sensors

Article
Standardization, Calibration, and Evaluation of
Tantalum-Nano rGO-SnO2 Composite as a Possible
Candidate Material in Humidity Sensors
Subbiah Karthick 1,2 , Han-Seung Lee 1, *, Seung-Jun Kwon 3 , Rethinam Natarajan 2 and
Velu Saraswathy 4
1 Department of Architectural Engineering, Hanyang University, 1271 Sa 3-dong, Sangrok-gu, Ansan 426791,
Korea; karthick.chemistry@gmail.com
2 PG and Research Department of Chemistry, Alagappa Government Arts College, Karaikudi 630003,
Tanilnadu, India; nataraajan12@yahoo.co.in
3 Department of Civil Engineering, Hannam University, Daejeon 306-791, Korea; jjuni98@hannam.ac.kr
4 Corrosion and Materials Protection Division, CSIR-Central Electrochemical Research Institute,
Karaikudi 630003, Tamilnadu, India; corrsaras@gmail.com
* Correspondence: ercleehs@hanyang.ac.kr; Tel.: +82-31-400-4181

Academic Editors: Francisco J. Arregui and Jesús M. Corres

Received: 9 September 2016; Accepted: 30 November 2016; Published: 7 December 2016

Abstract: The present study focuses the development and the evaluation of humidity sensors based
on reduced graphene oxide—tin oxide (rGO-SnO2 ) nanocomposites, synthesized by a simple redox
reaction between GO and SnCl2 . The physico-chemical characteristics of the nanocomposites were
analyzed by XRD, TEM, FTIR, and Raman spectroscopy. The formation of SnO2 crystal phase was
observed through XRD. The SnO2 crystal phase anchoring to the graphene sheet was confirmed
through TEM images. For the preparation of the sensors, tantalum substrates were coated with
the sensing material. The sensitivity of the fabricated sensor was studied by varying the relative
humidity (RH) from 11% to 95% over a period of 30 days. The dependence of the impedance
and of the capacitance with RH of the sensor was measured with varying frequency ranging from
1 kHz to 100 Hz. The long-term stability of the sensor was measured at 95% RH over a period of
30 days. The results proved that rGO-SnO2 nanocomposites are an ideal conducting material for
humidity sensors due to their high sensitivity, rapid response and recovery times, as well as their
good long-term stability.

Keywords: rGO-SnO2 ; nanocomposites; sensor; relative humidity

1. Introduction
Humidity sensors play a vital role in environmental, industrial, and agricultural applications.
Humidity is an important factor in physical, chemical, and biological processes. Optimal humidity
is essential for human health and wellbeing. Humidity measurement in industrial processes is also
critical because it may affect the quality and business cost of the product. Humidity sensors based
on SnO2 , TiO2 , ZnO, CuO, and cross linked polymers have been reported in recent years [1–10].
Among them, SnO2 nanomaterials exhibit a higher performance for humidity sensing applications.
It is due to their high surface area, high alkaline stability, excellent conductivity, good reversibility,
ease of functionalization, robust mechanical properties, and low production cost. Moreover, the size
and shape of the particles affect the humidity sensing capacity. Recently, high sensitivity humidity
sensors based on a uniform morphology of SnO2 nanowires have been reported. The enhanced
surface area and stable humidity sensing of the active material, which was prepared by adding GO,
allowed the achievement of good performance in sensor applications [11,12]. In particular, numerous

Sensors 2016, 16, 2079; doi:10.3390/s16122079 www.mdpi.com/journal/sensors

Sensors 2016, 16, 2079 2 of 13

attempts have been made to combine reduced graphene oxide (rGO) with nano metal oxide to enhance
their humidity sensing and photo catalytic properties, which are comparable with base materials.
Seema et al., reported rGO-SnO2 nanocomposites synthesized by a simple chemical method, that
they exhibited enhanced photo catalytic activity regarding the degradation of methylene blue under
sunlight [13]. Zhang et al., demonstrated the good performance of NO2 sensing at low temperatures
by SnO2 nanoparticles decorated with rGO nanocomposite [14]. Morimutu et al., reported on surface
modification of platinum and ruthenium over SnO2 particles for CO gas sensors [15]. However, to the
best of our knowledge, there have been few reports that have focused on SnO2 nanoparticle humidity
sensors anchored to a graphene sheet.
Most of the studies deal with highly conductive materials used in ceramic substrate coated with
noble metals such as Au, Pt, Pd, and Ag. This process can be achieved by physical or chemical
methods. These methods tend to be interactive in a number of cases due to random operation cost
effects. Alternative cost-effective materials like tantalum exhibit an excellent dielectric constant,
high capacitive behavior, and enhanced corrosion resistance to moisture and aqueous solutions [16].
Hence, tantalum is an ideal candidate for the base substrate material for humidity sensor applications.
In the present study, for the first time, attempts were made to attach SnO2 on a graphene sheet for
humidity sensing application. This investigation lead to a novel humidity sensor of nano-rGO-SnO2
over a tantalum support.

2. Materials and Methods

2.1. Materials
All used chemicals were of analytical grade and utilized without further purification.
Tin chloride dihydrate (SnCl2 ·2H2 O), Hydrochloric acid (HCl) and urea were purchased from
SRL Chem. Graphite powder, PVDF (Poly (vinylidene fluoride)), carbon black, and NMP
(1-N-methyl-2-pyrrolidinone) were purchased from Alfa Aesar. Tantalum was purchased from Manhar
Metal supply Corporation, Mumbai, in India.

2.2. Preparation of Nano SnO2 and rGO-SnO2 Composites

SnCl2 ·2H2 O (1.30 g) was dissolved in HCl (38 wt %, 0.7 mL) and diluted with distilled water
(20 mL) to give a SnCl2 :HCl solution. In order to form a uniform solution, urea (1.30 g) was added to
the SnCl2 :HCl solution under vigorous stirring. The resulting solution was then heated up and kept at
90 ◦ C for 12 h. The obtained precipitate was separated by centrifugation and washed with water to
remove excess chloride ions. The resulting product was dried in a vacuum oven at 110 ◦ C for 24 h.
GO was prepared from powdered flake graphite (400 mesh) by a modified Hummers method
as described elsewhere [17,18]. The obtained graphite oxide (10 mg) was dispersed in distilled water
(20 mL) using sonication to form a colloidal suspension. The GO solution was added to a SnCl2 :HCl
solution: then urea was added to the previously obtained solution and heated up and kept at 90 ◦ C for
12 h. The resulting precipitate was separated by centrifugation and subsequent washing, to remove
excess chloride ions. The resulting product was dried in a vacuum oven at 110 ◦ C for 24 h.

2.3. Characterization Techniques

The obtained SnO2 and rGO-SnO2 were analyzed by FTIR spectroscopy. The sample was
mixed with KBr crystal and the spectrum was recorded in the transmittance mode in the range
of 400–4000 cm−1 .
The phase structure of the nanocomposite was characterized by XRD. A computer controlled XRD
system—comprised of JEOL, JPX-8030 with Cu-Kα radiation (Ni filter = 13,418 Å), and a power source
with 40 kV and 20 A—was used to record the diffraction patterns. Identification of diffraction peaks
was done by a computer controlled software application (PAN analytical, X’pert High score plus).
Sensors 2016, 16, 2079 3 of 13

The surface defects, D and G peak, sp2 hybridization of GO, SnO2 , and rGO-SnO2 were determined
by Laser-Raman spectroscopy (Renishaw Invia Raman Microscope with Wire-2 software) with an
excitation wavelength of 633 nm and an exposure time of 50 s (100% intensity).
To visualize the nanocomposites, the particles were dispersed in water, sonicated for an hour and
Sensors 2016, 16, 2079 3 of 13
casted onto a copper grid to study the sizes and morphology of the particles on the GO sheet by TEM
(Transmission Electron
To visualize Microscopy)
the usingthe
nanocomposites, Tecnai 20G2-FEI,
particles with aninacceleration
were dispersed voltage
water, sonicated for of
an 200
hourkV.
and casted onto a copper grid to study the sizes and morphology of the particles on the GO sheet by TEM
2.4. Assembly and Measurement of Humidity Sensors
(Transmission Electron Microscopy) using Tecnai 20G2-FEI, with an acceleration voltage of 200 kV.
Devices with interdigital electrodes were used for humidity sensing measurement. The interdigital
2.4. Assembly and Measurement of Humidity Sensors
electrodes were fabricated by using a tantalum sheet of 1 mm thickness, applying an epoxy substrate,
and coating Devices
it withwith interdigital
rGO-SnO 2 . As electrodes were used
shown in Figure 1a, theforwidth
humidity
of a sensing
finger was measurement.
about 0.1 mm,The and
interdigital electrodes were fabricated by using a tantalum sheet of 1 mm
the distance between adjacent fingers around 75 mm. Two lead wires were connected to the tantalum thickness, applying an
epoxy substrate, and coating it with rGO-SnO 2. As shown in Figure 1a, the width of a finger was
electrodes by tin soldering, followed by masking with epoxy resin. Then, a thick slurry of rGO-SnO2
about 0.1 mm, and the distance between adjacent fingers around 75 mm. Two lead wires were
(90%), carbon black (5%), and Poly vinylidene fluoride (PVDF) (5%) in N-methyl-2-pyrrolidinone
connected to the tantalum electrodes by tin soldering, followed by masking with epoxy resin. Then,
(NMP) solvent was prepared and coated on top of the interdigital electrodes (each electrode has
a thick slurry of rGO-SnO2 (90%), carbon black (5%), and Poly vinylidene fluoride (PVDF) (5%) in N-
six arms) previously treated(NMP)
methyl-2-pyrrolidinone with an epoxy
solvent substrate
was prepared byand
thecoated
doctor
onblade
top oftechnique and dried
the interdigital at 80 ◦ C
electrodes
in air (each
for 12electrode
h in order hastosixevaporate the solvent.
arms) previously treatedFinally,
with an the
epoxyhumidity
substratesensor was fabricated
by the doctor and aged
blade technique
underand a relative
dried at 80humidity
°C in air (RH)
for 12 of h in95%, and
order with a sinusoidal
to evaporate voltage
the solvent. Finally,with an amplitude
the humidity sensorofwas 1 V, at
100 Hz, for 24 h.and
fabricated Figure
aged 1a shows
under a schematic
a relative humiditydiagram
(RH) ofof the and
95%, humidity
with a sensor.
sinusoidalThe total thickness
voltage with an of
amplitude
the sensor is 3 mmof 1 distributed
V, at 100 Hz,as forfollows:
24 h. Figure 1a shows
epoxy a schematic
substrate, 2 mm; diagram
tantalum, of 0.5
the mm;
humidity
and sensor.
rGO-SnO2
The total thickness of the sensor is 3 mm distributed as follows: epoxy substrate,
coating, 0.5 mm. The characteristic humidity sensitivity curves were measured on a Caddo LCR-9304 2 mm; tantalum, 0.5
mm; and rGO-SnO 2 coating, 0.5 mm. The characteristic humidity sensitivity curves were measured
analyzer. For that purpose, a sinusoidal voltage with an amplitude of 1 V, whose frequency varied
on a Caddo LCR-9304 analyzer. For that purpose, a sinusoidal voltage with an amplitude of 1 V,
from 100 Hz to 1 kHz at a temperature of 20 ◦ C, was used. The relative atmospheric humidity was
whose frequency varied from 100 Hz to 1 kHz at a temperature of 20 °C, was used. The relative
produced using different saturated salt solutions in their equilibrium states, including LiCl for 11%
atmospheric humidity was produced using different saturated salt solutions in their equilibrium
RH, MgCl 2 for
states, 33% RH,
including LiClNaCl forRH,
for 11% 75%MgCl RH,2 KCl for RH,
for 33% 85%NaCl
RH,forand K2RH,
75% SO4KClfor for
95%85%RH at and
RH, about
K2SO204 ◦for
C [19]:
the uncertainty of the RH values was about ± 1%. The humidity sensing measurement
95% RH at about 20 °C [19]: the uncertainty of the RH values was about ±1%. The humidity sensing system is shown
in Figure 1b.
measurement system is shown in Figure 1b.

Figure
Figure 1. Schematic
1. Schematic diagram
diagram ofof(a)
(a)the
theHumidity
Humidity sensor;
sensor;(b)
(b)the
theMeasurement
Measurementsystem.
system.

3. Results and Discussion

3. Results and Discussion
3.1. Formation Mechanism of SnO2 and rGO-SnO2 Nanocomposites
3.1. Formation Mechanism of SnO2 and rGO-SnO2 Nanocomposites
SnO2 nanoparticle decorated graphene sheets were synthesized via a redox reaction between
SnO 2 nanoparticle
graphene oxide anddecorated
SnCl2.2H2O.graphene
An aqueoussheets were synthesized
dispersion of GO was via a redox
mixed with reaction between
an SnCl2:HCl
graphene oxide and SnCl · 2H
solution. During the 2redox2 reaction, the anchored Sn cations were oxidized to SnO2,2 while solution.
O. An aqueous dispersion of
2+ GO was mixed with an SnCl :HCl the
graphene
During oxide
the redox sheets were
reaction, reduced to
the anchored 2+ cations
Sngraphene sheets.
were The even loading
oxidized to SnO2of, while
SnO2 nanoparticles
the grapheneonoxide
both sides of the graphene layer prevented the aggregation of the graphene layers. The possible
reaction mechanism can be written as follows: [20]
Sensors 2016, 16, 2079 4 of 13

sheets were reduced to graphene sheets. The even loading of SnO2 nanoparticles on both sides of the
graphene layer prevented the aggregation of the graphene layers. The possible reaction mechanism
can be written
Sensors as 2079
2016, 16, follows [20]: 4 of 13

SnCl2 +2 GO
SnCl
+ H O → rGO-SnO + 2HCl
+ GO + H22O → rGO-SnO2 2+ 2HCl (1)
(1)

CO(NH2 )2 + H2 O → CO2 + 2NH3 (2)

(2)
CO(NH2)2 + H2O → CO2 + 2NH3
NH3 + H2 O → NH4 OH (3)
NH3 + H2O → NH4OH (3)
NH4 OH + HCl → NH4 Cl + H2 O (4)
NH4OH + HCl → NH4Cl + H2O (4)
3.2. Characterization of Nano SnO2 and rGO-SnO2 Nanocomposites
3.2. Characterization of Nano SnO2 and rGO-SnO2 Nanocomposites
3.2.1. Fourier Transform Infrared Spectroscopy (FTIR)
3.2.1.GO,
The Fourier
SnOTransform Infrared Spectroscopy (FTIR)
2 , and rGO-SnO2 were recorded in the FT-IR spectra at transmittance mode and
are shownThe in GO,
Figure −1 and 1400 cm−1 , correspond
SnO2a–c,
2, andrespectively.
rGO-SnO2 were The peaks observed
recorded in the FT-IRatspectra
3453 cm at transmittance mode and are
to theshown
O–H in stretching of –COOH in GO and to the vibration of intercalated water,
Figure 2a–c, respectively. The peaks observed at 3453 cm and 1400 cm , correspond
−1 −1 respectively;
to the the
O–H stretching
characteristic peaks of ofoxygen
–COOHmoieties—located
in GO and to theat vibration − 1
1184 cm of, 1595 −
intercalated1
cm , and water, − 1
1747respectively; the
cm —correspond
to C–Ocharacteristic
(ν (epoxy orpeaks of oxygen
alkoxy)), C=Omoieties—located at 1184 cmmoieties
in –COOH, and carbonyl −1, 1595 cm−1, and 1747 cm−1—correspond
(ν (carbonyl), respectively. The GO
to C–Ogroups
functional (ν (epoxy
areorsignificantly
alkoxy)), C=Oreduced
in –COOH, andGO-SnO
from carbonyl moieties (ν (carbonyl), respectively. The
2 materials. It is clearly indicated that the
GO functional groups are significantly reduced from GO-SnO2 materials. It is clearly indicated that −1
GO is partially reduced to graphene. Moreover, the new peak (Figure 2b) appeared at 597 cm ,
the GO is partially reduced to graphene. Moreover, the new peak (Figure 2b) appeared at 597 cm−1,
is attributed to the Sn–O stretching. From this spectrum, it is clear that the rGO-SnO2 peak intensities
is attributed to the Sn–O stretching. From this spectrum, it is clear that the rGO-SnO2 peak intensities
are similar to the ones of the SnO2 sample.
are similar to the ones of the SnO
The above facts enunciate the possible compact chemical
2 sample. The above facts enunciate the possible compact chemical
bonding
bonding between SnO2 and rGO, which may be
between SnO 2 and rGO, which may be due
due totothe
theunique
uniquesynthetic
synthetic approach.
approach.

Figure 2. FTIR spectra for (a) GO; (b) SnO2; (c) rGO-SnO2.
Figure 2. FTIR spectra for (a) GO; (b) SnO2 ; (c) rGO-SnO2 .
3.2.2. X-ray Diffraction (XRD)
3.2.2. X-ray Diffraction (XRD)
Figure 3a–c shows the XRD pattern for GO (a), SnO2 (b), and rGO-SnO2 (c), respectively. Figure 3a
Figure 3a–cdiffraction
shows the shows thepeaks
XRDatpattern for GO (a), SnO
11.9° corresponding (b),exfoliation
to 2the and rGO-SnO 2 (c), respectively.
of graphitic Figure 3a
plane, i.e., (001)
crystal plane structure [21]. In ◦
Figure 3b, the diffraction peaks observed at 26.7°,
shows the diffraction peaks at 11.9 corresponding to the exfoliation of graphitic plane, i.e., (001) 34.2°, 37.9°, 51.9°
and
crystal 65.7°structure
plane correspond to In
[21]. SnO 2 (110),
Figure 3b,(101), (200), (211),peaks
the diffraction and (301) 26.7◦ , 34.2
crystalatphases,
observed ◦ , 37.9◦ , 51.9
respectively. The◦ and
◦ diffraction peaks of the synthesized rGO-SnO 2 match the ones of the tetragonal crystal phase of SnO2
65.7 correspond to SnO2 (110), (101), (200), (211), and (301) crystal phases, respectively. The diffraction
(ICDD NO: 88-0287). In Figure 3c, the observable diffraction peaks were compared with the patterns
peaks of the synthesized rGO-SnO2 match the ones of the tetragonal crystal phase of SnO2 (ICDD NO:
of GO and SnO2. Furthermore, the reduced intensity of the diffraction peak corresponding to the
88-0287). In Figure 3c, the observable diffraction peaks were compared with the patterns of GO and
graphitic plane confirms the reduction of GO (11.9°) [22]. The mean particle size (D) of the SnO2
SnO2nanoparticles
. Furthermore, the
was reducedusing
calculated intensity of the diffraction
the Scherrer formula: bypeak corresponding
applying it to the (110)toplane
the graphitic
diffractionplane
Sensors 2016, 16, 2079 5 of 13

Sensors 2016, 16, 2079 5 of 13

Sensors 2016, 16, 2079 5 of 13
confirms the reduction of GO (11.9◦ )
[22]. The mean particle size (D) of the SnO2 nanoparticles was
peak, it was found that D is ~30 nm for the rGO-SnO2 composite and ~50 nm for the SnO2
calculated
peak, it was found that D is ~30 by
using the Scherrer formula: nmapplying it to the 2(110)
for the rGO-SnO plane diffraction
composite and ~50 nmpeak, it was
for the SnOfound
2
nanoparticles alone.
that Dnanoparticles
is ~30 nm for the rGO-SnO2 composite and ~50 nm for the SnO2 nanoparticles alone.
alone.

Figure 3. XRD pattern for (a) GO; (b) SnO2; (c) rGO-SnO2.
Figure 3. XRD pattern for (a) GO; (b) SnO ; (c) rGO-SnO .
Figure 3. XRD pattern for (a) GO; (b) SnO22; (c) rGO-SnO22.
3.2.3. Raman Spectra
3.2.3.
3.2.3.Raman
RamanSpectra
Spectra
In Figure 4, the Raman spectra of GO (a), SnO2 (b), and rGO-SnO2 (c) are plotted respectively.
InInFigure
The observed
Figure 4,4,the
theRaman
Raman peakspectra
Raman shift
spectra of
at 576 GO
ofand
GO630 (a), SnO
(a),cm −1, in
SnO (b),
22 (b), and
Figure
and rGO-SnO
4b,c, respectively,
rGO-SnO (c) indicates
areplotted
2 2(c) are
plotted respectively.
therespectively.
presence
The observed Raman peak − 1
The of SnO2 [23].
observed Raman peakshift
Additionally, inat
shift at576
the and
and630
rGO-SnO
576 630 cm
cm−1,,in
2 spectrum, inFigure
Figure
the 4b,c,
peaks respectively,
atrespectively,
4b,c, 1329 indicates
and 1589indicates
cm −1 thepresence
correspond
the presence
to
ofofSnO [23]. Additionally, in the rGO-SnO spectrum, the peaks at 1329 and 1589 cm −1 correspond
the D and G band of GO. Previous reports have shown that the D band
SnO2 [23]. Additionally, in the rGO-SnO2 spectrum, the peaks at 1329 and 1589 cm correspond to
2 2 always appears whether
−1 any
tothe
theDform
Dand
andofGdisorders
Gband
band and
ofof
GO. defects
GO. arereports
Previous
Previous present;
reports e.g.,
have vacancies,
have
shown shown thatgrain
the boundaries,
that theband
D D bandalwaysand amorphous
always
appears appears carbon
whether whether
any
any species
form in carbon
of disorders materials. The G band is usually generated by the stretching of all sp 2 atoms in
form of disorders and and defects
defects are present;
are present; e.g., vacancies,
e.g., vacancies, grain boundaries,
grain boundaries, and amorphous
and amorphous carbon
carbon carbon
speciesringsin or carbon
carbon chains (E2g
materials. photons of sp 2 atoms). Namely, the ID/IG intensity ratio is closely
sp2 atoms
species in carbon materials. The GThe bandG band is usually
is usually generated
generated by the bystretching
the stretching of allofsp all2 atoms in
related with the concentration of defects and with the average size of the p-conjugation in carbon
incarbon
carbonrings
ringsoror carbon
carbon chains
chains (E2g(Ephotons
2g photons of spof sp2 atoms).
2 atoms). Namely,Namely,
the ID/Ithe ID /IG intensity
G intensity ratio is
ratio is closely
materials. Reasonably, the D band will disappear gradually when the GO is reduced for defect
closely
related related
with the with the concentration
concentration of defects of defects
and with and thewith the average
average size of the sizep-conjugation
of the p-conjugation in carbonin
decrease. In the present work, the ID/IG ratios are 0.92 for GO and 1.07 for rGO-SnO2 [24], respectively.
carbon materials.
materials. Reasonably,
Reasonably, the Dthe
bandD band
will will disappear
disappear gradually
gradually when when
Therefore, the existence of SnO2 in rGO results in more defects, as well as in the destruction ofthe the
GO GOis is reduced
reduced forsp
for defect
defect
2

decrease.
decrease. InInthe
domains. thepresent
present
From work,
anotherwork, the
pointtheofIDIDview,
/I ratios
/IGGratios are0.92
are
this change 0.92 forGO
for
also GOandand1.07
suggests 1.07
an forrGO-SnO
for rGO-SnO
interesting 2 [24],
2 [24],
connection respectively.
respectively.
between
Therefore,
Therefore,
the SnO the
the existenceofof
existence
2 nanoparticles SnO2and
SnO
(NPs) in rGO
2 in rGO[25].
rGO results in more defects,
results defects, as
as well
well as as in
in the
the destruction
destructionofofsp sp2 2
domains.From
domains. Fromanother
anotherpoint
pointofof view,
view, this
this change
change also also suggests
suggests anan interesting
interesting connection
connection between
between the
the SnO nanoparticles (NPs)
SnO2 nanoparticles (NPs) and rGO [25].
2 and rGO [25].

Figure 4. Raman spectra for (a) GO; (b) SnO2; (c) rGO-SnO2.

Figure4.4.Raman
Ramanspectra
spectrafor
for(a)
(a) GO;
GO; (b)
(b) SnO
SnO2;; (c) rGO-SnO2.
Figure 2 (c) rGO-SnO2 .
Sensors 2016, 16, 2079 6 of 13
Sensors 2016, 16, 2079 6 of 13

3.2.4. Transmission
3.2.4. TransmissionElectron
ElectronMicroscope
Microscope(TEM)
(TEM)
TEMimages
TEM imagesof ofGO,
GO,snOsnO22,, and rGO-SnO22 nanocomposites are shown in Figure 5a–c respectively.
Figure5a
Figure 5ashows
showsthetheTEM
TEMimages
imagesof ofultrasonically
ultrasonicallyexfoliated
exfoliatedgraphene
grapheneoxide.
oxide.ItItclearly
clearlyindicates
indicatesthethe
typical attributes of GO such as wrinkles and crumpled thin paper-like structure,
typical attributes of GO such as wrinkles and crumpled thin paper-like structure, with numerous folds with numerous
folds
at at theofedges
the edges the GO of sheet
the GO[26].sheet
This [26]. This
feature hasfeature has been
been reported reported by
previously previously by various
various researchers.
researchers.
As expected, theAs TEM
expected,
imagestheillustrate
TEM images illustrate
that GO that GOinto
was exfoliated wasvery
exfoliated into Figure
thin layers. very thin layers.
5b shows
Figure 5b shows the TEM image of the SnO nanoparticles. Interestingly, the structure
the TEM image of the SnO2 nanoparticles. Interestingly, the structure is composed of quasi-spherical
2 is composed
of quasi-spherical
nanoparticles. The nanoparticles.
size distribution Theand
sizeparticle
distribution and were
diameter particle diameter
estimated werethe
using estimated using the
ImageJ software
ImageJ software
application: it wasapplication:
found to lieitinwasthe found
range to lie in the
between range
40 nm andbetween
50 nm. A40similar
nm and SnO502nm. A similar
lattice fringe
SnO lattice fringe was also observed for the rGO-SnO nanocomposites (Figure
was also observed for the rGO-SnO2 nanocomposites (Figure 5c). The TEM studies further confirmed
2 2 5c). The TEM studies
further
the confirmedofthe
incorporation SnO incorporation
2 nanoparticles of SnO 2 nanoparticles
on the surface of rGOon [27].
the surface of rGO [27].

Figure5.5.TEM
Figure TEMimage
imagefor
for(a)
(a)GO;
GO;(b)
(b)SnO
SnO2; ;(c)
(c)rGO-SnO
rGO-SnO2..
2 2

3.3. Humidity
3.3. HumiditySensing
SensingProperties
PropertiesofofrGO-SnO
rGO-SnO2 SensorSensor
2
Todetermine
To determinethe theoptimal
optimalworking
workingparameters,
parameters,the theimpedance
impedanceof ofthe
therGO-SnO
rGO-SnO2 sensor
sensor under
under
2
differentRH
different RHatmospheres
atmospheresand andfor
fordifferent
differentfrequencies
frequencies(100,
(100,120,
120,and
and11kHz)
kHz)waswasmeasured
measuredat at20
20 ◦°C,
C,
and the results are shown in Figure 6a. The impedance of the sensor under
and the results are shown in Figure 6a. The impedance of the sensor under certain RH decreasedcertain RH decreased with
increasing
with working
increasing workingfrequency. It is worth
frequency. to noting
It is worth that the
to noting thatimpedance
the impedancevariation at lowatRH
variation lowisRH
much is
biggerbigger
much than that
thanobserved at high
that observed at RH.
highThe RH.sensing curves
The sensing almost
curves overlap
almost for RH
overlap forhigher than than
RH higher 80%,
indicating
80%, that the
indicating thateffect of frequencies
the effect on impedance
of frequencies on impedancewas very smallsmall
was very for this
for range. On the
this range. Onother
the
hand, the impedance decreased with the increasing RH, due to the increase
other hand, the impedance decreased with the increasing RH, due to the increase of absorbed water of absorbed water
molecules onto
molecules onto the
the sensitive
sensitive layer
layer [28].
[28]. It
It can
can be
be seen
seen that
that the
the impedance
impedance of of the
the sensor
sensor strongly
strongly
depends on the measuring frequency and the RH level. A large change is
depends on the measuring frequency and the RH level. A large change is observable for the lower observable for the lower
tested frequencies of 100 Hz and 120 Hz, while the change is inconspicuous for the higher tested
tested frequencies of 100 Hz and 120 Hz, while the change is inconspicuous for the higher tested
frequency of 1 kHz as reported by other authors [29]. This is because the electrical field direction
changes slowly at low frequencies and so polarization of the adsorbed water is strong. However, for
Sensors 2016, 16, 2079 7 of 13

Sensors 2016,
frequency of16,1 2079
kHz as reported by other authors [29]. This is because the electrical field direction 7 of 13

changes slowly at low frequencies and so polarization of the adsorbed water is strong. However,
the higher frequency ranges, the electrical field direction changes fast, and consequently water
for the higher frequency ranges, the electrical field direction changes fast, and consequently water
polarization cannot catch up with it: in consequence, the dielectric constant is small and does not
polarization cannot catch up with it: in consequence, the dielectric constant is small and does not
change with RH [30,31]. The sensing curve at 120 Hz exhibits the best linearity, and at this frequency
change with RH [30,31]. The sensing curve at 120 Hz exhibits the best linearity, and at this frequency
the sensor is very sensitive for the whole humidity range, with the impedance changing four orders
the sensor is very sensitive for the whole humidity range, with the impedance changing four orders of
of magnitude when RH varied from 11% to 95% RH. So the optimum measurement conditions were
magnitude when RH varied from 11% to 95% RH. So the optimum measurement conditions were fixed
fixed for the remaining experiments: sinusoidal voltage with amplitude of 1 V, and a frequency of
for120
theHz.
remaining
Figure 6b experiments: sinusoidal voltage
shows the dependence with amplitude
of the sensor capacitanceofon
1 V,
RHandat adifferent
frequency of 120 Hz.
frequencies
Figure 6b shows the dependence of the sensor capacitance on RH at different
(100 Hz, 120 Hz, and 1 kHz). The reported data are the mean values obtained from several frequencies (100 Hz,
120measurement
Hz, and 1 kHz). The reported data are the mean values obtained from several measurement
cycles at a temperature of 20 °C. As the RH level increases, the output capacitance cycles
of
at the
a temperature of 20 ◦ C. As the RH level asincreases, theby
output
sensor shifts higher monotonically observed othercapacitance of the
authors [32]. sensor shifts
Adsorbed waterhigher
can
monotonically
increase the as observedconstant
dielectric by otherand
authors
the [32]. Adsorbed
capacitance. water can increase
Furthermore, adsorbed the water
dielectric constant
molecules
and the capacitance. Furthermore, adsorbed water molecules strengthen the polarization
strengthen the polarization and increase the dielectric constant [33]. The sensitivity of the sensors, and increase
in
thepercentage,
dielectric constant [33].RHs
at different Thewas
sensitivity of the
calculated sensors,
using in percentage,
the following at different
equation [34]. RHs was calculated
using the following equation [34].
−
=S = CRH − C11 ××100100 (5) (5)
C11
where
where,C11C11and
andCRHCRHstand
stand for
for the
the capacitances measured atat 11%
capacitances measured 11%RH RHandandatata acertain
certainRHRHlevel,
level,
respectively. The calculated sensitivity of the sensor across the RH range of 11–95%
respectively. The calculated sensitivity of the sensor across the RH range of 11–95% was ~3900%, was ~3900%,
~4600%,
~4600%, and
and~1581%
~1581%for forthe
theexcitation
excitation signal
signal frequencies
frequencies ofof100
100Hz,
Hz,120
120Hz,
Hz,andand1 1kHz
kHzrespectively
respectively
TheThesensitivity
sensitivityofofour
oursensor
sensoratatthe
thefrequency
frequency ofof 120
120 Hz is higher
Hz is higher than
thanthat
thatfound
foundforforthe
thefrequencies
frequencies
of of
100 Hz
100 Hzandand1 1kHz
kHz[35].
[35].Therefore,
Therefore, inin the
the remainder
remainder of of the
the study,
study,the
thefrequency
frequencyofof120120HzHzwas
was
considered the best test frequency for the analysis of sensor characteristics.
considered the best test frequency for the analysis of sensor characteristics.

(a) (b)

(c)
Figure 6. (a)The dependence of impedance on the RH for the rGO-SnO2 sensor measured at various
Figure 6. (a) The dependence of impedance on the RH for the rGO-SnO2 sensor measured at various
frequencies; (b) The dependence of capacitance on the RH for the rGO-SnO2 sensor measured at
frequencies; (b) The dependence of capacitance on the RH for the rGO-SnO2 sensor measured at
various frequencies; (c) The sensitivity of the rGO-SnO2 sensor for different tested RH and
various frequencies; (c) The sensitivity of the rGO-SnO2 sensor for different tested RH and frequencies.
frequencies.
Sensors 2016, 16, 2079 8 of 13

3.4. Humidity Sensors’ Response-Recovery Time

The response and recovery times are important parameters to estimate the effectiveness of
humidity sensors. The measurement method was as follows. First, the sensor was put into a glass
container at 11% RH for several minutes until the impedance of the sensor became steady. Then,
the sensor was transferred into a glass vessel at 95% RH as quickly as possible (less than 2 s) in order
to reduce the effect of the laboratory atmosphere. Finally, the sensor was moved back to the chamber
containing 11% RH, once the sensor impedance stabilized at 95% RH [36].
The impedance modulus variation of the rGO-SnO2 sensor for four consecutive cycles of the above
described process of water adsorption and desorption is shown in Figure 7. The observed response
time is 10 s, while the recovery time is 60 s. The response and recovery properties are consistent with
the low humidity hysteresis exhibited by the sensor [32,37]. Comparison of response and recovery
times between the proposed sensor and other sensors reported in the literature is given in Table 1.

Table 1. Comparison of the proposed sensor with other reported sensors in the literature.

Sensor Sensor
Reference Electrode Substrate Sensing Material Response Recovery
Time (s) Time (s)
Bi et al. [32] Gold (Au) SiO2 Graphene oxide 10.5 41
Li et al. [38] Sliver (Ag) SiO2 SnO2 30–110 80–150
Kuang et al. [39] Platinum (Pt) SiO2 SnO2 120–170 20–60
Sin et al. [40] Gold (Au) SiO2 ZnO/SnO2 411 98
Zhang et al. [41] Platinum (Pt) SiO2 ZnO 10 30
Chen [42] Copper (Cu) SiO2 MWCNTs 45 15
Chen et al. [43] Silver (Ag) Si SiNWs 350 52
Chen et al. [43] Silver (Ag) Si HMDS modified SiNWs 132 62
Wang et al. [44] Porous Silicon Si Ta2 O5 18 40
Wang et al. [45] Silver (Ag) Ceramic TiO2 5 10
Sun et al. [46] Gold electrode Aluminum Polypyrrole 41 120
Proposed differentiate Tantalum electrode Epoxy rGO-SnO2 10 60

Li et al. [38] have studied the structure and humidity sensing properties of SnO2 zigzag belts and
the calculated response and recovery times based on different RHs (5%, 22%, 43%, 69%, and 97%) were
in the intervals 30–110 s and 80–150 s, respectively. Similarly, Qin Kuang et al. [39] have prepared
a high-sensitivity humidity sensor based on a single SnO2 nanowire: the calculated response and
recovery times, based on different RHs (5%, 30%, 48%, 76%, and 85%), were in the ranges 120–170 s
and 20–60 s, respectively. Sin et al. [40] have prepared a humidity sensor based on a film of nanocubic
ZnO:SnO2 with high sensitivity, by ultrasonic-assisted solution growth method with different Zn:Sn
precursor ratios. The calculated response and recovery times were of 411 s and 98 s, respectively.
Compared to the above values, the rGO-SnO2 nanoparticles have a better sensitivity factor and faster
response and recovery times. The fast response of the sensor is also attributed to the large quantity of
hydrophilic quaternary SnO2 groups in the rGO [47], which interact quickly with water molecules,
while the rapid recovery speed is due not only to the separation of sensitive points in the framework,
but also to the porosity, which is characteristic of rGO-SnO2 [48,49].
To test the long-term stability at high humidity, the rGO-SnO2 sensor was placed in the glass
container with 95% RH and the impedance measurements were repeated every five days over a period
of 30 days. As shown in Figure 8, a slight variation in impedance was observed with the passage of time,
proving that the rGO-SnO2 sensor has good stability and durability at high humidity. This is highly
probably due to the cross-linked porous framework of the rGO-SnO2 [50], which could effectively
prevent the composites from dissolving in the adsorbed water and immobilize the functional molecules
(rGO) in the pores.
Sensors 2016, 16, 2079 9 of 13
Sensors 2016, 16, 2079 9 of 13
Sensors 2016, 16, 2079 9 of 13

Figure 7. Response and recovery curves of the rGO-SnO2 sensor.

Figure 7. Response and recovery curves of the rGO-SnO2 sensor.
Figure 7. Response and recovery curves of the rGO-SnO2 sensor.

Figure 8. The long-term stability of the rGO-SnO2 sensor after being exposed to 95% RH for 30 days.
Figure 8. The long-term stability of the rGO-SnO2 sensor after being exposed to 95% RH for 30 days.
Figure 8. The long-term stability of the rGO-SnO2 sensor after being exposed to 95% RH for 30 days.
3.5. Sensing Mechanism of rGO-SnO2
3.5. Sensing Mechanism of rGO-SnO2
The sensing
3.5. Sensing mechanism
Mechanism of rGO-SnOis based
2 on humidity adsorption and desorption process on the surface
structure [51,52]. The
The sensing sensing is
mechanism adsorption
based on occurs
humidity in SnO 2 by its conduction
adsorption and desorption inside the water
process layers
on the and
surface
The sensing mechanism is based on humidity adsorption and desorption process on the surface
is shown in
structure FigureThe
[51,52]. 9. When
sensing a water molecule
adsorption occurscomes in contact
in SnO with the surface
2 by its conduction insideofthethewater
SnO2,layers
hydroxyl
and
structure [51,52]. The sensing adsorption occurs in SnO2 by its conduction inside the water layers
ions combine
is shown with 9.
in Figure Sn.When
The ionized
a water oxygen
molecule combined
comes inwith contactproton
withform a surface
the surface layer
of the on2,top
SnO of the
hydroxyl
and is shown in Figure 9. When a water molecule comes in contact with the surface of the SnO2 ,
SnO particles with
ions2combine [53]. Sn.
At this
The stage,
ionized water molecules
oxygen combined get with
condensed
protonand form cannot move
a surface freely
layer ondue
top toof the
hydroxyl ions combine with Sn. The ionized oxygen combined with proton form a surface layer on
two
SnO2hydrogen bonding.
particles [53]. At this The first water
stage, physically adsorbed
molecules layer has aand
get condensed higher
cannotorder
movethan the upcoming
freely due to the
top of the SnO2 particles [53]. At this stage, water molecules get condensed and cannot move freely
adsorbed
two hydrogen layer.bonding.
Continuous Thecondensing of water
first physically breakslayer
adsorbed the single
has a hydrogen
higher order bonding;
than the protons
upcomingstart
due to the two hydrogen bonding. The first physically adsorbed layer has a higher order than the
to move freely
adsorbed layer.[54]. SnO2 nanocrystals
Continuous condensing have of an effective
water breaks electronic
the single interaction
hydrogenwith rGO [55–57],
bonding; protonshence
start
upcoming adsorbed layer. Continuous condensing of water breaks the single hydrogen bonding;
the rGO-SnO
to move freely 2 facilitates
[54]. SnO2the detection have
nanocrystals of water molecule.
an effective The rGO-SnO
electronic 2 system
interaction withcanrGO detect the water
[55–57], hence
protons start to move freely [54]. SnO2 nanocrystals have an effective electronic interaction with
molecules
the rGO-SnO that2 facilitates
are normally the undetectable
detection of waterby rGO, since the
molecule. rGO-SnO
The rGO-SnO 2 system
2 system is potentially
can detect the superior.
water
rGO [55–57], hence the rGO-SnO2 facilitates the detection of water molecule. The rGO-SnO2 system
rGO-SnO
molecules2 thatexhibits higher sensitivity
are normally undetectablethanby pure
rGO, rGO,
sincesince SnO2 nanoparticles
the rGO-SnO 2 system is combined
potentiallywith rGO
superior.
can detect the water molecules that are normally undetectable by rGO, since the rGO-SnO2 system is2
offer
rGO-SnO more active sites
2 exhibits highersuch as vacancies,
sensitivity than puredefects,
rGO,and oxygen
since SnO2functional
nanoparticles groups,
combinedas does therGO
with sp
potentially superior. rGO-SnO2 exhibits higher sensitivity than pure rGO, since SnO2 nanoparticles2
bonded
offer more carbon
active regarding
sites such theas adsorption
vacancies,ofdefects,
water molecules;
and oxygen also due to the
functional high surface
groups, as doesarea theandsp
combined with rGO offer more active sites such as vacancies, defects, and oxygen functional groups,
electrical conductivity.
bonded carbon regarding The observed
the microstructure
adsorption of water of SnO
molecules; 2 and
also rGO-SnO
due to 2 is
the shown
high in
surface Figure
area 10.
and
as does the sp2 bonded carbon regarding the adsorption of water molecules; also due to the high
SnO 2 microstructure
electrical conductivity. hasThea smooth
observed surface (Figure 10a)
microstructure ofandSnOis2 and
morerGO-SnO
hydrophilic in nature
2 is shown [47]. This
in Figure 10.
surface area and electrical conductivity. The observed microstructure of SnO2 and rGO-SnO2 is shown
hydrophilic propertyhas
SnO2 microstructure of aSnO
smooth2 always
surfaceenhances
(Figure 10a)the and
fast issensing response towards
more hydrophilic in naturethe [47].water
This
in Figure 10. SnO2 microstructure has a smooth surface (Figure 10a) and is more hydrophilic in
molecules,
hydrophilicbut decreases
property of the
SnOrecovery
2 alwaystime. This isthe
enhances duefast to the condensed
sensing responsewater molecules
towards the on the
water
nature [47]. This hydrophilic property of SnO2 always enhances the fast sensing response towards the
surface
molecules,of SnO that cannot
but2 decreases themove freelytime.
recovery due This
to theis hydrogen
due to thebondingcondensed [54].water
After molecules
the anchoring on theof
SnO 2 on of
surface theSnOrGO sheet,
2 that it increases
cannot movethe surface
freely due roughness (Figurebonding
to the hydrogen 10b). Hence,[54].itAfter
decreases the physical
the anchoring of
adsorption
SnO2 on thebetween
rGO sheet, water molecules
it increases theand the sensing
surface roughnessmaterial,
(Figurewhich
10b).enhances
Hence, itthe recovery
decreases thetime.
physical
adsorption between water molecules and the sensing material, which enhances the recovery time.
Sensors 2016, 16, 2079 10 of 13

water molecules, but decreases the recovery time. This is due to the condensed water molecules on
the surface of SnO2 that cannot move freely due to the hydrogen bonding [54]. After the anchoring of
SnO2 on the rGO sheet, it increases the surface roughness (Figure 10b). Hence, it decreases the physical
adsorption between
Sensors 2016, 16, 2079 water molecules and the sensing material, which enhances the recovery time.10 of 13
Sensors 2016, 16, 2079 10 of 13

Figure 9.9.The schematic

Theschematic of
schematicof the
ofthe proposed
theproposed humidity sensing
proposed humidity sensing mechanismofofthe
the rGO-SnO 2 nanocomposite.
Figure9.
Figure The sensing mechanism
mechanism of therGO-SnO 2 2nanocomposite.
rGO-SnO nanocomposite.

(a) (b)
(a) (b)
Figure 10. SEM microstructure image for (a) SnO2; (b) rGO-SnO2.
Figure 10.
Figure 10. SEM
SEM microstructure
microstructure image
image for
for (a)
(a) SnO
SnO2;; (b)
(b) rGO-SnO
rGO-SnO2..
2 2
4. Conclusions
4. Conclusions
4. Conclusions
rGO-SnO2 nanocomposites were synthesized via redox reaction and used for humidity sensing
rGO-SnO2 nanocomposites were synthesized via redox reaction and used for humidity sensing
rGO-SnO
application. 2 nanocomposites
The humidity sensorwere was synthesized via redox
fabricated using reaction
rGO-SnO and usedsubstrate
2 on tantalum for humidity sensing
to access the
application. The humidity sensor was fabricated using rGO-SnO2 on tantalum substrate to access the
application. The humidity sensor was fabricated using
sensing platform. The sensitivity of the fabricated sensor was rGO-SnO on tantalum substrate to access
2 studied by varying the relative the
sensing platform. The sensitivity of the fabricated sensor was studied by varying the relative
sensing
humidity platform.
(RH) from The11%
sensitivity
to 95%of the afabricated
over period ofsensor was
30 days. studied
The by varying
impedance the relative humidity
and capacitance variation
humidity (RH) from 11% to 95% over a period of 30 days. The impedance and capacitance variation
(RH)
on RH as well as the long-term stability of the sensor measured at 95% RH over a period of 30RH
from 11% to 95% over a period of 30 days. The impedance and capacitance variation on as
days,
on RH as well as the long-term stability of the sensor measured at 95% RH over a period of 30 days,
well as the long-term stability of the sensor measured at 95% RH over a period of 30 days,
proving that rGO-SnO2 nanocomposite exhibited high sensitivity, rapid response and recovery times, proving that
proving that rGO-SnO2 nanocomposite exhibited high sensitivity, rapid response and recovery times,
rGO-SnO nanocomposite
and good2long-term exhibited high sensitivity, rapid response and recovery times, and good
stability.
and good long-term stability.
long-term stability.
Acknowledgments: This research was supported by Basic Science Research Program through the National
Acknowledgments: This research was supported by Basic Science Research Program through the National
Research Foundation (NRF) of Korea funded by the Ministry of Science, ICT and Future Planning (No.
Research Foundation (NRF) of Korea funded by the Ministry of Science, ICT and Future Planning (No.
2015R1A5A1037548).
2015R1A5A1037548).
Author Contributions: S.K. and R.N. conducted the experiments and wrote the initial draft of the manuscript.
Author Contributions: S.K. and R.N. conducted the experiments and wrote the initial draft of the manuscript.
H.S.L. and V.S. designed the experiments. S.K. and H.S.L. analyzed the data and wrote the final manuscript.
H.S.L. and V.S. designed the experiments. S.K. and H.S.L. analyzed the data and wrote the final manuscript.
H.S.L., S.-J.K. and S.K. reviewed and contributed to the final revised manuscript. All authors contributed to the
H.S.L., S.-J.K. and S.K. reviewed and contributed to the final revised manuscript. All authors contributed to the
analysis of the data and read the final paper.
analysis of the data and read the final paper.
Sensors 2016, 16, 2079 11 of 13

Acknowledgments: This research was supported by Basic Science Research Program through the National
Research Foundation (NRF) of Korea funded by the Ministry of Science, ICT and Future Planning
(No. 2015R1A5A1037548).
Author Contributions: S.K. and R.N. conducted the experiments and wrote the initial draft of the manuscript.
H.S.L. and V.S. designed the experiments. S.K. and H.S.L. analyzed the data and wrote the final manuscript.
H.S.L., S.-J.K. and S.K. reviewed and contributed to the final revised manuscript. All authors contributed to the
analysis of the data and read the final paper.
Conflicts of Interest: The authors declare no conflict of interest.

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