, the paper can soak up the CNTs by capillary action.
The adhesion between CNT and cellulose is also improved due
to van der Waals interaction. Thus, the individual CNTs may be
rmly bounded along the paper morphology. Therefore, when
the analyte molecules approach, the response occurs uniformly
across the lm surfaces.
Similar to ordinary gas sensors, water vapor can be an inter-
ferent in the carbon nanotube-based sensors. Several mecha-
nisms have been suggested to understand the humidity eect in
CNT-based sensors including electron donation, bonding of
hydrogen with the oxygen defects, and direct H
2
O adsoption.
15,24
The cross sensitivity with the analyte of NH
3
and background
humidity can be even more complex. Calibrationcurves produced
in Fig. 3(b) need to be generated for various humidity levels in
order to use a sensor element in an electronic nose, which would
allow interpolation of the stored data at the prevailing humidity
conditions. Sometimes, the humidity eect on the sensor
response (i.e. change in resistance due to humidity) may not be
linear as seen in the case of NO
2
.
24
In order to investigate the
impact of relative humidity, the NH
3
responses of the layer-by-
layer structures were measured under three additional relative
humidity levels as shown in Fig. 5. The relative humidity was
controlled constant at the specied value for the repeated NH
3
injection and purge cycles. Similar to NH
3
, the moisture causes
an increase in resistance of carbon nanotubes as water behaves
like a donor and injects electrons in the p-type carbon nanotube.
At constant RH, the presence of water vapor leads to an increase
in the NH
3
response, as moisture acts as a reaction catalyst
25
or
involves in a reaction mechanism with NH
3
by supportive
manner.
26
Under the ambient air with a substantial relative
humidity, such inuences of water vapor would prevent the use of
any NH
3
sensor independently. In this case, the inuence of
humidity should be accounted for by the use of a multisensor
array structure that independently measures humidity using
another sensor and perform humidity calibration.
4 Conclusions
In summary, CNT based ammonia sensors were demonstrated
on a cellulose paper and shown to give good response in the
tested range of 10100 ppm. The minimum detection limit of
5 ppm for the CNT-on-paper is comparable to a number of
previous studies on CNT-based sensors as listed in the review by
Kaufman and Star
15
and elsewhere.
27
The features of the present
sensors include exibility, low cost fabrication, and thus suit-
ability for disposable applications. In particular, reasonable
response and recovery characteristics were obtained at ambient
conditions. Compared to control sensors made on glass
substrates, the paper based sensor exhibited superior unifor-
mity and repeatability. The paper based gas sensor can be a
fundamental building block for future smart paper electronics.
Further work is needed to address several practical issues
including eects of humidity and other interfering or similar
analytes, sensor baseline dri, and sensor ageing.
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552 | RSC Adv., 2014, 4, 549553 This journal is The Royal Society of Chemistry 2014
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