Research Article

www.acsami.org

Wireless, Room Temperature Volatile Organic Compound Sensor

Based on Polypyrrole Nanoparticle Immobilized Ultrahigh Frequency
Radio Frequency Identification Tag
Jaemoon Jun,‡ Jungkyun Oh,‡ Dong Hoon Shin, Sung Gun Kim, Jun Seop Lee, Wooyoung Kim,
and Jyongsik Jang*
School of Chemical and Biological Engineering, College of Engineering, Seoul National University (SNU), 599 Gwanangno,
Gwanak-gu, Seoul 151-742, Korea
*
S Supporting Information
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ABSTRACT: Due to rapid advances in technology which have contributed to the development of portable equipment, highly
sensitive and selective sensor technology is in demand. In particular, many approaches to the modification of wireless sensor
systems have been studied. Wireless systems have many advantages, including unobtrusive installation, high nodal densities, low
cost, and potential commercial applications. In this study, we fabricated radio frequency identification (RFID)-based wireless
sensor systems using carboxyl group functionalized polypyrrole (C-PPy) nanoparticles (NPs). The C-PPy NPs were synthesized
via chemical oxidation copolymerization, and then their electrical and chemical properties were characterized by a variety of
methods. The sensor system was composed of an RFID reader antenna and a sensor tag made from a commercially available
ultrahigh frequency RFID tag coated with C-PPy NPs. The C-PPy NPs were covalently bonded to the tag to form a passive
sensor. This type of sensor can be produced at a very low cost and exhibits ultrahigh sensitivity to ammonia, detecting
concentrations as low as 0.1 ppm. These sensors operated wirelessly and maintained their sensing performance as they were
deformed by bending and twisting. Due to their flexibility, these sensors may be used in wearable technologies for sensing gases.
KEYWORDS: wireless, polypyrrole, sensor, volatile organic compound, RFID tag

■ INTRODUCTION
Recently, technologies to sense volatile organic compounds
(VOCs) such as acetone (CH3COCH3), ethanol (C2H5OH),
acetic acid (CH3COOH), and ammonia (NH3) with high
sensitivity and fast response times have been studied.1−4 These
technologies have a variety of potential applications such as
home health care, home automation, and disaster prevention.
In particular, NH3 is a widely used gas which contributes to the
nutritional needs of terrestrial organisms by serving as a
precursor for food and fertilizer.5,6 Additionally, NH3 is a
biomarker that can be rapidly and noninvasively detected from
breath analysis. Despite its usefulness, NH3 shows hazardous
effects on the human respiratory system when its concentration
exceeds the threshold limit value of 25 ppm.7−9 Therefore, cost-
effective and highly sensitive systems for detection of NH3 are
needed across industrial and commercial areas.
Due to their small size in the range of 1−100 nm, sensor
devices based on nanomaterials perform outstandingly well at
detecting the target substances.10,11 During the past decade, a
number of strategies have been proposed for enhancing sensor
performance using nanomaterials such as metal oxides, metal
nanowires, carbonaceous materials, and conducting polymer
nanomaterials.12−18 In particular, conducting polymer nanoma-
terials have been used as sensor transducers as they have
inherent electronic and mechanical transduction mechanisms,
operate at room temperature, and are cost-effective.4,19−22
Although these conducting polymer materials have attractive
properties, their use in commercial devices has been limited due
Received: July 8, 2016
Accepted: November 9, 2016
Published: November 9, 2016

© 2016 American Chemical Society 33139 DOI: 10.1021/acsami.6b08344

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to the lack of methods for integrating the sensor components step, poly(vinyl alcohol) (PVA) was dissolved in deionized
into electronic circuits.23 Difficulties arising due to the water, and iron cations were obtained from ferric chloride
properties of aggregates of these materials have also limited (FeCl3) (Figure 1a). The pyrrole solution, which contained
their use in sensor devices. Several approaches to integrating
the electronic circuit with a uniform distribution of the sensor
material have been proposed. One of the most promising
approaches is to integrate the nanomaterials into the wireless
network circuit as the sensors can be installed unobtrusively at a
low cost with high nodal densities.23,24 This approach has
potential commercial applications. Rapid advances in portable
technologies, such as improvements to smart phones, have
broadened the range of potential applications of wireless
sensors.25−31 For instance, they are used for real-time
monitoring of hospitalized patients, food freshness, military
personnel, and to detect the presence of harmful gases such as
carbon dioxide, nitrogen dioxide, oxygen, and flammables.32−34
Due to its simple architecture and broad detection range, the
radio frequency identification (RFID)-based sensor is the most
promising of the proposed wireless sensing systems.15,35−38
There are two types of RFID tag: the active type, which
requires an on-board power supply, and the passive type, which
does not.39,40 Although active RFID tags can be used as sensors
at distances from the reader antenna greater than those of
passive RFID tags, their large size and short life cycle possibly
limit their applicability.41 The passive RFID tags are more
attractive as they have a longer life span, are cost efficient, and
small in size. We studied a wireless sensor system which uses a
passive ultrahigh frequency (UHF)-RFID sensor tag with a
distance of 50 cm.42
The proposed wireless sensor system is composed of two
parts. The signal receiver is an RFID reader antenna connected
to a network analyzer.23 The signal transfer is performed by
carboxylated polypyrrole (C-PPy) nanoparticles bonded to a
passive UHF-RFID tag to form a sensing tag. The C-PPy Figure 1. (a) Preparation of the carboxyl functional groups controlled
nanoparticles were synthesized from a water-soluble polymer by polypyrrole nanoparticles (C-PPy NPs) in an aqueous solution with
and highly monodispersive metal cations. The C-PPy nano- polymer/metal cation complexes. (b) SEM image of the C-PPy NPs
particles, which had an average size of 60 nm, were mixed with (inset: photograph of a Petri dish containing C-PPy NPs), and (c)
an aqueous solution of functional groups of modified pyrrole low- and high-(inset) resolution TEM images of the C-PPy NPs.
monomers.43 The sensing area was created using a con-
densation reaction to pattern the antenna with the C-PPy pyrrole-3-carboxylic acid monomers, was then vigorously
NPs.44 This method was chosen as it creates covalent bonds stirred into the PVA/iron cation complex aqueous solution.
which help to maintain the stability of the nanoparticles in the The iron cations acted as both an oxidizing agent and a forming
sensor coating during exposure to gases. The presence of the C- agent for the PVA/iron cation complex during the polymer-
PPy NPs gave rise to a strong affinity between the PPy ization. We could easily tune the number of carboxyl functional
backbone and the NH3, as indicated by a shift in the reflectance groups of C-PPy NPs using carboxylic acid modified
of the RFID sensor. Furthermore, the reflectance of our monomers. We used C-PPy NPs with pyrrole monomer-to-
wireless sensor varied with the NH3 concentration and enabled pyrrole-3-carboxylic acid monomer weight ratios of 45:1 (C-
detection of low concentrations (0.1 ppm) of NH3 at room PPy_1), 30:1 (C-PPy_2), and 15:1 (C-PPy_3). A field-effect
temperature. To our knowledge, no reports have described the scanning electron microscopy (FE-SEM) image of the C-PPy
fabrication of an RFID-based wireless sensor using the C-PPy NPs is shown in Figure 1b. Nearly all of the C-PPy NPs were
NPs.

■
RESULTS AND DISCUSSION
Fabrication of the Materials. Two of the most desirable
properties of sensor transducers for wireless sensor systems are
a high surface-to-volume ratio and stability during the sensing
process. We used a chemical oxidation procedure to synthesize
C-PPy NPs that were highly uniform in distribution and size via
copolymerization of pyrrole with pyrrole-3-carboxylic acid in
aqueous solution.43 The C-PPy NPs can be tuned using
functional groups. The carboxyl functional groups in the C-PPy
NPs form covalent bonds on the aluminum pattern of the
RFID antenna, which provide stability and flexibility. In the first
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nanospheres with an average diameter of 60 nm. The
transmission electron microscopy (TEM) images in Figure 1c
and the inset also revealed that C-PPy NPs were highly
monodispersed, spherically shaped, and uniform in size. Our
method enables rapid subkilogram-scale fabrication of a high
quality nanoparticle product. For laboratory scale production,
quantities on the order of kilograms are considered very large
(inset of Figure 1b). To confirm that our solutions contained
the expected ratios of the 3-carboxyl functional groups, we
made Fourier-transform infrared (FT-IR) measurements of the
C-PPy NPs, as shown in Figure 2. The green curves indicate
pristine polypyrrole (PPy) NPs, which have peaks indicating
C−C stretching vibrations in the pyrrole ring at 1554 cm−1,
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Figure 2. Fourier-transform infrared (FT-IR) spectra of the solutions
containing different ratios of carboxyl functional groups: C-PPy 1
(blue), C-PPy 2 (red), and C-PPy 3 (green).
conjugated C−N stretching at 1473 cm−1, and C−H planar
vibrations at 1294 and 1195 cm−1. The same peaks were
observed in all the samples, as they originated from the
polypyrrole structure. However, the C-PPy NPs have distinctive
peaks at 1700 and 3200 cm−1 from, respectively, the − CO
and − OH bands of the carboxyl functional group.19,45 The
intensities of these peaks slightly increased with the ratio of
carboxyl functional groups in the C-PPy NPs using the internal
standard at the C−C stretching band. To make up these results,
we conducted an XPS analysis on C-PPy NPs.
X-ray photoelectron spectroscopy (XPS) was used to
characterize the chemical bonds in the samples. Figure 3a
displays that all of the samples had peaks at around 285, 399,
and 532 eV, which are related to the C 1s, N 1s, and O 1s
orbitals of the polypyrrole molecules. High-resolution XPS
analysis of the C 1s peak confirmed the ratios of carboxylic
functional groups present in the C-PPy samples, as shown in
Figure 3. X-ray photoelectron spectroscopy (XPS) analysis of (a) a fully scanned spectrum (0−1000 eV) and high-resolution spectra of the C 1s
orbitals of the carboxyl functional groups: (b) C-PPy_1, (c) C-PPy_2, and (d) C-PPy_3.
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Figures 3b−d. The C 1s peak had four components. The
positions that the components were centered at (284.6, 286,
287.5, and 288.85) indicate the presence of C−C, C−N, C−
O−C, and O−CO or CO molecules, respectively. The
strength of the peak associated with the O−CO or CO
molecules in the carboxyl functional group increased as the
ratio of carboxyl groups increased. The semiquantitative
analysis was performed using internal standard (C−C in
pyrrole rings). The ICO/IC−C ratio increased from 0.04 to 0.1,
which demonstrates that it is possible to have control over the
ratios of functional groups in C-PPy NPs. We present the
additional data of C−C peaks about C-PPy NPs in Tables S3
and S4.
Electrical Performance Measurements. Before testing
the capabilities of the samples as wireless sensors, we made
electrical performance measurements using an interdigitated
array (IDA) substrate which was composed of a total of 40 2
μm alternating gold fingers. The spin-coating method was used
to convert the C-PPy NPs into a close-packed crystalline array
on the IDA substrate. Figure S1 describes an FE-SEM image of
the C-PPy NP-based IDA sensor electrode, and we can see that
it was coated with highly uniform, dense, close packed
nanoparticles.
To evaluate the electrical contact between the C-PPy NPs
and the IDA substrates, current−voltage (I−V) curves were
measured over voltages from −0.1 to 0.1 V, as shown in Figure
4a. The dV/dI values increased slightly at the electrodes,
possibly due to the decreased conductivity of the C-PPy NPs.
The nominal resistance values of the C-PPy NPs are 0.2564,
0.3125, and 0.4167 kΩ for C-PPy_1, C-PPy_2, and C-PPy_3,
respectively. The carboxylic functional groups act as insulating
materials. The linear relationships displayed in the I−V curves
for each of the nanoparticle-coated substrates indicate excellent
electrical contact (Ohmic contact), in contrast to the
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Figure 4. (a) Current−voltage (I−V) curves for the coated interdigitated array (IDA) electrode with different ratios of the carboxyl functional
groups. The normalized resistance changes are shown after (b) sequential exposure to acetic acid and (c) periodic exposure to 100 ppm acetic gas
and with (d) a range of acetic acid concentrations. For panels a and d, the results for the different functional group ratios are C-PPy_1 (blue), C-
PPy_2 (red), and C-PPy_3 (green).

Figure 5. (a) Schematic diagram of the UHF-RFID sensor tag with carboxyl functional groups covalently bonded to the aluminum tag in the desired
position. (b) Photograph of the proposed UHF-RFID-based gas sensor tag. (c) Field effect scanning electron microscopy image of the C-PPy_NP
immobilized sensing area.

33142 DOI: 10.1021/acsami.6b08344

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Figure 6. Change in the reflectance properties of different C-PPy NP-based wireless sensors: (a) C-PPy_1, (b) C-PPy_2, and (c) C-PPy_3. (d)
Relationship between the concentration of ammonia in the gas exposed to the sensor and the measured change in reflectance, where the reflection is
calculated using ΔRe/Re0 = (Re − Re0)/Re0, where Re0 is the initial reflectance and Re is the reflectance after an exposure time of 2 min.
nonlinearity observed in measurements of components which
have poor electrical contact.13,19
The sensing performance of the C-PPy NP-based sensors
was recorded in real time by measuring changes in the
resistance to various gases. The conductivity of the C-PPy NPs
was influenced by external stimuli such as oxidation and
reduction reactions, swelling and doping, or dedoping of the
sensor surfaces. Figure 4b exhibits the real-time responses of
the C-PPy NPs on the IDA substrate to a range of
concentrations of ammonia and acetic acid. To better
understand the results, we calculated the normalized resistance
change using
ΔR /R 0 = (R − R 0)/R 0 (1)
where R and R0 are the real-time and initial resistances,
respectively. The sensors rapidly responded to and recovered
from exposure to gases. Interestingly, the electrical resistance of
the C-PPy NP sensors were opposite for the two gases tested;
the resistance gradually increased after exposure to NH3 and
decreased after exposure to acetic acid. This results in the
introduction of an electron-donating group (NH3) into the
conducting polymer backbone as a p-type transducer,
decreasing the charge carrier (electron−hole) concentration
via a redox reaction and resulting in enhanced resistance. The
carboxylic groups on the surface of the PPy act as additional
active sites for ammonia interaction thorough hydrogen
bonding. Therefore, different amount of carboxylic groups
also affect the sensing performance during introduction of
ammonia.46,47 On the other hand, the resistance was decreased
when acetic acid was applied to the sensors because negatively
charged counterions (CH3HOO−) were incorporated into the
polymer to compensate for the positive charges in the polymer
backbone.48 The emergence of polarons or bipolarons
enhanced the conductivity. As the ratio of carboxylic functional
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groups increased, the polymer/gas partition coefficient was
enhanced, increasing the sensitivity of the sensors. The
minimum detectable levels (MDL) of the C-PPy NPs were
0.1 and 1 ppm for NH3 and acetic acid, respectively.
Figure 4c shows the resistance changes observed in the C-
PPy NPs after periodic exposure to 25 ppm of NH3 and 100
ppm of acetic acid at room temperature. The resistance varied
in a similar way to the enhancement in sensing performance
without retardation of the response and recovery times, as can
be seen in Figure S2. This performance is superior to that of
many other conducting polymer-based gas sensors at room
temperature (Table S1). In Figure 4d, we plot the sensitivity
(S) of the C-PPy NP sensors as a function of the NH3 and
acetic acid concentrations. At concentrations less than 0.1 ppm,
the sensitivity varied nonlinearly. In contrast, the sensitivity
varied linearly over the concentrations of 1 to 100 ppm for NH3
and acetic acid. These results indicate that the C-PPy NP
sensors can detect NH3 and acetic acid reversibly and reliably,
even in very small concentrations. Additionally, Figure S3
shows the sensitivity of C-PPy NP sensors to various volatile
organic compounds at 100 ppm. This result indicates that the
sensitivity and selectivity were greatest for ammonia.
Wireless Sensor Measurements. We fabricated wireless
sensors using our C-PPy NP solutions and UHF-RFID tag
antenna. The sensor systems were composed of an RFID-
reader antenna, which was connected to a network analyzer,
and an RFID tag antenna modified by sensing material.23
The C-PPy NPs were bonded to the passive UHF-RFID tags
which contained a dipole antenna and an integrated circuit (IC)
chip. Figure 5a shows the steps used to modify the UHF-RIFD
tags to convert them into wireless gas sensors. In the first step,
the UHF-RFID tag, apart from the section reserved for the
sensing area, was covered with commercially available plastic
tape. Then, we treated the tape-covered RFID tags with oxygen
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Figure 7. Photographs of the RFID tag sensor under different deformations: (a) flat, (b) twisting, and (c) rolling. (d) Normalized reflectance change
under different deformations (flat, twisting, and rolling).
plasma and 3-aminopropyltrimethoxysilane (APS) to create a
specific functionalized region on the UHF-RFID tag. The C-
PPy NPs were then bound to the functionalized region of the
antenna pattern through covalent bonding of the amino groups
in the antenna pattern to the carboxylic groups in the C-PPy
NPs. Symbolically, the procedure is described as:
condensation: C − PPy NPs − COOH + H 2N(CH 2)3 Si
(O)3 − RFID pattern
→C − PPy NPs − CONH(CH 2)3 Si(O)3 − RFID pattern
(2)
The covalent anchoring has the advantages of improving the
stability of the sensor and enabling the formation of efficient
electrical pathways during wireless sensing.
To initiate the wireless sensing, the RFID reader antenna,
which was connected to the network analyzer, emitted an
interrogation signal (Figure S8). The emitted electromagnetic
field activated the UHF-RFID wireless sensor. Then, the signal
was reflected back to the RFID reader antenna, a process
known as backscattering.23,33,42 The response was monitored in
real time by the network analyzer. When the UHF-RFID
wireless sensor was exposed to the gases, the resistance changes
in the chemiresponsive materials caused impedance mismatches
between the dipole tag antenna and the IC chip. As a result, the
network analyzer detected changes in the backscattering signal.
Figures 6a−c displays the change in the level of backscatter
power from the tag of the different RFID sensor tags (C-
PPy_1, C-PPy_2, and C-PPy_3, respectively), which was used
to determine the responses of the wireless sensors to the gas
concentration at a distance of 50 cm. The reflection change is
expressed as power of the radio waves reflected (Re, in dB)
versus the frequency, as measured by the network analyzer.
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The sensor was exposed to concentrations of NH3 ranging
from 0.1 to 25 ppm. The reflection of the radio wave decreased
with the NH3 concentrations due to increasing resistance on
the sensor surface. As mentioned above, an electron-donating
group (NH3) into the pyrrole backbone (p-type transducer)
decreased the charge carrier (electron−hole) concentration.
The increasing resistance of the sensor tag leads to impedance
mismatches between the IC chip and antenna without gas
exposure, and then the RFID tag decreases the radar cross
section, resulting in diminished reflection.49,42 On the other
hand, the increasing reflection was displayed when the sensor
tag was exposed to acetic acid. The resistance of the C-PPy NPs
decreased because of interactions with negatively charged
counterions (CH3HOO−) (Figure S4). In addition, similar to
the IDA-based sensing system, the sensitivity of the RFID
sensor increased with an increasing ratio of carboxylic
functional group concentrations on the C-PPy NPs (0.1 ppm
for C-PPy_3, 1 ppm for C-PPy_2, and 5 ppm for C-PPy_1).
This result is higher value compared to those of many other
RFID-based ammonia sensors (Table S1). Additionally, we
performed the control experiment using the UHF-RFID tag
without a sensing area (Figure S7).
As shown in Figure 6d, the percentage of signal reflected
back (normalized reflection change) by the sensor increased
with the ratio of carboxyl functional groups with 14.2, 7.35, and
5.8% reflected back for C-PPy_3, C-PPy_2, and C-PPy_1,
respectively, in the case of a concentration of 25 ppm. The
normalized reflection change is expressed as (Re − Re0)/Re0,
where Re is the reflection after 2 min of acetic acid exposure
and Re0 is the initial reflectance. These results indicate that the
sensitivity of the wireless sensors increased with the ratio of
carboxylic functional groups on the surface. These responses
are similar to those observed in the case of the IDA substrate
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sensor electrode. Additionally, the sensing performance of the
C-PPy-based UHF-RFID wireless sensor was significantly lower
than that of other materials-based RFID sensor (Table S2).
The flexibility of the sensor substrate enabled consistent
sensing performance as the sensor was deformed in a number
of ways, such as by bending, rolling, or twisting. Figure 7d
displays the change in the resonance reflection, which has a
similar wave of modulation with deformation such as rolling
and twisting. We tested the performance of the sensor as it was
bent through a range of folding angles, which subjected the
substrate to compressive forces, as shown in Figure S5. Due to
the covalent bonds between the C-PPy NPs and the RFID tag,
the bending did not have a significant effect on the sensor tag.
This indicates that our polymer nanoparticle-based sensors
have promising potential for applications as wearable and
implantable wireless sensor systems.
■ CONCLUSION
We fabricated wireless sensors using carboxyl functional groups
controlled by C-PPy NPs and passive UHF-RFID tags. To our
knowledge, this is the first demonstration of the manufacture of
C-PPy NPs for wireless sensor transducers at room temper-
ature. The C-PPy NPs were synthesized from a highly uniform
and monodispersed aqueous solution using a chemical
oxidation polymerization technique. The UHF-RFID-based
wireless sensor system was fabricated by covalently bonding the
C-PPy NPs to the UHF-RFID tag. The stability of the covalent
bonds gave rise to advantages during ammonia exposure and
deformation of the sensor. The sensors investigated in this
paper were highly sensitive, detecting ammonia in concen-
trations as low as 0.1 ppm, operated at wireless system (50 cm)
without a battery, and were flexible, maintaining their sensing
performance as they were bent through a range of angles. Thus,
this study demonstrated an effective way to fabricate UHF-
RFID-based wireless sensors using conducting polymer NPs.
■
MATERIALS AND METHODS
Materials. PVA (MW 9000), dodecyltrimethylammonium bromide
(DTAB), ferric chloride (FeCl3) (97%), pyrrole (98%), and (3-
aminopropyl)triethoxysilane (APS) were purchased from Sigma-
Aldrich Co. (St. Louis, United States) and used without purification.
Pyrrole-3-carboxylic acid hydrate (95%) and 4-(4,6-dimethoxy-1,3,5-
triazin-2-yl)-4-methyl morpholinium chloride (DMT-MM) were
purchased from Acros Organics (United States) and Fluka (Buchs,
Switzerland), respectively.
Preparation of Carboxylated Pyrrole Nanoparticles. A
microemulsion method was used to obtain the C-PPy NPs. To
synthesize the C-PPy NPs, PVA was dissolved in distilled water to
make 1 wt % PVA aqueous solution. This solution was stirred for 12 h
at 60 °C with a uniform stirring rate. DTAB (0.2 g) and a 7 M aqueous
FeCl3 solution (0.5 mL) were injected into the PVA solution, which
was then stirred for 1 h at a rate of 1000 rpm. Subsequently, a pipet
was used to add the mixture of pyrrole and pyrrole-3-carboxylic acid
hydrate monomers for different molar ratios (6:0.4 mM for C-PPy_3,
6:0.2 mM for C-PPy_2, and 45:0.1 mM for C-PPy_1) with stirring at
1000 rpm for 2 h. This solution was centrifuged to remove reagents
without removing resultants and then diluted with distilled water and
stirred for 4 h at a rate of 400 rpm at a temperature of 60 °C. After this
process had been repeated four times, the solid C-PPy NPs were
placed in a 60 °C oven to dry.
Electrical Measurement of the C-PPy NPs on the IDA
Substrate. To measure the electrical properties of the polymer
coating, the aqueous C-PPy NP solution was sonicated and drop-
casted onto an IDA electrode. The microarray consisting of a gold IDA
electrodes with 40 fingers (2 μm in width, 2 μm in spacing, 4000 μm
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in length, and 50 nm in thickness on a 50 nm Cr adhesion layer) was
patterned on a glass substrate through a photolithographic process.
The spin-coating method at a rate of 1000 rpm was used for a duration
of 60 s to obtain a uniformly coated electrode array. To reduce the
resistance between the IDA electrode and the C-PPy NPs, the coated
electrode array was stored in an inert atmosphere for 24 h at room
temperature. To measure the influence of NH3 gas exposure on the
electrical properties of the C-PPy NP-coated IDA electrodes, they
were placed in a vacuum chamber which was custom designed for gas
sensing with a vapor inlet/outlet pressure of 100 Torr. Various gas
concentrations of NH3 (0.1−100 ppm) were controlled by a mass flow
controller (KNH Instruments, Korea) system. The real-time resistance
monitoring was conducted with a constant applied current of 10−6 A
(defined as ΔR/R0 = (R − R0)/R0, where R and R0 are the real-time
resistance and the initial resistance, respectively). After the sensor
electrode had been exposed to gases for several minutes, compressed
inert gas was introduced to the vacuum chamber to remove any
molecules that had become attached to the C-PPy NPs. This step
refreshed the electrode, enabling its reuse and hence repeated
measurements of the sensor performance.
Fabrication of the C-PPy NP-Based UHF-RFID Smart Sensor.
To attach the C-PPy NPs firmly along the line of the UHF-RFID tag,
the RFID tag was treated with APS. The passive UHF-RFID tags were
composed of an antenna pattern and microcontroller integrated circuit
(IC) chip (EPC global Class-1 Generation-2 (GEN2) protocol) on the
plastic substrate ($2 US dollars by the piece) (EMPO Corp., Korea).
The passive UHF-RFID reader antenna is MT-242025 (ThingMagic
Corp., United States). The frequency range of the reader antenna was
865−956 MHz. The passive UHF-RFID tag (nominal frequency:
∼904 MHz) was wrapped with commercially available plastic tape
everywhere apart from at the desired position of the C-PPy NP
coating. To form the oxygen functional groups, O2 plasma treatment
was used. The tape-wrapped UHF-RFID tag was soaked in 5 wt %
APS aqueous solution, and the solution was rotated for 6 h at a
constant slow rate. After the stirring treatment, the tag was removed
from the solution and dried at room temperature. A glass bath was
glued onto the section of the RFID tag that had been treated with
APS, and then the C-PPy NPs and DMT-MM aqueous solutions were
introduced to the glass bath simultaneously. The sensor was left to dry
in standard atmospheric conditions for 24 h.
Characterization. FE-SEM and high resolution transmission
electron microscopy images were obtained using a JEOL 6700 and a
JEOL JEM-200CX, respectively (JEOL Ltd., Japan). TEM images were
acquired by a JEM-2100 (JEOL Ltd., Japan) installed at the National
Center for Interuniversity Research Facilities at Seoul National
University. XPS spectra were recorded using an M16XHF-SRA
(Mac Science Co., Japan). The four-probe method was used to
measure the electrical conductivity at ambient temperature with a
source meter using SMU 2400 (Keithly Instruments Inc., United
States).
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b08344.
(1) Schematic diagram of IDA electrode substrate, (2)
response and recovery times of electrodes after exposure
to VOCs, (3) sensing performance histogram of C-
PPy_3, (4) measured change in reflectance of wireless
sensor, (5) resistance change with different bending
angles, (6) comparison of sensor performance with other
conducting polymer-based nanomaterials, (7) compar-
ison of RFID tag-based wireless sensor performance with
other materials (PDF)
DOI: 10.1021/acsami.6b08344
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■ AUTHOR INFORMATION
Corresponding Author
*Tel: 82-2-880-8348; Fax: +82-2-888-7295; E-mail: jsjang@
plaza.snu.ac.kr.
Author Contributions
‡ Lee, C. J. Field-Emission Characteristics of Electrochemically
J. Jun and J. Oh contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by Development Fund of Seoul
National University funded by Dongjin Semichem Co., Korea
(Grant 0458-20130066).
■
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33147 DOI: 10.1021/acsami.6b08344

ACS Appl. Mater. Interfaces 2016, 8, 33139−33147