Copyright © 2014 by American Scientific Publishers

All rights reserved.

Printed in the United States of America
Science of Advanced Materials
Vol. 6, pp. 1–7, 2014
(www.aspbs.com/sam)

Low Operable Temperature Chemiresistive

Gas Sensing by Graphene-Zinc Oxide
Quantum Dots Composites
K. R. Nemade and S. A. Waghuley∗
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444602, India

ABSTRACT
Chemiresistors based on graphene-ZnO QDs composite have been fabricated and tested for CO2 detection.
Structure and morphology of composites were analysed through X-ray diffraction, high resolution-transmission
electron microscopy, and Raman spectroscopy. The optical properties were studied through ultraviolet-visible
and fluorescence spectroscopy. The graphene-ZnO chemiresistor exhibits significant sensing response at low
operating temperature and it enhanced linearly with addition of graphene. The 80 wt.% graphene-ZnO chemire-
sistor exhibits the highest sensing response among all chemiresistors, low operating temperature, high selec-
tivity, good stability, and fast response and recovery time. The particle size effect and defects chemistry was

ARTICLE
employed to analyse the enhancement in sensing response with an increase in wt.% of graphene. Also, there
was excellent correlation observed between the defects density and sensing response as a function of wt.% of
graphene.
KEYWORDS: Chemiresistor, Sensing Response, Defect Density.

1. INTRODUCTION Graphene exhibits remarkably good gas sensing proper-

Rising carbon dioxide (CO2
levels in atmosphere is
mainly responsible for increased global warming. There
are many processes including industrial revolution, which
inevitably produce CO2 . As CO2 is an essential part of
earth atmosphere, it constantly being exchanged among the
atmosphere, sea, and soil surface. Ocean absorbing carbon
dioxide (CO2
from the atmosphere, this result in ocean
acidification and subsequently cause to climate change.1
Thus, there is much need of monitoring CO2 concentration
at low operating temperature and concentration. In the vast
area of chemical sensors, mostly sensors based on metal
oxide are known to be promising due to their fast response
than any other materials, but high operating temperature2 3
and poor stability4 are the serious problems. Also, the high
operating temperature results in enhancement of the opera-
tion cost. Therefore, development of low cost CO2 sensors
for an effective monitoring is required. Correspondingly,
the low level monitoring of CO2 is essential in a variety of
biology and chemistry experiments including biochemistry
of healthy respiration system. Hence, the present work
comprises a bold attempt to develop a chemiresistor based
upon graphene-ZnO composite as a sensing material.
∗
Author to whom correspondence should be addressed.
Email: sandeepwqghuley@sgbau.ac.in
Received: xx Xxxx xxxx
Accepted: xx Xxxx xxxx
ties due to fast adsorption process.5 6 Graphene decorated
with metal oxides can modify electronic properties and
materialize with potential results.7 Whereas, zinc oxide
(ZnO) is one of the most important material demon-
strated as a chemical sensors. Chu et al. reported the ace-
tone sensing properties of ZnO based chemi-senosrs.8 Bal
et al. explored the ammonia sensing characteristics of ZnO
based material.9 Wu et al. firstly reported the graphene-
ZnO nanocomposite synthesized through solvothermal
method.10 Chen et al. verified the electrochemical prop-
erties of ZnO/reduced graphene oxide.11 Chang et al.
demonstrated the gas sensing properties of SnO2 -reduced
graphene oxide composites towards the ethanol and H2 S.12
Singh et al. reported the remarkable room temperature gas
sensing of CO and NH3 and photoluminescence properties
of ZnO decorated graphene oxide sheets.13
In the light of above discussion, present work is
designed in view of the possibility of finding gas sens-
ing response in graphene-ZnO quantum dots (QDs) com-
posite. From literature survey, it is observed that few
reports are made on graphene-ZnO composites and this
is the first time, we investigate CO2 sensing properties
of graphene-ZnO QDs composite. The CO2 sensing prop-
erties of materials were studied at room temperature as
a function of concentration of gas as well as tempera-
tures. The chemiresistor shows the high sensing response,
low operating temperature, fast response, and recovery and

Sci. Adv. Mater. 2014, Vol. 6, No. 1 1947-2935/2014/6/001/007 doi:10.1166/sam.2014.1691 1

 Low Operable Temperature Chemiresistive Gas Sensing by Graphene-ZnO Quantum Dots Composites
good stability. The gas sensing mechanism for prepared
chemiresistors analysed by using defects chemistry. Our
experiment results; clearly shows that graphene-ZnO com-
posites chemiresistors operable at low temperature, this
reduced the operation cost significantly.
2. EXPERIMENTAL DETAILS
2.1. Synthesis of Graphene-ZnO QDs Composites
The analytical grade (SD Fine, India) chemicals were used
in this work. The ZnO QD was arrested by one pot chem-
ical route. The 1 M hexamethylenetetramine (HMT) was
dissolved in 10 ml distilled (DI) water separately. After
rigorous stirring, 1 M zinc nitrate was added into the solu-
tion. The reaction was stood for 2 h at room temperature.
The precipitate so obtained was vacuum filtered and fil-
trate was first dried at room temperature for 24 h and
sintered at 100  C for 3 h. The graphene samples used
in this study were prepared by a previously reported elec-
trochemical exfoliation method.14 The graphene-ZnO QDs
composite was prepared by changing the wt.% of graphene
ARTICLE
in constant 1 g ZnO QDs in organic media (acetone). The
solution was mixed by magnetic stirrer for 30 min at room
temperature. The obtained product was kept for over night
for evaporation of acetone. For complete evaporation of
acetone, composite was sintered at 373 K for 1 h. In this
way, four samples were prepared by varying the wt.% of
graphene from 20–80 wt.%.
2.2. Material Characterization
The structural analysis of prepared materials was done
through X-ray diffraction (XRD) (Bruker diffractome-
ter D8, Advance) analysis with CuK radiation ( =
15406 nm). The high resolution-transmission electron
microscopy (HR-TEM) (Philips Tecnai F-30107) was
employed to analyse the morphology. The Raman spectro-
scopic measurements were performed on BRUKER RFS
27: Raman Spectrometer using Nd: YAG laser source
of excitation 514 nm. Optical characterizations were
done using ultraviolet-visible (UV-VIS) spectrophotome-
ter (Perkin Elmer) and fluorescence Spectrophotometer
(Hitachi, F-7000).
2.3. Chemiresistor Fabrication and Gas
Sensing Response Measurements
The sensing response is measured in term of resistance
change. The chemiresistors were fabricated by screen-
printing on glass substrate of size 25 mm × 25 mm. Before
screen-printing, glass substrates were thoroughly washed
with DI water and acetone, and then dried under argon
atmosphere. For surface resistance measurements, high
conducting silver paint contacts were deposited on adja-
cent sides of the film. The ohmic contact was achieved by
2 Sci. Adv. Mater., 6, 1–7, 2014
Nemade and Waghuley
annealing the chemiresistors at 200  C for 5 min in argon.
The average thickness of screen-printed layer was about
8 m, as determined by Digimatic Outside Micrometer
(Series-293, Japan). The CO2 sensing properties of materi-
als were studied in a home build gas sensor assembly. The
resistance of the chemiresistor was measured by using a
voltage divider method.15 All experiments are carried out
using dry air as carrier gas having H2 O lower than 3 ppm.
Before each gas detection test, the chemiresistor was mea-
sured under air flow until a stable response is obtained
(set as the baseline resistance). The concentration inside
the chamber was maintained by injecting known volume
of the CO2 . The sensing response is defined as:15
Rg − Ra 
S= (1)
Ra
where, Ra is the baseline resistance of the chemiresistor in
dry air and Rg is the resistance of chemiresistor in gas. The
value of Rg measured at constant interval of time (15 s).
The response time was measured by injecting 100 ppm
CO2 gas into the chamber at the room temperature. The
time required to achieve 90% of its highest value was con-
sidered as response time. Similarly, the recovery time of
the chemiresistor was defined as the time required for its
resistance to be reduced by 90% from its highest value. To
assess the reproducibility of the results, each measurement
is repeated several times.
3. RESULTS AND DISCUSSION
3.1. XRD Analysis
Figure 1 shows the XRD patterns of the graphene (pre-
viously reported), ZnO QDs and (20–80 wt.%) graphene-
ZnO QDs composites. There are two prominent peaks
in the XRD pattern (Fig. 1(a)), (002) and (100) which
are characteristic peaks of graphene. The peak at 2 =
263 shows a highly organised structure with an inter-
layer spacing of 0.339 nm. The broad peak at 2 = 442
may be assigned for lower degree of crystallization.16
Likewise, the structural purity of ZnO QDs reflects in
Figure 1(b). The diffraction peaks for ZnO are in agree-
ment with the standard PDF card number 01-075-1533
(Fig. 2). The reflecting planes observed in graphene and
ZnO are appeared at the same 2 positions in compos-
ites Figures 1(c)–(f), this indicative of good coordination
between the graphene and ZnO. Besides that, the broad
width appeared in composites with an increasing wt.% of
graphene also shows the well interaction between the com-
ponents of composites that is graphene and ZnO. Debye–
Scherrer formula was used to calculate the crystallite size.
The crystallite size decreases with an increase in the wt.%
of graphene.
The average crystallite size of ZnO QDs was found to
be 4.17 nm and for composites, it was found to be ranges
Nemade and Waghuley Low Operable Temperature Chemiresistive Gas Sensing by Graphene-ZnO Quantum Dots Composites

Table I. Average crystallite sizes of all samples.

Sample Particle size (nm)

Graphene 56
ZnO QDs 417
20 wt.% 394
40 wt.% 380
60 wt.% 374
80 wt.% 368

3.2. TEM Analysis

Figure 3 shows the TEM images of ZnO QDs. The average

crystallite size of ZnO QDs estimated from XRD analy-
sis concurs with TEM investigation. However, the separate
ZnO QDs can be clearly distinguished in figure, which
meant the aggregation of ZnO was well barred.
Figure 4 shows the TEM image of the 80 wt.%
graphene-ZnO QDs composite. The TEM image presented
the graphene surface is densely decorated with ZnO QDs.
The inset of Figure 4 depicts the selected area electron
diffraction (SAED) image of composite. The good coor-

Fig. 1. XRD patterns of (a) graphene, (b) ZnO QDs along with
(c) 20 wt.%, (d) 40 wt.%, (e) 60 wt.% and (f) 80 wt.% of graphene-ZnO
QDs composite.
ARTICLE
dination between the graphene and ZnO QDs observed
through the broad rings in image. From magnified image
of the white section, hybridised structure of graphene and
ZnO QDs reflects. The ZnO QDs engaged surface and
edges of graphene. This has been directly visualised by
HR-TEM, shown in Figure 5.

between the 3.94–3.68 nm. The average crystallite values 3.3. UV-VIS and Fluorescence Measurements
for samples listed in Table I. The smallest crystallite size
was found to be 3.68 nm for 80 wt.% graphene-ZnO QDs Figure 6 shows the UV-VIS spectrum of graphene and
composite. ZnO QDs. The intense absorption at 268 nm assigned to

Actual Curve

Standard PDF card curve

(Card No. PDF 01-075-1533)

Fig. 2. Standard XRD card curve for ZnO.

Sci. Adv. Mater., 6, 1–7, 2014 3

 Low Operable Temperature Chemiresistive Gas Sensing by Graphene-ZnO Quantum Dots Composites
Fig. 3. TEM image of ZnO QDs.
the few layered two-dimensional graphene.17 The UV-VIS
spectrun of ZnO QDs shows intense absorption at 341 nm.
The value of particle size estimated from XRD analysis
and absorption in UV region confirms the presence of
ARTICLE
quantum confinment in ZnO QDs.18
The sensing properties are appreciably influence by
defects concentration on the sensing surface.19 20 So, deter-
mination of defects concentration on sensing surface is
important. Figure 7 shows the fluorescence spectrum of
(20–80 wt.%) graphene-ZnO QDs composites. From plot,
it is clearly observed that the intensity value of ultravio-
let (IUV
increases with an increase in wt.% of graphene.
This shows that the graphene surface becomes more defec-
tive in the presence of ZnO QDs. This may be due to
ZnO QDs create vacancies or dangling bonds on graphene
surface.21 Hence, as the defects density increases, inten-
sity also increases. The intensities ratio of the ultravio-
let (IUV
to visible deep levels (IDL
is direct measure of
defect density.19 The fluorescence spectroscopy is straight-
forward approach of measurements of defects density and
the ratio of fluorescence intensities of deep level and near
band edge emission is postulated to be an index of defect
density.20
Fig. 4. TEM image (left) of 80 wt.% graphene-ZnO QDs compos-
ite. Inset shows the selected area electron diffraction pattern. Magnified
image (right) of the white section, reflecting the hybridised structure of
graphene and ZnO QDs.
4 Sci. Adv. Mater., 6, 1–7, 2014
Nemade and Waghuley
Fig. 5. HR-TEM image of 80 wt.% graphene-ZnO QDs composite.
3.4. Gas Sensing Characteristics
To know about the selective behaviour of chemiresistors
towards the oxidizing and reducing species, its response to
CO2 (50 ppm) and LPG (50 ppm) at 423 K was studied,
respectively. It is well known that LPG is composition of
CH4 , C3 H8 , C4 H10 etc., hence this gas choose to study the
selective behaviour as a representative of reducing species.
The results are presented in Figure 8. It is notable that
selective behaviour of composites enhanced with wt.%
of graphene. The highest value of sensing response was
obtained for the 80 wt.% graphene. The reason may be
that CO2 has a higher redox activity compared to the LPG.
Furthermore, the sensing response of chemiresistors was
also measured as a function of concentration at room tem-
perature (Fig. 9). The chemiresistors exhibited an increase
in response as a function of CO2 concentration. Moreover,
the responses of 20–80 wt.% graphene-ZnO composites
chemiresistors have almost linear behaviour. From the plot,
it is analysed that composition with 80 wt.% graphene-
ZnO has the maximum sensing response. This may be due
the smaller crystallite size, which provides a larger surface
100
Graphene
268 nm
80
ZnO QDs
% Absorption
60
40
341 nm
20
0
260 300 340 380
Wavelength (nm)
Fig. 6. UV-VIS spectrum of graphene and ZnO QDs.
Nemade and Waghuley Low Operable Temperature Chemiresistive Gas Sensing by Graphene-ZnO Quantum Dots Composites

60 7
IUV 20 wt.% Graphene

40 wt.% 6 ZnO QDs

20 wt.%
Fluorescence Intensity

60 wt.%
40 5 40 wt.%
80 wt.%

Sensing Response
60 wt.%
4
80 wt.%

20 3

2
IDL
1
0
300 400 500 600 700
Wavelength (nm) 0
0 50 100 150 200
Fig. 7. Fluorescence spectrum of (20–80 wt.%) graphene-ZnO QDs Carbon Dioxide Concentration (ppm)
composites.
Fig. 9. Chemiresistor response as a function of concentration of CO2 .
22
to volume ratio for gas-solid interaction. Another rea-
son for enhancement in sensing response with wt.% of response related to defects density through the oxy-
graphene attributed to an increase in defects density. The gen vacancies, which can act as adsorption sites for
variation of IUV /IDL ratio and CO2 sensing response with atmospheric oxygen. Therefore, more number of defects

ARTICLE
the wt.% of graphene is shown in Figure 10. From the adsorbed more oxygen ions. This is one of the possible
plots, it is scrutinized that sensing response increases with reason for an increase in sensing response with increasing
defects density that is (IUV /IDL
ratio linearly as a function defects density and wt.% of graphene.
of wt.% graphene. This result is consistent well with the From Figure 9, it is demonstrated that the addition
observation made by previous reports.20 23 of graphene make composite to improve the gas sens-
In chemiresistors, the change in resistance is mainly ing properties. This may be due to ZnO is a readily
originated due to the adsorption atmospheric oxygen, electron donor and carbon based materials are compara-
forming ionic species such as24 tively good electron acceptors.25 Hence, ZnO QDs act as
O2 gas
→ O2 ads
(2) active sensing sites by damageing to the graphene sur-
face, which may create vacancies or dangling bonds on
O2 ads
+ e− → O−
2 ads
(3) graphene surface and subsequently, enhance defects den-
O− − − sity. Therefore, atmospheric oxygen more rapidly interacts
2 ads
+ e → 2O ads
(4)
with defects generated due to interaction between ZnO
This scheme hold good for semiconducting metal oxide QDs and graphene. This statement is supported by flu-
i.e., for ZnO QDs in chemiresistor. As gas sensing orescence spectroscopy. As displayed in Figure 7, under
excitation wavelength of 254 nm, a broad band at 330–
6 450 nm is detected in all samples, which is attributed to
the defects density. Another possible reason for increase
5
Carbon Dioxide
LPG
Sensing Response

0
Graphene ZnO QDs 20 wt.% 40 wt.% 60 wt.% 80 wt.%
graphene graphene graphene graphene

Fig. 8. Response of chemiresistors towards CO2 (50 ppm) and LPG Fig. 10. The variation of IUV /IDL ratio and CO2 sensing response with
(50 ppm) at 423 K. the wt.% of graphene.

Sci. Adv. Mater., 6, 1–7, 2014 5

 Low Operable Temperature Chemiresistive Gas Sensing by Graphene-ZnO Quantum Dots Composites
6
Graphene
ZnO QDs
5
20 wt.%
40 wt.%
Sensing Response
4 60 wt.%
80 wt.%
3
0
323 373 423
Temperature (K)
Fig. 11. Chemiresistor response as a function of operating temperature
to 30 ppm CO2 .
in sensing response is that at low graphene wt.%, electron
transfer mainly due to ZnO QDs and electrons are flow by
hopping between QDs. On the other hand, at high wt.%
ARTICLE
of graphene, it overlaps on to the ZnO QDs and the resis-
tance of graphene is lower than that of ZnO QDs. Hence,
the adsorption of CO2 increases with wt.% of graphene
and ZnO played important to make graphene sheets defec-
tive. Therefore, the synergistic effect between these two
materials would effectively increase gas sensing proper-
ties. When chemiresistor exposed to the CO2 environment,
CO2 molecules adsorbed on oxygen ions. This adsorp-
tion result in the formation of a surface carbonates and
increases the resistance of chemiresistor.26 Therefore, the
physical adsorption of CO2 on the graphene surface is the
dominant sensing mechanism.6 27–29
The gas sensing response of chemiresistors towards the
30 ppm CO2 gas as a function of operating temperature
shown in Figure 11. Each curve shows a maximum sensing
response values corresponding to temperature, excluding
pure ZnO chemiresistor. This may be due to operating
temperature value of ZnO chemiresistor exist beyond the
473 K.30 31 From the plot, it is observed that all compos-
ites possess operating temperature at 448 K. This value is
relatively low that result in the low power consumption.
The results demonstrated that the chemiresistors response
to 30 ppm CO2 increases with an increasing wt.% of
graphene. The 80 wt.% graphene-ZnO composites exhib-
ited the optimum value of sensing response (5.31) at
448 K. The sensing response value from certain temper-
ature decreases, this may be due to desorption of oxygen
ions from chemiresistor surface. When the thermal vibra-
tion becomes sufficiently enough, adsorbed oxygen will
get desorbed.32
The stability chacateristics of 80 wt.% graphene-ZnO
composite is shown in Figure 12. Inset shows the tran-
sient response characteristics. The stability was measured
for 30 days, at an interval of 5 days for 100 ppm of
6 Sci. Adv. Mater., 6, 1–7, 2014
Nemade and Waghuley
473
Fig. 12. Stability and transient response (inset) characteristics of
80 wt.% graphene-ZnO chemiresistor to 100 ppm CO2 .
CO2 . From plots, it is clearly observed that chemiresistor
has almost constant sensing response indicating the good
stability. The transient response characteristic shows that
the response time of 80 wt.% graphene-ZnO compos-
ite chemiresistor exhibited fast response time (12 s). The
recovery time of chemiresistor was found to be 24 s.
In regards to the selectivity, sensing response, operat-
ing temperature, stability and fast response time, 80 wt.%
graphene-ZnO QDs chemiresistor is superior among the
prepared chemiresistors.
4. CONCLUSIONS
In this work, we made an attempt to study the influ-
ence of graphene concentration on gas sensing properties
of ZnO QDs. The gas sensing properties of graphene-
ZnO composites chemiresistors indicated that 80 wt.% of
graphene-ZnO composite chemiresistors exhibits the high-
est sensing response among all chemiresistors, low oper-
ating temperature, good stability and fast response and
recovery time. Besides that, the selectivity response of
graphene-ZnO composite chemiresistors to CO2 and LPG
(CH4 , C3 H8 , C4 H10
was also measured and the results
implied that 80 wt.% of graphene-ZnO composite chemire-
sistor has a well selectivity to CO2 . This enhancement in
sensing response attributed to small crystallite size and
high defects density, which evident from XRD and fluores-
cence analysis. The 80 wt.% of graphene-ZnO composite
chemiresistors enables detection of CO2 at low tempera-
ture operation, which reduce the power consumption and
subsequently operation cost. This is attractive accomplish-
ment of present work. On account of good characteristics
mentioned above, 80 wt.% of graphene-ZnO composite
chemiresistors can be good practical sensor for detection
of CO2 .
Nemade and Waghuley Low Operable Temperature Chemiresistive Gas Sensing by Graphene-ZnO Quantum Dots Composites
Acknowledgments: Authors are very much thankful to
Head, Department of Physics Sant Gadge Baba Amravati
University, Amravati for providing necessary facilities.
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7
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Strontium oxide quantum dot

decorated graphene composites for
liquid petroleum gas sensing
a a
Kailash R. Nemade & Sandeep A. Waghuley
a
Department of Physics , Sant Gadge Baba Amravati University ,
Amravati , India
Published online: 26 Sep 2013.

To cite this article: Kailash R. Nemade & Sandeep A. Waghuley (2013) Strontium oxide quantum dot
decorated graphene composites for liquid petroleum gas sensing, Journal of the Chinese Advanced
Materials Society, 1:3, 219-228, DOI: 10.1080/22243682.2013.838375

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Vol. 1, No. 3, 219–228, http://dx.doi.org/10.1080/22243682.2013.838375

Strontium oxide quantum dot decorated graphene composites for

liquid petroleum gas sensing
Kailash R. Nemade and Sandeep A. Waghuley*
Downloaded by [Amravati University], [Sandeep Waghuley] at 02:42 27 September 2013

Department of Physics, Sant Gadge Baba Amravati University, Amravati, India

(Received 16 July 2013; revised 17 August 2013; accepted 23 August 2013)

Liquid petroleum gas-sensing behaviour of graphene/SrO quantum dots (QDs) compo-

sites was investigated. Structure and morphology of prepared materials were analysed
through X-ray diffraction (XRD) and transmission electron microscopy along with
selected-area diffraction pattern. The optical properties were analysed through
fluorescence spectroscopy. The thermal behaviour of optimized sensing material was
examined using thermogravimetric differential thermal analysis (TG-DTA). The
gas-sensing properties of composites were measured by resistance change as a
function of gas concentration. A notable better sensing performance was observed for
liquefied petroleum gas (LPG). The enhanced gas-sensing properties with increasing
amount of graphene are discussed by using defect chemistry. A good correlation is
observed between the fluorescence intensity ratio (IUV/IDL) and the sensing response
as a function of the amount of graphene.
Keywords: chemiresistor; graphene; SrO; quantum dots

1. Introduction
Liquefied petroleum gas (LPG) has only a very faint odour, and consequently, it is neces-
sary to add some odorant, which makes it detectable. When mixed with air at very high
concentrations, LPG vapour is an anaesthetic and subsequently asphyxiates by diluting
the available oxygen. The auto-ignition temperature of LPG is around 410–580
C and
hence it will not ignite at normal temperature. However, any electrical apparatus larger
than a digital wristwatch has the potential to generate sufficient energy to ignite LPG
vapour.[1] This is why it is necessary to find out efficient LPG-sensing material. There-
fore, objective of this research is to produce a highly selective and sensitive LPG-sensing
material. Hence, the present work comprises development of chemiresistors based upon
unattempted sensing material graphene/SrO quantum dots (QDs) composite.
Graphene-based composites have wide range of applications such as gas sensor,[2]
optics and energy-based applications.[3] The graphene-based, field-effect transistors have
reported the detection of absorption of a single gas molecule.[4] The gas-sensing mecha-
nism of graphene is based on the adsorption of gas molecules on the surface.[5] Jain et al.
reported the barium strontium titanate ceramic powder as a gas-sensing material for
detection of ammonia gas.[6] As the electronic property of material is mainly affected by
defects concentration, the gas response measured in terms of resistance is therefore
closely correlated to the intrinsic defects.[7,8] Kaur et al. [9] reported the sensing of H2S
gas at ppb level and demonstrated the sensing parameters strongly affected by defects

*Corresponding author. Email: sandeepwaghuley@sgbau.ac.in

Ó 2013 Chinese Advanced Materials Society

 220 K.R. Nemade and S.A. Waghuley

density. Lupan et al. [10] discussed the sensing mechanism for hydrogen gas and focused
on the role of defect chemistry.
In the present work, we are reporting the material graphene/SrO QDs composites for
LPG sensing, which is first time in the literature of material science. LPG sensing perfor-
mance of materials was studied at room temperature as well as at different temperatures.
The present work is devoted to the detection of LPG at low concentration and operating
temperature.

2. Experimental
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Graphene and SrO QDs were synthesized as reported previously.[11,12] The graphene/
SrO QDs composites were prepared by mixing graphene in constant 1 g SrO QDs in
20 ml acetone as organic media. The solution was mixed using magnetic stirrer for
30 min at room temperature. The obtained solution was kept overnight for evaporation of
acetone. In this manner, the prepared composite was sintered at 373 K for 1 h for com-
plete evaporation of acetone. The graphene was varied from 20 to 80 wt.%.
The X-ray diffraction (XRD)
patterns of samples were recorded on a Rigaku Miniflex
using CuKa radiation (λ ¼ 1.54 A) in the range 20
70
. The morphology of the samples
was studied using electron-imaging techniques, transmission electron microscopy
selected-area diffraction pattern (TEM-SADP) (JEOL-1200ex) and high-resolution trans-
mission electron microscopy (HR-TEM) (Philips Tecnai F-30107). The fluorescence
analysis was done on FL Spectrophotometer (Model: HITACHI, F-7000). The thermogra-
vimetric differential thermal analysis (TG-DTA) was carried out on Shimadzu DTG-60H
thermal analyser under nitrogen atmosphere. The temperature of the sample was varied
from room temperature to 775 K.
The chemiresistors were prepared by screen-printing technique on glass substrate of
size 25 mm  25 mm. The prepared chemiresistors were dried at room temperature for
24 h. Heating treatment was given to the film at 373 K for 3 h. For surface resistance
measurement, electrodes of silver were deposited on adjacent sides of the film and then
kept for heating at 353 K for 15 min in an argon atmosphere to make an Ohmic contact.
The sensing response was measured from resistance change of the chemiresistor with dif-
ferent concentrations (ppm) and at different temperatures. The electrical resistance was
measured by using a voltage drop method used by Waghuley et al.[13] The gas-sensing
response of the chemiresistor is defined as follows:

DR jRg  Ra j
S¼ ¼ ð1Þ
Ra Ra

where Ra is the resistance of chemiresistor in air and Rg is the resistance chemiresistor in

gas. The response time was determined by injecting the required amount of gas in the
chamber keeping the chemiresistor at room temperature. The required gas concentration
inside the system was achieved by injecting a known volume of test gas using a gas-
injecting syringe of volume 50 ml. The time taken by the chemiresistor to achieve 90%
of its highest value was considered as response time. Similarly, the recovery time of the
chemiresistor was defined as the time taken for its resistance to be reduced by 90% from
its highest value. The heater was fixed on the base plate to heat the sample under test up
to required operating temperatures. A Cr–Al thermocouple was used to determine the
operating temperature.
 Journal of the Chinese Advanced Materials Society 221

3. Results and discussion

3.1. Materials characterization
Figure 1(a)–(f) shows the XRD patterns of (20–80 wt.%) graphene/SrO QDs composites
along with graphene and SrO QDs. XRD pattern shown in Figure 1(a) indicates the for-
mation of graphene. There are two peaks, (002) and (100), which are main peaks of gra-
phene. The sharp peak at 2u ¼ 26.3
indicates a highly organized structure.[14] The
broad peak at 2u ¼ 44.2
may be assigned for lower degree of crystallization. Figure 1(b)
indicating the structural purity of SrO QDs. There are five peaks observed in the XRD
pattern, (111), (200), (220), (311) and (222), which are characteristic peaks of SrO QDs.
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All the peaks are exactly

indexed to cubic structure of SrO, and the cell parameters are
a ¼ b ¼ c ¼ 5.16 A (PDF 01-075-6979). The average crystallite size was determined
using the Debye–Scherrer equation, and was found to be 5.5 nm. The XRD patterns of
20–80 wt.% composites are shown in Figure 1(c)–(f). It is observed that average crystal-
lite size for composites ranges between 4.7 and 6.2 nm.
Figure 2(a) and 2(b) depicts the TEM, SADP and HR-TEM image of the optimized
sample discussed later, 80 wt.% graphene/SrO QDs composite. Figure 2(a) shows the dis-
tinct grain boundaries and less spherical shape of the 80 wt.% composite. The inset shows

Figure 1. XRD patterns of (a) graphene, (b) SrO QDs, (c) 20 wt.% graphene/SrO QDs,
(d) 40 wt.% graphene/SrO QDs, (e) 60 wt.% graphene/SrO QDs and (f) 80 wt.%. graphene/SrO
QDs.
 222 K.R. Nemade and S.A. Waghuley
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Figure 2. (a) TEM image of 80 wt.% graphene/SrO QDs composites and the inset shows the
SADP image; (b) HR-TEM image of SrO QDs.

SADP image indicating the presence of finely dispersed nanocrystals. Figure 2(b) shows
that SrO QDs strongly anchored on the surface of graphene.
As discussed in Section 1, defects concentration strongly influences the sensing
properties. Fluorescence spectroscopy is a straight approach of measurement of defects
density in the material. The defect concentration can be estimated by using the intensities
ratio between the ultraviolet (IUV) and visible deep levels (IDL).[10] As the QDs are fluo-
rescent nanocrystals due to quantum confinement, their fluorescence analysis becomes
important. The emission spectrum of graphene, SrO QDs along with 20–80 wt.%
graphene/SrO QDs composites recorded under irradiation by 254 nm in the range
300–700 nm is shown in Figure 3. The IUV, IDL and (IUV/IDL) ratio values for graphene,
SrO QDs and 20–80 wt.% graphene/SrO QDs composites are listed in Table 1.
Figure 4 shows the TG-DTA of 80 wt.% graphene/SrO QDs composites, in order to
study the thermal stability during the heat treatment to the material. The TG-DTA analy-
sis was carried out from room temperature to 775 K in nitrogen atmosphere.
According to the % TGA curve, the sample shows a sharp weight loss upto 345 K and
the DTA curve shows an endothermic pick at 344 K corresponding to the evaporation of

Figure 3. Emission spectra of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites.
 Journal of the Chinese Advanced Materials Society 223

Table 1. IUV/IDL ratio for graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites.

Sample IUV IDL IUV/IDL ratio

Graphene 26.51 1.51 17.55

SrO QDs 25.99 4.52 5.75
20 wt.% 26.85 1.37 19.59
40 wt.% 31.07 1.34 23.18
60 wt.% 38.84 1.37 28.35
80 wt.% 46.66 1.27 36.47
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absorbed water. The total mass loss from room temperature to 425 K was about 14.41%.
This mass loss is continued up to 625 K.

3.2. LPG sensing characterization

To know about the selective behaviour of the chemiresistors towards the oxidizing and
reducing species, its response to CO2 (30 ppm) and LPG (30 ppm) at 398 K was studied,
respectively. As LPG is composed of CH4, C3H8, C4H10, etc., these gases were chosen
for studying selective behaviour as a representative species. The results are presented in
Figure 5. It is notable that selective behaviour of composites towards the LPG enhanced
with wt.% of graphene. The highest value of sensing response was obtained for the
80 wt.% chemiresistor.
The gas-sensing properties of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs
composites chemiresistors for LPG were examined at room temperature as a function of
concentration of LPG is as shown in Figure 6. We have reported that the 80 wt.% gra-
phene/SrO QDs composites chemiresistor possesses good sensing response for LPG at
room temperature. Moreover, the responses of 20–80 wt.% graphene/SrO composites

Figure 4. TG-DTA curve of 80 wt.% graphene/SrO QDs composites.

 224 K.R. Nemade and S.A. Waghuley
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Figure 5. Response of chemiresistors towards CO2 (30 ppm) and LPG (30 ppm) at 398 K.

chemiresistors have almost linear behaviour. From the plot, it is analysed that sensing
response increases with an increase in the amount of graphene. This may be due the
smaller crystallite size which provides a larger surface-to-volume ratio for gas–solid
interaction.[15]
The response of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites
chemiresistor towards LPG as a function of temperatures was illustrated for 50 ppm dis-
played in Figure 7.
It can be seen that graphene/SrO QDs composites chemiresistors exhibited the maxi-
mum response at 423 K for LPG. This may be due to an oxygen adsorption rate is maxi-
mum around 423 K.[16] The maximum response value was found to be for 80 wt.%
graphene/SrO QDs composites chemiresistor. The 80 wt.% chemiresistor possesses maxi-
mum sensing response value at room temperature as well as a function of temperature.
This may be due to small particle size, which is related with the surface-to-volume ratio.

Figure 6. Sensing responses of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites
chemiresistors as a function of LPG concentration.
 Journal of the Chinese Advanced Materials Society 225
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Figure 7. Sensing responses of graphene, SrO QDs and 20–80 wt.% towards LPG as function of
temperatures at 50 ppm.

Another reason may be defects density. The decrease in particle size is recognized from
XRD analysis, as the peaks are broadened with the increase in the amount of graphene.
The smaller particle size affords a larger surface area for gas–solid interface that
improved sensing response. Similarly, the increase in defects density was confirmed from
fluorescence measurements. As the temperature increases, defect density on graphene
surface also increases, resulting in enhancement of sensing response at high temperature .
The sensing response decreases beyond particular temperature. This may be due to
removal of adsorbed oxygen by thermal excitation.[17]
The increase in defects concentration on the graphene surface confirmed through
(IUV/IDL) ratio using fluorescence measurement. Figure 8 shows the variation of IUV/IDL
ratio (obtained from fluorescence measurements) and sensing response (estimated from
sensing response measurements) with the wt.% of graphene.
It is noticeable that excellent correlation exists between the IUV/IDL ratio (defects den-
sity) and gas-sensing response. It is also observed that the defects density linearly

Figure 8. The variation of IUV/IDL ratio and LPG sensing response with the wt.% of graphene.
 226 K.R. Nemade and S.A. Waghuley

increased with wt.% of graphene. The density of defects may increase due to damage to
the graphene surface during addition into SrO QDs, or by the interaction between SrO
QDs and graphene. This may produce vacancies or dangling bonds.[18] This is one of the
possible reasons for enhancement in sensing response with the amount of graphene.
Another possible reason for the increase in sensing response is that at low graphene level,
electron transfer is mainly due to SrO QDs and electrons flow by hopping between QDs.
On the other hand, at high grapheme level, it overlaps on to the SrO QDs and the
resistance of graphene is lower than that of SrO QDs. Thus, the adsorption of LPG on
sensing surface increases with an increase in defect density. Therefore, the synergistic
effect between these two materials would effectively increase gas-sensing properties.
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Gas-sensing action is related to defects through the oxygen vacancies, which can act as
adsorption sites for gas molecules. The reaction for adsorbed oxygen ions are as
follows [17]:

O2 ðgasÞ ! O2 ðadsÞ ð2Þ

O2 ðadsÞ þ e ! O
2 ðadsÞ ð3Þ
O
2 ðadsÞ
 
þ e ! 2O ðadsÞ ð4Þ

When the chemiresistor is exposed to LPG that is composed of CH4, C3H8, C4H10,
etc., it interacts with the adsorbed oxygen ions and forms H2O and CO2. The reaction
between LPG and adsorbed oxygen ions are as follows [15]:

Cn H2nþ2 þ 2O ðadsÞ ! H2 O þ Cn H2n : O þ e ð5Þ

 
Cn H2n : O þ O ðadsÞ ! CO2 þ H2 O þ e ð6Þ

For stability measurements of chemiresistors, its sensing responses towards 100 ppm
of LPG at room temperature were measured for 30 days. This result is depicted in
Figure 9. The chemiresistors possess nearly constant response to LPG, indicating good
stability. The transient response characteristics for 80 wt.% chemiresistor towards LPG is
shown in the inset of Figure 9. In this measurement, gas is inserted in the chamber and

Figure 9. (a) Transient and (b) stability response of 80 wt.% graphene/SrO QDs composite to LPG
at room temperature.
 Journal of the Chinese Advanced Materials Society 227

chemiresistor is set to achieve its highest stable sensing response value. The fast response
of around 16 s for LPG is shown by 80 wt.% chemiresistor. While the chemiresistor is
exposed to air, the time taken by it to reduce by 90% of its highest value is known as
recovery time. The 80 wt.% chemiresistors achieved recovery in 22 s for both gases.

4. Conclusions
We have demonstrated the chemiresistive gas-sensing application of graphene/SrO QDs
composites towards LPG. The structural purity of samples were analysed by XRD. The
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TG-DTA study suggested that the material is stable thermally. The 80 wt.% chemiresistor
is a good candidate for practical use in detection of LPG as it shows good sensing
response, stability, fast response and recovery. The gas-sensing mechanism is discussed
effectively using defect chemistry.

Acknowledgements
The authors wish to thank the Head, Department of Physics, Sant Gadge Baba Amravati University,
Amravati, and the Head, Department of Chemical Science, North Maharashtra University, Jalgaon,
for providing necessary facilities. One of the authors, K.R. Nemade, also extends thanks to Sant
Gadge Baba Amravati University, Amravati, for awarding the late M.N. Kale scholarship for the
PhD work.

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 Available online at www.sciencedirect.com

CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 6109–6113
www.elsevier.com/locate/ceramint

Low temperature synthesis of semiconducting α-Al2O3 quantum dots

K.R. Nemade, S.A. Waghuleyn
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444602, India
Received 16 July 2013; received in revised form 14 November 2013; accepted 14 November 2013
Available online 25 November 2013

Abstract

A simple low temperature chemical route, which was based on the reactions of aluminium nitrate and hexamethylenetetramine in aqueous
medium at 473 K for 36 h, was proposed for the synthesis of α-Al2O3 quantum dots (QDs). The characterisation results from X-ray diffraction,
Fourier transform infrared spectroscopy and transmission electron microscopy along with selected area diffraction pattern are revealed the
formation of α-Al2O3. Ultra-violet spectra indicated that the as-synthesised α-Al2O3 has a direct band gap of about 3.6 eV and also disclosed
semiconducting behaviour of α-Al2O3 QDs using defect chemistry.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: B. Defects; Semiconductor; Quantum dots; Chemical route

1. Introduction phase at relatively low temperature (473 K) than reported in

Among many metal oxides, aluminium oxide (Al2O3) is
currently one of the most useful oxide ceramics [1]. Okubo
et al. [2] reported the Al2O3/InN composite material. This
material is one of the most promising materials for high-speed
electronic devices because of its high electron mobility [3] and
high saturation drift velocity [4]. French et al. studied the
optical and electronic properties of α-Al2O3 by using the
vacuum ultraviolet spectroscopy, confirms the insulating
nature of Al2O3 due to its large band gap of the order 14 eV
[5]. Mirjalili et al. reported synthesis of nanocrystalline
α-Al2O3 at 1473 K for about 1 h by the sol–gel method [6].
Weber et al. discussed the presence of band gap in Al2O3 on
the basis of native defects [7]. Li et al. [8] reported the
synthesis of ultrafine α-Al2O3 powder by a simple aqueous
sol–gel process at 1273 K. Zaki et al. [9] prepared highly pure
α-Al2O3 nanoparticles at relatively low temperatures 1198 K
by using the Pechini method.
Here, a relatively simple, efficient and low temperature
method has been developed to synthesis α-Al2O3 quantum dots
(QDs). The novelties of present work are we achieved α-Al2O3
n
Corresponding author. Tel.: þ91 9423124882.
E-mail address: sandeepwaghuley@sgbau.ac.in (S.A. Waghuley).
the literature and semiconducting band gap for α-Al2O3.
2. Experimental methods
All chemicals used were of analytical grade (SD fine, India).
The sample was prepared with deionized water of resistivity
not less than 18.2 MΩ/cm. The aluminium nitrate and hexam-
ethylenetetramine (HMT) were used for the synthesis of Al2O3
QDs. In a typical synthesis, 1 M aluminium nitrate was mixed
with 1 M HMT in 30 ml deionized water under magnetic
stirring for 15 min at room temperature. Subsequently,
obtained product kept for a centrifuge operating at 3000 rpm
for 30 min. After this procedure, solution was separated into
two gradations. At the bottom a white layer of Al2O3 QDs
observed and over it more transparent and dispersed layer
appeared. This centrifuged precipitate was collected through
cellulose nitrate filter paper. The filtrate was dried at room
temperature for overnight in vacuum chamber and then
sintered at 473 K for 36 h. After sintering the synthesised
material appears white coloured powder in visible light. The
reaction is shown in Eq. (1).
Al(NO3)2 þ C6H12N4-Al2O3 þ C6N6 þ 6H2O (1)
X-ray diffraction (XRD) patterns were recorded using a
Rigaku miniflex-II diffractometer with CuKα radiation in the

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.11.062
6110 K.R. Nemade, S.A. Waghuley / Ceramics International 40 (2014) 6109–6113

range 20–701. The morphology and grain size of the sample As the quantum confinment effect present in α-Al2O3 QDs,
was observed by using (transmission electron microscopy its radius was estimated by using the hyperbolic band model
along with selected area diffraction pattern) TEM-SADP (HBM). The QDs radius was estimated from 350 nm intense
(JEOL-1200ex). The ultraviolet–visible (UV–vis) spectrum absorption using Eq. 1 [14]
recorded on Perkin Elmer UV spectrophotometer in the range sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
300  450 nm in solution of Al2O3 QDs dispersed in double 2π 2 h2 Ebulk
distilled water. The Fourier transform infrared (FTIR) spec- R¼ ð2Þ
mn ðE 2nano  E2bulk Þ
trum was recorded on Shimadzu (Model-8201) spectrophot-
ometer. The fluorescence analysis was done on FL where Ebulk ¼ 2.6 eV is the bulk band gap of Al2O3 [16],
Spectrophotometer (Model: HITACHI, F-7000). The thermo- Enano ¼ 3.6 eV is the band gap of Al2O3 QDs, mn is the
gravimetric–differential thermal analysis (TG–DTA) was effective mass of electron in Al2O3 (mn ¼ 0.28m0) [17]. The
obtained with a Shimadzu DTG-60h thermal analyser under QDs radius was found to be 2.14 nm, hence particle size is
nitrogen atmosphere. 2R ¼ 4.28 nm.
This value of band gap shows Al2O3 QDs possesses
semiconducting behaviour. This could be due to the presence
3. Results and discussion of different sub-energy levels in the bandgap, which are related
to surface defects. This semiconducting behaviour can be
The XRD pattern of the final product is shown in Fig. 1. explained using the defect chemistry. The band gap is
α-Al2O3 has a trigonal structure with space group R3c and is controlled, fundamentaly, by the concentration of defects.
commonly described in terms of hexagonal Miller–Bravais Defects ionised to some extent, at room temprature, by thermal
indices with a¼ 4.76 Å and c ¼ 12.99 Å [10,11]. The diffrac-
tion peaks appears at various 2θ positions, exactly indexed to
the formation of this compound (PDF-01-081-1667). No other
peaks for impurities were detected. The average crystallite size
was calculated from diffraction peaks using the Debye–
Scherrer equation, which was found to be 4.2 nm [12].
The surface topography of Al2O3 QDs was examined
through TEM. Fig. 2 shows the TEM image of Al2O3 QDs.
The distribution of grains are of irregular shapes through all
the regions of image. The inset is the corresponding SAED
pattern of Al2O3 QDs. The diffraction planes were obtained
from XRD analysis, are consistent with the rings on the
diffraction pattern.
Fig. 3(a) shows UV visible absorption spectrum of α-Al2O3
QDs and it clearly shows an intense band-to-band absorption
in the ultra violet region. Band gap value was determined by
extrapolation of the linear portion of (αhν)1/2 curve versus the
photon energy (hν) as 3.6 eV as shown in Fig. 3(b). The
observation of blue shift in band gap shows the formation of
smaller sized α-Al2O3 QDs and the presence of strong Fig. 2. TEM image of as-synthesized α-Al2O3 QDs and the inset shows SADP
quantum confinement effect [13–15]. pattern.

8.0e+003
6.0e+003
4.0e+003
2.0e+003
0.0e+000
Intensity

10 20 30 40 50 60 70
100
alpha-Al2 O3, Al2 O3, 01-081-1667
80
60
40
20
0
10 20 30 40 50 60 70
2θ Position
Fig. 1. XRD of as-synthesised α-Al2O3 QDs.
 K.R. Nemade, S.A. Waghuley / Ceramics International 40 (2014) 6109–6113 6111

the donor defects (oxygen vacancies) create their energy level

80
below the conduction band, whereas the acceptor defects (Al
interstitials) create energy level above the valence band [19].
60 The Al interstitials/defects arise from the Frenkel reaction
whereas the oxygen vacancies/defects are from the Schottky
reaction [19].
%T

40 Fig. 5(a) reveals the FTIR spectrum of α-Al2O3 QDs. In

Fig. 2, there is transmission band entered at about 3250 cm  1,
20 characteristic of hydrogen bonded –O–H of the adsorbed
water. The band at 1108 cm  1 is corresponding to the phonon
lengthways stretching band of Al2O3 [20,21], while the band at
0 500–1000 cm  1 can be interpreted to the bending stretching
300 350 400 450 band of Al–O [22]. The transmission band at 1631 cm  1 is the
Wavelength (nm) characteristic of the bending stretching of the adsorbed H2O,
while the bands at 2358 and 2260 cm  1 are the characteristics
250 of the adsorbed CO2. The FTIR peaks of precursor molecules
that is HMT such as 2958, 2882, 1462, 1358, 1234, 1010, 816,
200 669 cm  1 do not appear notably [23].
The size tunable absorption and emission properties of QDs
150 are extremely valuable for quantum confinement analysis. Due
(αh )1/2

to this reason, QDs are said to be fluorescent nanocrystals [14–

100
50
0
2.5 3 3.5 4
Energy (eV)
Fig. 3. (a) UV–vis spectrum and (b) plot of (αhν)1/2 as a function of photon
energy of Al2O3 QDs dispersed in aqueous medium.
Fig. 4. Energy levels of donor defects (V0) and acceptor defects (VAl). As these
defects readily ionised at room temperature, therefore resultant band gap of
Al2O3 QDs at room temperature is 3.6 eV.
fluctuations and hence electrons may promoted into the
conduction band. In the metal oxide, vacant oxygen sites
played the role of defects. In neutral state they contain two
electrons one of which is readily ionised [18]. This electron is
easily promoted into conduction band even at room tempra-
ture. This is one of the possible reasons for the mearging of
insulating band gap of Al2O3 into semiconducting region. The
electronic energy levels of donor and acceptor defects are
shown in Fig. 4. The Kroger Vink notations are used to explain
this energy levels, where V ¼ vacancy, O ¼ oxygen,
Al ¼ Aluminium. The Al interstitials and oxygen vacancies
are known to be the predominant ionic defects. This shows that
24]. In the present work, QDs shows the emission of intense
blue luminescence under the irradiation by 254 nm at room
temperature. In order to calculate particle size, a fluorescence
measurement was made from 275 to 625 nm and displayed in
Fig. 5(b). The peak value of emission was observed at 383 nm,
which is assigned to the presence of defects. This value
demonstrates the concentration of defects responsible for
emission. This value is used for the manipulation of quantum
dots' size from effective mass approximation (EMA).
The optical band gap and particle size are correlated with
Eq. 2 [25].
 
h2 1 1 e2
Eg ¼ Ebulk þ 2 þ n  ð3Þ
8r me mhn 4πε0 εr γ e
where r is the radius of the particle, γe ¼ 20 nm is the Bohr
exciton radius of Al2O3 [26], Ebulk is the bulk band gap, εr is
the relative dielectric constant, ε0 is the dielectric constant of
air, mne ¼ 0.28m0 [17] effective mass of electron in Al2O3 QDs
and mnh ¼ 0.38m0 is effective mass of hole in Al2O3 QDs [27].
These calculations are resulted in the radius of QDs. It was
found that r¼ 1.92 nm. Thus, QD size is 2r ¼ 3.84 nm. The
HBM and EMA studied using UV–vis and fluorescence
spectroscopy respectively confirm the presence of quantum
confinement in Al2O3 QDs.
Fig. 5(c) offers a clear thermal analysis of the α-Al2O3 QDs.
Endothermic peaks at 397 and 437 K correspond to the
decomposition remaining contents of α-Al2O3 QDs, i.e.
Al(OH)3 and AlO(OH) respectively. The exothermic peak at
418 K is accompanied by a drastic mass loss in the temperature
range 340–500 K. The mass loss (1.97 mg) associated with
these exothermic and an endothermic process is about 87%.
This drastic mass loss attributed to the limited number of
possible slip systems in α-Al2O3 behaves in a brittle manner at
lower temperatures. Three dislocation slip systems have
commonly been identified for α-Al2O3 above its brittle–ductile
transition temperature of about 400 K. Deformation in α-Al2O3
6112 K.R. Nemade, S.A. Waghuley / Ceramics International 40 (2014) 6109–6113

2260
%T

2358

1631

1108
Wavenumber (cm-1)

300 10 16

250
0
Fluorescence (a.u.)

418 K
200 15

TGA (mg)
DTA (uV)
-10 1.93 mg
150 437 K

100
-20 14
50

0 -30
397 K
275 375 475 575 13
Wavelength (nm) 300 400 500 600 700 800
Temperature (K)

Fig. 5. (a) FTIR spectrum, (b) fluorescence spectrum, and (c) TG–DTA of α-Al2O3 QDs.

Table 1 semiconducting behaviour of α-Al2O3 QDs discussed effec-

Particle size determined from XRD, TEM, UV–vis and tively by using defects chemistry.
fluorescence analysis.

Characterization technique Particle size (nm) Acknowledgements

XRD 4.2
TEM 4 Authors are very much thankful to Head, Department of
UV–vis 4.28 Physics Sant Gadge Baba Amravati University, Amravati for
Fluorescence 3.84 providing necessary facilities.

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 Author's personal copy

Optical Materials 36 (2014) 712–716

Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Role of defects concentration on optical and carbon dioxide gas sensing

properties of Sb2O3/graphene composites
K.R. Nemade, S.A. Waghuley ⇑
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India

a r t i c l e i n f o a b s t r a c t

Article history: Sb2O3 quantum dots (QDs) anchored graphene composites were prepared by in situ chemical route, fol-
Received 4 September 2013 lowed by the subsequent annealing. The chemiresistors in the form of thin film fabricated using compos-
Received in revised form 15 November 2013 ites powder exhibit considerable response to carbon dioxide (CO2) gas. The resulting samples were
Accepted 21 November 2013
characterized by X-ray diffraction and electron microscopy for structural and morphological analysis.
Available online 8 December 2013
Ultraviolet–visible spectroscopy was performed to the quantum confinement effect in Sb2O3 quantum
dots. Fluorescence spectroscopy was employed to study the dependence of gas sensing response on opti-
Keywords:
cal properties and defects density. The chemiresistors shows almost linear response up to 50 ppm CO2.
Graphene
Optical properties
Among those chemiresistors, 1.6 wt% graphene chemiresistor shows the best response. The response
Gas sensing and recovery times to 50 ppm CO2 for 1.6 wt% graphene chemiresistor at room temperature are 16 and
22 s, respectively.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction graphene used in this work was prepared by a previously reported

Carbon dioxide (CO2) is an essential part of earth atmosphere, it
continuously being exchanged between the atmosphere, sea and
soil surface. Ocean absorbing CO2 from the atmosphere, this result
in ocean acidification and subsequently cause to climate change
[1]. Moreover, CO2 is green house gas. Graphene sheets decorated
with metal oxide quantum dots might result in the good gas sens-
ing properties [2–4]. Also, graphene surface anchored metal oxide
nanoparticles can provide greater usefulness in gas adsorption and
sensing processes [5–7].
With this mind, we developed efficient chemiresistors for an
effective monitoring of CO2. In this regards, present work comprises
a bold attempt to develop a chemiresistor based upon unattempted
sensing material graphene/Sb2O3 composite. During literature sur-
vey, there are few reports related to the graphene/Sb2O3 composite
and it is for the first time, we explored graphene/Sb2O3quantum
dots composites as a CO2 sensing material. Our experiment clearly
focused onto reduce the operation cost by operating chemiresistors
at low temperatures with effective sensing of test gas. Some inter-
esting accomplishments are also reported.
2. Experimental
In this work, we adopted a convenient in situ method to prepare
Sb2O3 quantum dots (QDs) anchored graphene composites. The
⇑ Corresponding author. Tel.: +91 9423124882; fax: +91 07212662135.
E-mail address: sandeepwaghuley@sgbau.ac.in (S.A. Waghuley).
method [8]. The preparation of Sb2O3 QDs anchored graphene com-
posites could be divided into two steps: First, in two separate beak-
ers, SbCl5 and NaOH dissolved in deionized water of resistivity not
less than 18.2 MX/cm with molar ratio 1:5. The solution was put in
an ultrasonic bath for 8 h. Second, graphene was mixed in solution
placed in oven to dry at 100 °C. The dried products were sintered in
a quartz tube at 200 °C for 8 h under a nitrogen atmosphere. In this
way, four samples were prepared by varying wt% of graphene from
0.4 to 1.6 wt%.
The X-ray diffraction patterns were acquired on Rigaku (Mini-
flex (II)) diffractometer with Cu Ka radiation in the range from
10° to 70°. The morphology of sample was analysed through FE-
SEM and TEM by using JEOL JSM-7500F and (JEOL-1200ex), respec-
tively. Raman spectroscopy (RFS 27; Bruker; Raman spectrometer)
was employed to illustrate the interaction between pristine graph-
ene and Sb2O3 QDs using a Nd:YAG laser excitation source of wave-
length 514 nm. The UV–vis analysis performed on Perkin Elmer UV
spectrophotometer in the range 205–705 nm. The fluorescence
analysis was performed on FL Spectrophotometer (Model:
HITACHI, F-7000).
The chemiresistors in the form of thin film were prepared by
screen-printing technique on glass substrate of size
25 mm  25 mm by using temporary binder, composed of butyl
carbitol and ethyl cellulose. For sensing measurements, ohmic con-
tact was achieved by using highly conducting silver paint depos-
ited on adjacent sides of the chemiresistor and heating the
chemiresistors at 100 °C for 30 min in argon atmosphere. The aver-
age thickness of chemiresistors was about 6 lm, measured by
Digimatic Outside Micrometer (Series-293, Japan). In order to

0925-3467/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.optmat.2013.11.024
 Author's personal copy

K.R. Nemade, S.A. Waghuley / Optical Materials 36 (2014) 712–716 713

investigate gas sensing properties, the gas sensor unit was spe- individuals’ peaks of Sb2O3 QDs suppressed under the characteris-
cially designed. Dry air (H2O lower than 2 ppm) was used as carrier tics peaks of graphene. This statement is well supported by se-
gas. The sensing response is defined as given below [9]: lected area electron diffraction analysis. The average crystallite
 size for composites was estimated by using Scherrer’s formula,
DR Rg  Ra j
S¼ ¼ ð1Þ
Ra Ra
where Ra and Rg are the resistance of chemiresistor in air and gas,
respectively.
3. Results and discussion
Fig. 1 shows the typical X-ray diffraction (XRD) pattern of the
graphene and as-prepared Sb2O3/graphene composite, clearly sug-
gestive of the formation of Sb2O3 quantum dots with very small
size reflects from highly broadened diffraction peaks. These results
are also confirmed by FE-SEM and TEM as described later. No sharp
peaks corresponding to Sb2O3 QDs are observed in the powder pat-
tern, which might attribute to the appearance of broad character-
istics peaks of graphene that is (0 0 2) and (1 0 0) [10]. Hence,
1.6 wt.%Graphene
1.2 wt.%Graphene
Intensity (Arb. Unit)
which ranges between 4 and 8 nm.
The morphology and structural features of as-synthesized
1.6 wt% graphene/Sb2O3 QDs composite were elucidated by
FE-SEM and TEM, as it is optimized sample discussed later.
Fig. 2(a) shows the FE-SEM micrograph of 1.6 wt% graphene/
Sb2O3 QDs composite, indicates that Sb2O3 QDs are entirely
anchored on graphene sheets. The small amount of agglomeration
is present in sample. Fig. 2(b) shows the TEM image, reflects that
large amount of Sb2O3 QDs were distributed on the graphene
sheets.
As XRD analysis unable to specify clearly presence of Sb2O3 QDs,
selected area electron diffraction (SAED) analysis was performed to
support the presence of Sb2O3 QDs. The SAED image is presented in
inset of Fig. 2(b). The several broad diffracting rings could be iden-
tified in the diffraction pattern. The rings observed in diffraction
pattern attributed to presence of Sb2O3 QDs, because pristine
graphene shows only hexagonal symmetry with clear six spot pat-
terns [11]. This stipulates that white platelets observed in FE-SEM
image are Sb2O3 QDs.
Fig. 3 presents UV–vis spectrum of pristine graphene and
graphene/Sb2O3 QDs composites. The UV–vis spectrum of graph-
ene shows sharp absorption at 268 nm, whereas spectrum of com-
posites exhibits absorption around the 206–210 nm. The blue shift
is observed in case of composites. This shifting towards the lower
wavelength attributed to the synergetic effect of graphene and

Sb2O3 QDs. This confirmed the existence of strong quantum con-

finement, which is fundamental characteristic of quantum dots
[12].
Fig. 4 displays fluorescence spectrum of as-obtained composites
0.8 wt.%Graphene
and pristine graphene, recorded in the range 315–715 nm under
excitation. The fluorescence spectrum shows that composite sam-
ples possess broad emission in ultraviolet region, whereas in visi-
ble region shows the nearly flat emission.
0.4 wt.%Graphene
To establish the interaction between pristine graphene and
Sb2O3 QDs Raman spectroscopy was performed. Fig. 5 depicts the
(002)
Raman spectra of graphene and 1.6 wt% graphene/Sb2O3 QDs com-
Graphene posite recorded at room temperature. The intensities of almost all
bands shown in the Raman spectrum were appreciably affected.
(100) Along with these bands, the D band is strappingly affected. This
may be due to Sb2O3 QDs affect the one-phonon lattice vibration
10 20 30 40 50 60 process. Furthermore, this demonstrate that Sb2O3 QDs act as ac-
2θ Position tive sensing sites by damaging to the graphene sheets, which
may generates vacancies or dangling bonds on graphene surface.
Fig. 1. XRD patterns of graphene and graphene/Sb2O3 QDs composites.
The X-ray photoelectron spectroscopy (XPS) measurements could

(a) (b)
Sb2O3 QDs

Graphene

10 nm 10 nm

Fig. 2. (a) FE-SEM and (b) TEM image of 1.6 wt% graphene/Sb2O3 QDs composite from the edge-side view. Inset shows SAED image.
 Author's personal copy

714 K.R. Nemade, S.A. Waghuley / Optical Materials 36 (2014) 712–716

80 0.7
Graphene Carbon Dioxide
0.4 wt.% graphene 0.6
70 LPG

Sensing Response
0.8 wt.% graphene
60 1.2 wt.% graphene 0.5
1.6 wt.% graphene
% Absorption

50 0.4
40 0.3
30 0.2
20 0.1
10
0
0 0.4 wt.% 0.8 wt.% 1.2 wt.% 1.6 wt.%
Wt.% of graphene
200 250 300 350 400
Wavelength (nm) Fig. 6. Comparative gas sensing responses of chemiresistors towards CO2 and LPG
for 50 ppm at room temperature.
Fig. 3. UV–vis spectrum of graphene and graphene/Sb2O3 QDs composites.

selective towards the CO2 as compare to liquid petroleum gas

(LPG). It is directly notable that 1.6 wt% graphene/Sb2O3 QDs com-
80 posites chemiresistor is highly selective than other chemiresistors.
IUV Graphene
As the composites samples more selective towards the CO2,
70 0.4 wt.% Graphene
sensing capability is tested by recording chemiresistor resistance
Fluorescence Intensity

60 0.8 wt.% Graphene change when the chemiresistor is exposed to CO2 with different
1.2 wt.% Graphene concentrations. Fig. 7 shows the sensing response to various CO2
50 1.6 wt.% Graphene concentrations at room temperature. The sensing response of the
40 chemiresistors to CO2 is roughly linear, as shown Fig. 7 and it is
IDL also scrutinized that sensing response increases with an increase
30 in wt% of graphene.
Fig. 8 shows the operating temperature dependence of the sens-
20
ing response to 30 ppm CO2. In the measured temperature range,
10 the responses to 30 ppm CO2 increases at first, undergoes a maxi-
mum, and finally drops. The response value start to drop from par-
0 ticular temperature, this may be due to desorption of atmospheric
315 415 515 615
oxygen ions from sensing surface due to thermal vibrations [14].
Wavelength (nm) The highest value of the sensing response was found at 423 K.
Fig. 4. Fluorescence spectrum of graphene and graphene/Sb2O3 QDs composites.
Thus, for CO2 gas detection, the operating temperature of the che-
miresistor can be 423 K. This value of operating temperature
clearly shows that prepared chemiresistor was operable at low
temperature. As the chemiresistor operable at low temperature,
1000
gas sensing set up achieve this temperature value by using low
Graphene electricity. This shows that operation of chemiresistor at low tem-
800 1.6 wt.% Graphene perature is results in low power consumption. This significantly re-
Raman Intensity

duced the operation cost.

600

400 0.25
Graphene
200 0.4 wt.% Graphene
0.2
0.8 wt.% Graphene
Sensing Response

0
1000 1500 2000 2500 3000 1.2 wt.% Graphene
0.15 1.6 wt.% Graphene
Raman Shift (cm-1)
Fig. 5. Raman spectrum of graphene and 1.6 wt% graphene/Sb2O3 QDs composites.
0.1
also provide the direct evidence of the interaction between graph-
ene and Sb2O3 QDs. But in the presence of high density of vacancies
0.05
and dangling bonds, XPS analysis suffered from adsorbed atmo-
spheric oxygen. As adsorbed atmospheric oxygen have high ten-
dency to adsorb on high vacancies materials. At the same time,
0
Raman spectroscopy effectively shows the interaction between
0 10 20 30 40 50
graphene and Sb2O3 in the presence of adsorbed atmospheric oxy-
gen through change in D band [13]. Carbon Dioxide Concentration (ppm)
Fig. 6 shows the selectivity response of as-fabricated chemire- Fig. 7. The variation of sensing response of chemiresistors with the concentration
sistors towards CO2 and LPG for 50 ppm. The composites are highly of CO2 at room temperature.
 Author's personal copy

K.R. Nemade, S.A. Waghuley / Optical Materials 36 (2014) 712–716 715

0.6 As the sensing response depends upon defects density, fluores-

cence measurement becomes crucial. The emission spectrum of
0.55 composites was used to estimate defects density using intensities
ratio of the ultraviolet (IUV) to visible deep levels (IDL) [16]. The
Sensing Response

0.5 oxygen vacancies are the most probable point defects, which in-
crease the probability of adsorption of oxygen on the sensing sur-
0.45 face [17]. The variation of IUV/IDL ratio and CO2 sensing response
with the wt% of graphene is shown in Fig. 9(b). From the plots, it
is scrutinized that sensing response increases with defects density
0.4
that is (IUV/IDL) ratio linearly as a function of wt% graphene. As wt%
of graphene increases, more and more graphene sheets comes in
0.35
contact with Sb2O3 QDs and damaged. This may be due to Sb2O3
QDs act as active sensing sites by damaging to the graphene sheets,
0.3
which may generates vacancies or dangling bonds on graphene
323 373 423 473
surface and subsequently, enhance defects density [18]. This result
Temperature (K) is consistent well with the observation made by previous reports
[17,19]. Also, this result well supported by Raman spectroscopy.
Fig. 8. Chemiresistor response as a function of operating temperature to 30 ppm
CO2. Therefore, 1.6 wt% graphene/Sb2O3 QDs shows high selectivity
and sensing response towards the CO2.
Fig. 10 shows stability response of the 1.6 wt% graphene/Sb2O3
In order to explain primary mechanism for CO2 detection, we chemiresistor at room temperature to 50 ppm concentration of
suggest that the oxygen adsorbed on the surface of samples may CO2. In order to check the stability of chemiresistor, its response
be involved in the sensing process of CO2. The interaction between was measured for 30 days, at an interval of 5 days. The chemiresis-
adsorbed atmospheric oxygen and sensing surface are shown be- tor has almost constant sensing response. This indicates that sta-
low [15]. bility of chemiresistor is good against CO2.

O2 ðgasÞ ! O2 ðadsÞ

O2 ðadsÞ þ e ! O2 ðadsÞ 0.25

O2 ðadsÞ þ e ! 2O ðadsÞ 0.2

Sensing Response

As gas sensing response depends upon defects density through

0.15
the oxygen vacancies, which can act as adsorption sites for atmo-
spheric oxygen. Therefore, more number of defects adsorbed more
atmospheric oxygen. CO2 may initially adsorb on pre-adsorbed 0.1
oxygen and form surface carbonate. This surface carbonates as
shown in Fig. 9(a) inject certain electrons from samples, leading 0.05
an increase in resistance. This shows that formation of surface car-
bonates was responsible for the CO2 detection through resistance
change. 0
0 10 20 30
Time (Days)
Fig. 10. Stability characteristics of 1.6 wt% graphene/Sb2O3 QDs chemiresistor to
50 ppm CO2.

0.25
Gas in Gas out

0.2
Sensing Response

0.15

0.1

0.05

0
0 10 20 30
Time (s)
Fig. 9. (a) Plausible sensing mechanism for CO2 detection. (b) The variation of Fig. 11. Transient response of 1.6 wt% graphene/Sb2O3 QDs chemiresistor to
defects density (IUV/IDL) ratio and CO2 sensing response with the wt% of graphene. 50 ppm CO2.
 Author's personal copy

716 K.R. Nemade, S.A. Waghuley / Optical Materials 36 (2014) 712–716

The transient response characteristic of 1.6 wt% graphene/Sb2O3 University, Amravati for awarding Late M N Kale scholarship for
QDs composite chemiresistor to 50 ppm CO2 was studied at room the Ph.D. work.
temperature and displayed in Fig. 11. In this measurement, gas
introduces in the chamber and resistance of chemiresistor was References
measured in air and in presence of gas. The chemiresistor shows
fast response time towards the CO2 of the order 16 s. For measur- [1] C.E. Booth, D.G. McDonald, P.J. Walsh, Mar. Biol. Lett. 5 (1984) 347–358.
[2] K.R. Nemade, S.A. Waghuley, Solid State Sci. 22 (2013) 27–32.
ing the recovery time, chemiresistor was uncovered to air. The che- [3] K.R. Nemade, S.A. Waghuley, AIP Conf. Proc. 1536 (2013) 1258–1259.
miresistor achieve fast recovery in 22 s. [4] K.R. Nemade, S.A. Waghuley, Int. J. Mod. Phys.: Conf. Ser. 22 (2013) 380–384.
[5] R. Pasricha, S. Gupta, A.K. Srivastava, Small 5 (2009) 2253–2259.
[6] J.B. Liu, S.H. Fu, B. Yuan, Y.L. Li, Z.X. Deng, J. Am. Chem. Soc. 7279 (2010) 132–
4. Conclusions 153.
[7] J. Li, C.Y. Liu, Eur. J. Inorg. Chem. 8 (2010) 1244–1248.
[8] K.R. Nemade, S.A. Waghuley, J. Elec. Mater. 42 (2013) 2857–2866.
In summary, the present work shows that CO2 sensing response
[9] B.C. Yadav, S. Singh, A. Yadav, Appl. Surf. Sci. 257 (2011) 1960–1966.
increases with an increase in wt% of graphene. The possible sensing [10] Y. Wu, B. Wang, Y. Ma, Y. Huang, N. Li, F. Zhang, Y. Chen, Nano. Res. 3 (2010)
mechanism for CO2 detection is discussed by using defect chemis- 661–669.
try. The present study shows that sensing response is defect den- [11] N.K. Memon, S.D. Tse, J.F. Al-Sharab, H. Yamaguchi, A.B. Goncalves, B.H. Kear, Y.
Jaluria, E.Y. Andrei, M. Chhowalla, Carbon 49 (2011) 5064–5070.
sity based phenomenon, which effectively analyzed by [12] K.R. Nemade, S.A. Waghuley, Res. Phys. 3 (2013) 52–54.
fluorescence spectroscopy. [13] L. Meng, S. Park, Bull. Korean Chem. Soc. 33 (2012) 209–214.
[14] K.R. Nemade, S.A. Waghuley, J Chin. Adv. Mater. Soc. 1 (2013) 219–228.
[15] K. Fan, H. Qin, L. Wang, L. Ju, J. Hu, Sens. Actuators, B 177 (2013) 265–269.
Acknowledgements [16] O. Lupan, V.V. Ursaki, G. Chai, L. Chow, G.A. Emelchenko, I.M. Tiginyanu, A.N.
Gruzintsev, A.N. Redkin, Sens. Actuators, B 144 (2010) 56–66.
The authors of present work are very much thankful to Head, [17] S. Pati, S.B. Majumder, P. Banerji, J. Alloys Comp. 541 (2012) 376–379.
[18] Z. Ni, Y. Wang, T. Yu, Z. Shen, Nano. Res. 1 (2008) 273–291.
Department of Physics Sant Gadge Baba Amravati University, [19] M.W. Ahn, K.S. Park, J.H. Heo, J.G. Park, D.W. Kim, K.J. Choi, J.H. Lee, S.H. Hong,
Amravati for providing necessary facilities. One of the authors, Appl. Phys. Lett. 93 (2008) 263103–263106.
K.R. Nemade is very much thankful to Sant Gadge Baba Amravati
 Optical investigation of polyphenylene sulfide composite
A. S. Rahate, K. R. Nemade, and S. A. Waghuley

Citation: AIP Conf. Proc. 1536, 809 (2013); doi: 10.1063/1.4810474

View online: http://dx.doi.org/10.1063/1.4810474
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 Optical Investigation Of Polyphenylene Sulfide Composite
A S Rahate, K R NemadeI and S A WaghuleyI *

Department of Applied Physics, Babashaeb Naik College of Engineering, Pusad 445 215, India
I
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India.
*Corresponding author email: sandeepwaghuley@sgbau.ac.in

Abstract. The synthesis of Polyphenylene sul 

 

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AIP Conf. Proc. 1536, 809-810 (2013); doi: 10.1063/1.4810474
© 2013 AIP Publishing LLC 978-0-7354-1160-9/$30.00

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 LPG sensing application of graphene/CeO2 quantum dots composite
K. R. Nemade and S. A. Waghuley

Citation: AIP Conf. Proc. 1536, 1258 (2013); doi: 10.1063/1.4810698

View online: http://dx.doi.org/10.1063/1.4810698
View Table of Contents: http://proceedings.aip.org/dbt/dbt.jsp?KEY=APCPCS&Volume=1536&Issue=1
Published by the American Institute of Physics.

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 LPG Sensing Application Of Graphene/CeO2 Quantum Dots
Composite
K.R.Nemade and S.A.Waghuley*

Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India.
*Email: sandeepwaghuley@sgbau.ac.in

Abstract. Graphene/CeO2 quantum dots (QDs) composite was investigated towards the liquid petroleum gas (LPG) at
room temperature. Graphene was synthesized by electrochemical exfoliation of graphite. The composites of graphene/
CeO2 QDs was prepared by mixing 20 wt.% of graphene in constant 1g of CeO2. The chemiresistor of 20 wt.%
composite possesses optimum value of sensing response and excellent stability.
Keywords: Graphene, CeO2, Quantum dots.
PACS: 81.07.Ta Quantum dots

INTRODUCTION centrifuge operating at 3000 rpm for 30 min. This

Solid-state semiconductor sensors have gained
large attraction due to the serious disquiet of global
warming [1] and the detection of inammable gases
[2]. The sensing principle of semiconducting metal
oxide lms is based on the change in the electron
density in the conduction band of a semiconductor
oxide lm when specic gases interact with its surface.
In this paper, the synthesis of graphene/CeO2 QDs
composite by simple route has been reported. Their
gas sensing properties to LPG was investigated.
EXPERIMENTAL
Graphene was synthesized by the electrochemical
exfoliation of graphite using silver as a cathode. The
graphite flake and silver electrode were inserted into
the ionic solution with separation of 5 cm. The ionic
solution was prepared by taking 4.8 g of sulphuric acid
diluted in 100 ml of double distilled water [3].
Exfoliation process was carried out by DC bias
arrangement (10V) at room temperature. An exfoliated
graphene was collected through cellulose nitrate filter
paper and washed with double distilled water. The
obtained sample was dried at 100 qC for 2 h.
The CeO2 QDs were synthesized using cerous
nitrate and hexamethylenetetramine (HMT) through
chemical route.
centrifuged precipitate was collected through cellulose
nitrate filter paper. The filtrate dried at room
temperature for over night in vacuum chamber and
then sintered at 100°C for 3 h. The graphene/CeO2
QDs composite were prepared by mixing graphene in
constant 1 gm CeO2 QDs in 30 ml acetone as organic
media. Then, chemiresistors were prepared by screen-
printing. The electrical resistance was measured by
using a voltage drop method adopted by Waghuley et
al [4].
RESULTS AND DISCUSSION
Fig. 1 (a) and (b) depicts the XRD patterns of
graphene and CeO2 QDs, indicates the formation of
graphene and CeO2. The average crystallite size was
determined using Debye-Scherrer equation, which was
found to be 5.6 nm for graphene and 9.6 nm for CeO2
QDs.

Ce(NO3)2+C6H12N4oCeO2+C6N6+6H2O

The 1M cerous nitrate was mixed with 1M HMT in FIGURE 1. XRD patterns of (a) graphene and (b) CeO2
QDs.
30 ml double distilled water. The solution was
thoroughly mixed by magnetic stirrer for 2 h at room
temperature. Subsequently, the product kept for a
Proceeding of International Conference on Recent Trends in Applied Physics and Material Science
AIP Conf. Proc. 1536, 1258-1259 (2013); doi: 10.1063/1.4810698
© 2013 AIP Publishing LLC 978-0-7354-1160-9/$30.00

1258

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 Fig. 2 shows the UV-VIS spectrum of CeO2 QDs. In order to check the stability of chemiresistors, its
The intense absorption is observed at 352 nm.This response towards 50 ppm of LPG at room temperature
confirms the presence of quantum confinment. were measured for 30 days at an interval of 5 days
after the rst measurement. The stability response
shows in Fig. 5. The chemiresistors have nearly
constant response to LPG indicating the good stability.

FIGURE 2. UV-VIS spectrum of CeO2 QDs.

The TEM images of graphene and CeO2 QDs are

shown in Fig. 3 (a) and (b). The TEM shows the
surface area is not perfectly leveled and surface giving FIGURE 5. Stability response of graphene, CeO2 QDs and
different levels of trasperency in case of graphene. The 20 wt.% composite.
TEM of CeO2 QDs shows the presence of irregular
shape particle having average crystallite size 9 nm.
CONCLUSIONS
The chemiresistor based on graphene/CeO2 QDs
composites (20 wt.%) exhibits the highest sensing
response for LPG at room temperature. The
chemiresistor of 20 wt.% composite exhibits attractive
performance at room temparature with optimum value
of sensing response and excellent stability.

FIGURE 3. TEM image of (a) graphene and (b) CeO2 QDs. ACKNOWLEDGMENTS
Fig. 4 depicts the sensing responses of Authors are very much thankful to Head,
chemiresistors to LPG at room temperature. It was Department of Physics Sant Gadge Baba Amravati
observed that the resistance of chemiresistor decreases University, Amravati for providing necessary
in the presence of LPG. This shows the reducing facilities.
character of LPG. The optimum value of sensing
responses at room temperature was found to be 1.3 for
20 wt% of chemiresistor. It was varying nearly linear
REFERENCES
up to 100 ppm.
1. Z. Seeley, Y.J. Choi and S. Bose, Sens. Actuators B 140
98–103 (2009).
2. A. Salehi, A. Nikfarjam and D.J. Kalantari, Sens.
Actuators B 113 419–427 (2006).
3. C. Su, A. Lu, Y. Xu, F. Chen, A. Khlobystov and L. Li,
ACS nano 5 2332-2359 (2011).
4. S.A. Waghuley, S.M. Yenorkar, S.S. Yawale, S.P.
Yawale, Sens. Actuators B 128 366-373 (2008).

FIGURE 4. Gas sensing response of graphene, CeO2 QDs

and 20 wt.% composite.

1259

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 Copyright © 2013 by American Scientific Publishers Advanced Science,
All rights reserved. Engineering and Medicine
Printed in the United States of America Vol. 5, pp. 1–3, 2013
(www.aspbs.com/asem)

Synthesis and Characterization of

Bismuth Oxide Quantum Dots
K. R. Nemade and S. A. Waghuley∗
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444602, India

Present study was designed to scrutinize the synthesis of semiconducting metal oxide to act as a material
capable of supporting to contemporary application. The synthesis of bismuth oxide (Bi2 O3
quantum dots (QDs)
was done through chemical rout. The Bi2 O3 QDs was synthesized by hexamethylteramine (HMT) as nitrate
remover. The ratio of HMT and bismuth nitrate was 1:1 M. The characterization of QDs was done thorough
UV-VIS analysis, transmission electron microscophy (TEM) and selected area diffraction pattern (SADP). The
particle size was estimated 9.44 nm from UV-VIS analysis. The conformation was done through TEM. The
structural analysis was done through SADP.

KEYWORDS: Bismuth Oxide Quantum Dots, UV-VIS Spectroscopy, SADP.

1. INTRODUCTION
Bismuth oxide has been extensively studied due to
its potential application such as terahertz devices,1 gas
sensors,2 Photovoltaic Devices etc.3 The Bi2 O3 is also used
as an additive in paints. From the gas sensing point of
scrutiny, 0D materials are expected to have significantly
enhanced performance due to their ultrahigh surface to vol-
ume ratios and a Debye length comparable to their dimen-
sions, which makes their electrical properties extremely
sensitive to surface-adsorbed species, as recent work has
shown with Fe2 O3 and SnO2 nanowires. Therefore, great
effort has been devoted to synthesize Bi2 O3 nanowires
over the last years. Several groups reported similar self-
sacrificing template routes to prepare Bi2 O3 nanowires
and Bi–Bi2 O3 core–shell nanowires by high-temperature
oxidation.4
Lee et al.5 demonstrate the synthesis of Yttria-doped
bismuth oxide (YBO) powders by ammonium carbonate
coprecipitation for the preparation of electrolytes of an
intermediate temperature solid oxide fuel cell. The start-
ing salts were yttrium and bismuth nitrate. The results
showed that the ammonium carbonate co-precipitation pro-
cess could be used as the cost-efficient method of produc-
ing YBO electrolytes for an intermediate temperature solid
oxide fuel cell.
Dubey et al.6 studied the particle size dependent optical
band gap of Bi2 O3 QDs. In their research highest value
∗
Author to whom correspondence should be addressed.
Email: sandeepwaghuley@sgbau.ac.in
Received: 27 August 2012
Accepted: 26 October 2012
ARTICLE
of optical band gap observed for smallest particle. Gondal
et al.7 reported the synthesis of bismuth oxide (Bi2 O3 )
nanostructured particles by pulsed laser ablation (PLA)
technique by irradiating solid bismuth target in 3% H2 O2
solution using 355 nm laser radiations generated by third
harmonic Nd:YAG laser.
The present work demonstrates the single step synthe-
sis of Bi2 O3 QDs through chemical route. The charac-
terization of QDs was done thorough UV-VIS analysis,
transmission electron microscopy (TEM) and selected area
diffraction pattern (SADP).
2. EXPERIMENTAL DETAILS
The AR grade (SD fine, India) chemicals were used in this
investigation. The bismuth nitrate and hexamethylenete-
tramine (HMT) used for the preparation of Bi2 O3 QDs.
The 1 M-bismuth nitrate mixed with (1 M) HMT dissolved
in 30 ml water. The mixture stir with magnetic stirrer for
15 min. The prepared sample were first dried at room tem-
perature for over night and sintered at 100  C for 3 h.
Optical absorption studies were carried out using UV-VIS
spectrometer (Perkin Elmer). The TEM and SADP analy-
sis was done through JEOL 1200ex.
3. RESULTS AND DISCUSSION
The UV-VIS analysis was carried out to know the optical
properties of Bi2 O3 QDs. The particle size was estimated
roughly from optical band gap value using hyperbolic band
model.8 The relation between optical band and radius is
shown in Eq. (1). The UV-VIS spectra of samples were

Adv. Sci. Eng. Med. 2013, Vol. 5, No. xx 2164-6627/2013/5/001/003 doi:10.1166/asem.2013.1309 1

 Synthesis and Characterization of Bismuth Oxide Quantum Dots
Fig. 1. UV-VIS spectra of Bi2 O3 QDs.
displayed in Figure 1. This analysis provides optical infor-
mation of synthesized materials. The optical band gap
determined for Bi2 O3 QDs from intensed absorption at
ARTICLE
∼ 260 nm found to be 3.44 eV.

Imaging a small dot through electron microscopy tech-
2 2 h2 Ebulk
R= (1)
m Enano
∗ 2 − Ebulk
2


where, R is quantum dot radius (2R is the diameter and
hence the average particle size) Ebulk is bulk band gap
(2.85 eV),6 Enano is band gap of nanomaterial (3.44 eV),
m∗ is effective mass of electron (m∗ = 2915 × 10−31 Kg
for Bi2 O3 QDs). The average particle size was found to be
9.44 nm.
The TEM images of Bi2 O3 QDs are provided in
Figure 2. The small amount of agglomerations is observed
in the micrographs. The average crystallite size observed
from TEM analysis was found to be ∼ 9 nm. This value
agrees with UV-VIS analysis of Bi2 O3 QDs through hyper-
bolic band model. The divergence in particle size from
both analysis may be due to the limitation of hyperbolic
band model i.e., particles strictly spherical.
Fig. 2. TEM image of Bi2 O3 QDs.
2 Adv. Sci. Eng. Med., 5, 1–3, 2013
Nemade and Waghuley
Fig. 3. SADP image of Bi2 O3 QDs.
The SADP of Bi2 O3 QDs displayed in Figure 3. This
dispersed and nearly spheroid with irregular shape. The
rings on the diffraction pattern depicted a principal planes
in Bi2 O3 QDs (020), (121), (031), (231), (300).
niques is not enough to say it is in quantum dots state.9
The optical absorption is a technique that allows one to
directly probe the band gap of QDs. The band gap edge
of a material should be blue shifted if the material is con-
fined. This blue-shifted spectrum confirmed the formation
of QDs. In our case, the intense absorption observed at
∼ 260 nm.
4. CONCLUSIONS
The synthesis of Bi2 O3 QDs through chemical route is a
simple and cost effective technique. The conformation of
QDs was done through TEM and UV-VIS analysis. The
partical size (9.44 nm) estimated from UV-VIS analysis is
very well agree with the TEM analysis. The divergence
in particle size from both analysis may be due to the
limitation of hyperbolic band model i.e., particles strictly
spherical. The strong confinement in Bi2 O3 QDs is also
confirmed from UV-VIS analysis. The principal planes in
Bi2 O3 QDs are observed to be (020), (121), (031), (231),
(300).
Acknowledgments: Authors are very much thankful to
Head, Department of Physics Sant Gadge Baba Amravati
University, Amravati for providing necessary facilities.
References and Notes
1. B. Arash and Q. Wang, Comput. Mater. Sci. 60, 245 (2012).
2. R. G. Dubey, K. R. Nemade, and S. A. Waghuley, Proc. Nat. Conf.
Laser and Advanced Materials (2012), p. 40.
3. Z. Liu and F. Yan, J. Am. Cer. Soc. 95, 1944 (2012).
Nemade and Waghuley Synthesis and Characterization of Bismuth Oxide Quantum Dots

4. P. A. Pawar, K. R. Nemade, and S. A. Waghuley, Proc. Nat. Conf.
Laser and Advanced Materials (2012), p. 160.
5. J. G. Lee, S. H. Kim, and H. H. Yoon, J. Nanosci. Nanotechnol.
11, 820 (2011).
6. R. G. Dubey, K. R. Nemade, and S. A. Waghuley, Sci. Revs. Chem.
Commun. 2, 436 (2012).
7. M. A. Gondal1, T. A. Saleh, and Q. Drmosh, Sci. Adv. Mater. 4, 507
(2012).
8. S. S. Nath, M. Choudhury, G. Gope, and R. K. Nath, J. Sens. Technol.
1, 86 (2011).
9. T. J. Bukowski, T. M. Neidt, R. Ochoa, and J. H. Simmons, J. Non-
Cryst. Solids 274, 87 (2000).

ARTICLE

Adv. Sci. Eng. Med., 5, 1–3, 2013 3

 International Conference on Ceramics, Bikaner, India
International Journal of Modern Physics: Conference Series
Vol. 22 (2013) 380–384
 World Scientific Publishing Company
DOI: 10.1142/S2010194513010404

CARBON DIOXIDE GAS SENSING APPLICATION OF GRAPHENE/Y2O3

QUANTUM DOTS COMPOSITE
Int. J. Mod. Phys. Conf. Ser. 2013.22:380-384. Downloaded from www.worldscientific.com

K. R. NEMADE
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India.
krnemade@gmail.com

S. A. WAGHULEY
by 14.139.121.194 on 05/27/13. For personal use only.

Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India.
sandeepwaghuley@sgbau.ac.in

Graphene/Y2O3 quantum dots (QDs) composite was investigated towards the carbon dioxide
(CO2) gas at room temperature. Graphene synthesized by electrochemical exfoliation of graphite.
The composite prepared by mixing 20-wt% graphene into the 1 g Y2O3 in organic medium
(acetone). The chemiresistor of composite prepared by screen-printing on glass substrate. The
optimum value of sensing response (1.08) was showed by 20-wt% graphene/Y2O3 QDs composite.
The excellent stability with optimum sensing response evidenced for the composite. The gas
sensing mechanism discussed on the basis of electron transfer reaction.

Keywords: Graphene, Y2O3, quantum dots, CO2.

1. Introduction
Graphene incorporated composites materials have emerged as a new class of materials
with interesting electron-transport behavior and a material with strong potential in
technological applications. Their ease of synthesis together with their chemically tunable
properties makes them especially useful in electronic, optoelectronic, and
electromechanical devices [1]. Graphene is a promising candidate as gas sensing
materials due to its functional morphology [2]. Cao et al [3] reported a cataluminescence
sensor using Y2O3 nanoparticles as the sensing materials proposed for the determination
of ethyl acetate. This ethyl acetate sensor showed high sensitivity and specificity at the
optimal temperature of 264°C. The CO2 is one of the most common gases evolved in the
combustion responsible for increasing global warming. It is chemically stable oxidising
gas. Therefore, strong sensing material required for detection of CO2 concentrations [4].
In the present investigation, 20 wt% of graphene/Y2O3 nanocomposite is investigated
for CO2 gas sensing. The materials are analyzed by ultraviolet-visible (UV-VIS) and
transmission electron microscopy (TEM) analysis. The gas sensing response and stability
of composite are studied at room temperature.

380
 Carbon Dioxide Gas Sensing Application 381

2. Experimental
Graphene was synthesized by the electrochemical exfoliation of graphite. The graphite
flake was used as an anode and source of graphene. The silver electrode was used as a
cathode. The graphite flake and silver electrode were inserted into the ionic solution with
separation of 5 cm. AR-grade chemicals were used in this investigation for the
preparation of ionic solution. The ionic solution was prepared by taking 4.8 g of sulphuric
acid diluted in 100 ml [5]. Exfoliation process was carried out by DC bias arrangement
(10 V). An exfoliated graphene was collected through cellulose nitrate filter paper and
washed with double distilled water. The obtained sample was dried at 100 °C for 2 h.
Int. J. Mod. Phys. Conf. Ser. 2013.22:380-384. Downloaded from www.worldscientific.com

Commercial high-purity Y2O3 powder (SD-Fine) was used in the synthesis of composite.
The graphene/Y2O3 composite were prepared by mixing 20 wt% of graphene in constant
1 gm Y2O3 in 30 ml acetone as organic media. The solid-state chemiresistive method was
adopted for gas sensing. The chemiresistor was prepared by screen-printing technique on
chemically clean glass substrate. The silver electrode deposited on the both side of
by 14.139.121.194 on 05/27/13. For personal use only.

chemiresistor for resistance measurement. The electrical resistance was measured by

using a voltage drop method adopted by Waghuley et al [6]. The CO2 gas concentration
inside the chamber was maintained by gas injecting method.

3. Results and discussion

The UV-VIS analysis was employed to know the optical properties of materials. It is
straightforward technique to probe the optical band gap of material. Hence, imaging
small structures through electron microscopy techniques is not enough to say it is in
quantum confinement state [7] The UV-VIS spectra of graphene and Y2O3 displayed in
Figs 1 and 2 respectively, inset shows their band gap. These values of band gap are used
to compute the particle size of materials with the help of hyperbolic band model (HBM)
[8]. As the band gap is particle size dependent, we can estimate the particle size. The
particle size found to be for graphene and Y2O3 is 6.06 and 28 nm respectively.

Fig.1. UV-VIS spectra of graphene and inset shows the plot between (hν)/(αhν)1/2
 382 K. R. Nemade & S. A. Waghuley
Int. J. Mod. Phys. Conf. Ser. 2013.22:380-384. Downloaded from www.worldscientific.com

Fig.2. UV-VIS spectra of Y2O3 and inset shows the plot between (hν)/(αhν)1/2
by 14.139.121.194 on 05/27/13. For personal use only.

The TEM analysis was employed to study the morphology of material displayed in Fig.3
(a) and (b). Fig.3 (a) shows the TEM of graphene giving different levels of transparency.
Fig 3 (b) shows the TEM of Y2O3, showed particle are not perfectly spherical. The
average stacking size of graphene sheet from TEM analysis found to be 8 nm. The
average crystallite size of Y2O3 was found to be 30 nm. The average crystallite size found
from TEM investigations are in agreement with UV-VIS analysis.

Fig.3. TEM of (a)graphene and (b) Y2O3

The gas sensing response of Y2O3, graphene and 20-wt% of graphene/Y2O3 composite
depicts in Fig. 4. As the CO2 is oxidizing, resistance increases with increasing
concentration. The sensing response of graphene and 20-wt% of graphene/Y2O3
composite shows the good dependence on the concentration of CO2 gas. The gas sensing
response value of Y2O3 attends saturation onwards 20 ppm. The optimum value of
sensing response found to be 1.08 for 20-wt% of graphene/Y2O3 composite at 35 ppm.
 Carbon Dioxide Gas Sensing Application 383
Int. J. Mod. Phys. Conf. Ser. 2013.22:380-384. Downloaded from www.worldscientific.com

Fig.4. Sensing response of Y2O3, graphene and 20-wt% of graphene/Y2O3 composite

by 14.139.121.194 on 05/27/13. For personal use only.

The stability characteristics of Y2O3, graphene and 20-wt% of graphene/Y2O3 composite

were examined with 25 ppm concentration of CO2 for 15 days at room temperature
shown in Fig. 5. The chemiresistors shows almost constant response, indicating good
stability.

Fig.5. Stability of Y2O3, graphene and 20-wt% of graphene/ Y2O3 composite

Gas sensing action basically depends on electron transfer reactions, which are redox
reactions. In this reactions the electron donor is oxidised and the acceptor reduced. The
basic assumption of the theory is a weak electronic interaction of the two reacting species
is required for a simple electron transfer process to occur. The reactants may be ions or
molecules. The free energy that drives the reaction is the difference in reduction
potentials between donor and acceptor [9]. The gas-sensing mechanism based on the
surface reaction between the adsorbed oxygen ions and the gas molecules. Oxygen may
 384 K. R. Nemade & S. A. Waghuley

be either physisorbed as uncharged molecules or chemisorbed as charged species on the

surface of material. As the CO2 having tendency to withdrawing electron from the
surface, electrical resistance of material increase.

4. Conclusions
The synthesized graphene/Y2O3 QDs composites possess good gas sensing response and
stability at room temperature. The particle size determined from UV-VIS and TEM
analysis are in agreement. The morphological study pointed out that the graphene and
Y2O3 surface functional for gas sensing application. The optimum value of sensing
Int. J. Mod. Phys. Conf. Ser. 2013.22:380-384. Downloaded from www.worldscientific.com

response was found to be 1.08 for 20-wt% of graphene/Y2O3 QDs composite.

References
1. X.Huang, Z.Yin, S.Wu, X.Qi, Q.He, Q.Zhang, Q.Yan, F.Boey and H.Zhang, Small, 7,
1876 (2011).
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2. K.R.Ratinac, W.Yang, S.P.Ringer and F.Braet Environ. Sci. Technol., 44, 1167 (2010).
3. X.Cao, Y. Tao, L. Li, Y. Liu, Y. Peng and J. Li, Luminescence, 26, 5 (2011).
4. S.A.Waghuley, R.S.Bobade, A.V.Kohle, G.G.Muley, S.S.Yawale, F.C. Raghuvanshi,
S.P.Yawale and S.S.Yawale, Optoelectron. Adv.Mater. Rapid. Commun., 4, 97, 2010.
5. C. Su, A. Lu, Y. Xu, F. Chen, A. Khlobystov and L. Li, ACS nano, 5, 2332(2011).
6. S.A.Waghuley, S.M.Yenorkar, S.S.Yawale and S.P.Yawale. Sens Actuators B Chem, 128, 66
(2008).
7. T.J.Bukowski, T.M.Neidt, R.Ochoa, J.H.Simmons, J. Non. Cryst. Solid. 274, 87 (2000).
8. S.S.Nath, M.Choudhury, G.Gope, R.K.Nath, Nanotrends, 8, 1 (2010).
9. R.A. Marcus, Canadian J. Chemistry. 37, 155 (1959).
Chemiresistive Gas Sensing by Few-Layered
Graphene

K. R. Nemade & S. A. Waghuley

Journal of Electronic Materials

ISSN 0361-5235
Volume 42
Number 10

Journal of Elec Materi (2013)

42:2857-2866
DOI 10.1007/s11664-013-2699-4

1 23
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1 23
 Author's personal copy
Journal of ELECTRONIC MATERIALS, Vol. 42, No. 10, 2013
DOI: 10.1007/s11664-013-2699-4
Ó 2013 TMS

Chemiresistive Gas Sensing by Few-Layered Graphene

K.R. NEMADE1 and S.A. WAGHULEY1,2

1.—Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India.
2.—e-mail: sandeepwaghuley@sgbau.ac.in

A chemiresistive gas sensor based on few-layered graphene (FLG) has been

fabricated and evaluated for carbon dioxide (CO2) and liquid petroleum gas
(LPG) sensing. The electrochemical exfoliation method was used to synthesize
FLG. The resulting sample of FLG was characterized by x-ray diffraction,
Raman spectroscopy, atomic force microscopy, and transmission electron
microscopy with selected-area diffraction. Ultraviolet–visible and fluorescence
spectroscopy were employed to study the optical properties. Thermal behavior
was analyzed through thermogravimetric–differential thermal analysis. The
sensing response of the chemiresistor is defined as the ratio of resistance in
gas to air at the stabilized resistance in air. The FLG chemiresistor exhibited
good sensing response (3.83 for CO2, 0.92 for LPG), response time (11 s for
CO2, 5 s for LPG), recovery time (14 s for CO2, 18 s for LPG), and resolution
limit (3 ppm for CO2, 4 ppm for LPG), and excellent stability at room tem-
perature. The gas sensing mechanism is discussed on the basis of marginal
difference in Raman intensity and also by using defect chemistry through
fluorescence measurements.

Key words: Few-layered graphene, carbon dioxide, liquid petroleum gas,

defects

INTRODUCTION consequently their efficient and cost-effective sens-

ing becomes even more essential.
Global warming has become a pressing environ-
In the light of this discussion, graphene is a po-
mental issue related to increasing atmospheric
tential gas-sensing material with enormous sensi-
concentrations of greenhouse gases. Carbon dioxide
tivity. As defined by the International Union of Pure
(CO2) is one of the most common gases evolved in
and Applied Chemistry, graphene is formed of 10 or
combustion, also being a greenhouse gas.1 CO2 is a
fewer carbon atom layers, being divided into three
stable oxidizing gas, so its detection is challenging.
major categories: (i) single-layer, (ii) 2-layer, and
In many fields, such as industrial emission control,
(iii) 3- to 10-layer graphene, known as monolayered,
household security, and vehicle emission control,
bilayered, and few-layered graphene (FLG),
monitoring of CO2 is mandatory. Therefore, cost-
respectively. Yoon et al.3 reported CO2 sensing with
effective and robust sensing materials are required
FLG. Recent study has verified the detection of
for CO2 detection. Correspondingly, liquid petro-
molecules by pristine graphene, attracting great
leum gas (LPG) has found useful application as a
research interest from both the scientific and engi-
clean source of energy. However, its explosive nat-
neering communities.4 Many researchers have
ure means that reliable and efficient gas sensors
reported on gas-sensing applications of graphene.5–8
that can detect even minute LPG concentrations
Graphene is a highly promising material for use in
are required.2 Both of these gases are widely
terahertz devices, opening a new field of nanoma-
used for many domestic and industrial purposes;
terial wave characteristics.9–11 Graphene-based
devices have low Johnson noise due to its low
resistivity.5
(Received March 13, 2013; accepted July 9, 2013; Sensing responses can mainly be attributed to
published online August 14, 2013) electron transfer between a material and chemisorbed

2857
 Author's personal copy
2858 Nemade and Waghuley

Fig. 1. Scheme of electrochemical exfoliation of graphite.

gaseous molecules. This is a redox-type reaction,

leading to changes in the depletion layer of the
grains that change the electrical resistance. There
are many possible reactions for the change in elec-
trical resistance; the most common reaction that
leads to changes in the resistance/conductance is
adsorption of gases on the surface of sensing mate-
rials. The transport properties of materials are
mainly dependent on defect concentrations. Great
emphasis should be placed on defect concentrations,
as adsorption of gases and the sensing response are
measured in terms of resistance.12,13 Kaur et al.14
reported sensing of H2S gas at ppb levels and Fig. 2. Gas sensing setup.
demonstrated that the sensing parameters are
strongly affected by the concentration of defects.
Lupan et al.15 discussed the sensing mechanism for
hydrogen gas, focusing on the role of defect chem-
istry. Hwang et al.16 recently reported synthesis of 10000
(002)
graphene sheets from highly oriented pyrolytic
graphite through mechanical cleavage in order to 8000
Intensity (Arb. Unit)

investigate its response in chemical vapor sensing.

In this work, we introduce a highly responsive 6000
chemiresistor based on FLG as a gas-sensing
material for CO2 and LPG. During literature sur- 4000
vey, it was observed that researchers have reported
synthesis of graphene by electrochemical exfoliation
2000 (100)
of graphite using platinum as a cathodic electrode.
For the present investigation, we used a silver
electrode for the electrochemical exfoliation process 0
10 20 30 40 50 60
of graphite. This significantly reduced the prepara-
2θ Position (deg.)
tion cost. The chemiresistor exhibits strong sensing
response with fast response and recovery charac- Fig. 3. XRD pattern of FLG.
teristics. The stability of the chemiresistor was
found to be excellent. Some interesting accom-
plishments are reported.
electrode. For electrochemical exfoliation, graphite
flake and the silver electrode were inserted into an
EXPERIMENTAL PROCEDURES
ionic solution with separation of 5 cm. The ionic
FLG was synthesized from graphite flake using a solution was prepared by taking 4.8 g sulfuric acid
modified electrochemical exfoliation method, in (99.99%; SD Fine) diluted in 100 mL double-distilled
which a silver electrode was used as the cathodic water. The process was carried out in a direct-current
 Author's personal copy
Chemiresistive Gas Sensing by Few-Layered Graphene
(DC) bias (10 V) arrangement at room temperature
(303 K).17 Exfoliated FLG was collected through
cellulose nitrate filter paper and washed with dou-
ble-distilled water. The obtained sample was dried
at 100°C for 2 h. Figure 1 shows the electrochemical
exfoliation process of graphite.
The structural and phase purity of the as-pre-
pared FLG were determined by x-ray diffraction
(XRD, PW 1830; Philips). The morphology and few-
layered structure were examined by atomic force
microscopy (AFM, Webinar series; Bruker) and
high-resolution transmission electron microscopy
(HR-TEM, Tecnai F-30107; Philips) with selected-
area diffraction pattern (SADP) analysis. Raman
spectroscopy (RFS 27; Bruker; Raman spectrometer
using a Nd:YAG laser excitation source at 514 nm)
was employed to characterize the few-layered
structure and quality of graphene. Optical charac-
terization was done through ultraviolet–visible
(UV–Vis; PerkinElmer) and fluorescence spectros-
copy (FL spectrophotometer model F-7000; Hitachi).
The thermal behavior of FLG was analyzed using
thermogravimetric–differential thermal analysis
(TG–DTA, DTG-60h; Shimadzu).
A chemiresistor is a type of variable-resistance
sensor whose resistance changes in the presence
of gases. For measurement of the gas-sensing
response, dried FLG was dispersed with a tempo-
rary binder in a mixture of organic solvents to form
a paste, prepared using a previously reported
method.18 For strong adhesion to a substrate, the
ratio of FLG to binder was kept at 90:10 in formu-
lating the paste. A thick film of FLG was depos-
ited on a chemically cleaned glass substrate of
25 mm 9 25 mm size by screen-printing, then dried
at room temperature (303 K) for 24 h. Further heat
treatment was applied to the film at 373 K for 3 h
for evaporation of volatile organic compounds from
the binder. The thickness of the chemiresistor
was measured using a Digimatic (Japan) outside
micrometer (series 293) having resolution of
±0.001 mm and found to be 7 lm. For surface
resistance measurements, highly conducting silver
paste was used to make ohmic contacts on adjacent
sides of the film with electrode thickness of 12 lm,
and then it was subjected to heating at 353 K for
15 min to dry the silver paint. The gap dimension of
the chemiresistor was 21 mm 9 25 mm. To check
the gas-sensing response, the chemiresistor was
loaded into a gas-sensing chamber. The tempera-
ture and humidity inside the chamber were pre-
cisely controlled. The sensing response was studied
by using air as reference gas. The gas-sensing
response (S) is defined as S = |Ra  Rg|/Ra, where
Ra is the resistance in air (baseline resistance) and
Rg represents the resistance in gas. During this
experiment, the resistance of the chemiresistor was
measured using the voltage drop method adopted
by Waghuley et al.18 The sensing parameters of
the chemiresistor were analyzed at different
concentrations (ppm) and temperatures. The gas
2859
concentration required inside the 5-L chamber was
maintained by injecting a known volume of test gas
using a gas-injection syringe of different vol-
umes. The concentration inside the chamber was
increased by adding a particular amount of gas; For
example, 0.025 mL of gas added into the 5-L
chamber was defined as 0.025 mL/5000 mL = 5/106,
i.e., 5 ppm. An outline of the gas-sensing system is
shown in Fig. 2.
RESULTS AND DISCUSSION
Figure 3 shows the XRD pattern of the FLG, well
supporting its structural and phase purity. There
are two prominent peaks in the XRD pattern, (002)
and (100), which are characteristic peaks of graph-
ene. The sharp peak at 2h = 26.3° indicates a highly
organized structure with interlayer spacing of
0.339 nm.19 This is consistent with the layer spac-
ing of typical graphite. The broad peak at 2h = 44.2°
may be assigned to a lower degree of crystallization
and the presence of some defects. This may be due to
adsorption of oxygen molecules with amorphous
carbon present on the FLG surface, as CO2 mole-
cules are known as a buffer gas.19
Atomic force microscopy and HR-TEM observa-
tions were employed to explore the surface mor-
phology of the FLG. Raman spectroscopy was used
to determine the number of graphene layers present
in the stacked structure of graphene and its quality.
Figure 4a shows an AFM image and height profile
for the FLG. The average of the height distribution
(H) of FLG was 1.7 nm. As the interlayer spac-
ing between two graphene sheets (d) is 0.339 nm
(H/d = 5.01), the stacked graphene was five-layered.
Figure 4b shows the Raman spectrum of the FLG.
The most important Raman features of FLG are the
D band (1300 cm1), G band ( 1580 cm1), and 2D
band (2720 cm1). The D band is associated with
the density of defects. The intensity of the D band is
directly proportional to the concentration of defects.
This band is the result of a one-phonon lattice
vibrational process, which is typically very weak in
graphene. In our case, the D band is less notably
than the G and 2D bands. The G band is assigned to
in-plane vibration of sp2 carbon atoms.20 The 2D
band originates from a two-phonon double-reso-
nance process.21 The intensity ratio of the G to 2D
band is related to the number of graphene layers.22
The relation between the number of graphene lay-
ers (N) and the intensity ratio of the G to 2D band is
N = (IG/I2D), where IG is the intensity of the G band
and I2D is the intensity of the 2D band. The value of
N is less than one for mono- and bilayered graph-
ene.23 This value ranges from 1.3 to 2.4 for 5 to 10
layers of graphene.24 In the present work, the value
of N was found to be 1.64, which lies between 1.3
and 2.4, reflecting the few-layered structure of the
graphene. This confirms that the synthesized
graphene was few-layered. The full-width at half-
maximum of the 2D peak is 80 cm1, also reflecting
 Author's personal copy
2860 Nemade and Waghuley

Fig. 4. (a) AFM image with height distribution of FLG. (b) Raman spectrum of FLG and (c) HR-TEM image showing the layered structure of the
graphene. The inset shows a SADP image of the FLG.

the few-layered graphene structure.25 The few-

layered structure of graphene can be visualized 7
directly by HR-TEM, as shown in Fig. 4c (high- 90
lighted in a red box). The inset of Fig. 4c shows a 6
% Transmission

SADP image of the FLG, agreeing with the results 85

5
% Transmission

obtained from XRD analysis. The rings in the dif-

80
fraction pattern match the principal (002) and 4
(100) peaks of graphene. The clear SADP image is 75
due to the layered structure of graphene, showing 3
the hexagonal symmetry.23 70
400 500 600 700
UV–Vis spectroscopy provides a tentative idea 2
Wavelength (nm)
about the layered structure of the graphene. The
optical transmission spectrum of FLG is shown in 1
Fig. 5.
The intense absorption at 268 nm may be exhib- 0
230 240 250 260 270 280
ited due to the few-layered structure of graphene.
This is assigned to p–p* transitions of C–C bonds.26 Wavelength (nm)
The linear increase in the ultraviolet region around Fig. 5. Transmission spectrum of FLG in the UV and visible region
268 nm and nearly flat transmission on the order of (inset).
 Author's personal copy
Chemiresistive Gas Sensing by Few-Layered Graphene 2861

56 I UV RT percentage curve, the sample shows a sharp weight

49
323 K loss up to 373 K, and the DTA curve shows an
A 373 K
endothermic peak at 342 K, corresponding to evap-
Fluorescence intensity

423 K
42 473 K
oration of absorbed water. The total mass loss from
35 A
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room temperature to 450 K was about 15.22%. The
A
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DTA curve shows another exothermic peak at
28 AAA

740 K, which may correspond to generation of

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disorder defects.
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Figure 8 shows the dependence of the sensing

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response of the FLG chemiresistor on the concen-
tration of CO2 and LPG at room temperature. The
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300
Fig. 6. Fluorescence measurements of FLG against sintering tem-
perature with excitation at 254 nm.
Table I. IUV, IDL, and IUV/IDL ratio values for FLG
for different sintering temperatures
Temperature (K)
303
323
373
423
473
86% in the visible region (400 nm to 700 nm) may be
assigned to six-layered graphene.23,26,27 Analyzing
and combining the results from AFM, Raman,
HR-TEM, SADP, and UV–Vis spectroscopy, it can
be concluded that five or six layers of graphene are
present in the stacked graphene.
Fluorescence spectroscopy can assess the con-
centration of defects in a material, which is relevant
as the sensing parameters are strongly affected by
the defect concentration.28,29 To calculate the defect
concentration, fluorescence measurements were
carried out from 300 nm to 700 nm, as shown in
Fig. 6. The intensity ratio of ultraviolet (IUV) to
visible deep levels (IDL) is a measure of the defect
concentration.15 As shown in the figure, the (IUV/
IDL) ratio was found to increase with the sintering
temperature. In the present work, the FLG emitted
intense blue luminescence under irradiation at
254 nm. The peak value of the emission was
observed at 343 nm. The IUV, IDL, and (IUV/IDL)
ratio values for the FLG are listed in Table I against
sintering temperature. This shows that defects are
present on the surface of the FLG and increase with
the sintering temperature.
Figure 7 shows the TG–DTA results for the FLG,
to show the thermal stability during heat treat-
ment. The TG–DTA analysis was carried out from
room temperature to 775 K in nitrogen atmosphere.
There are two major mass change steps with
increasing temperature. According to the TGA
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350 400 450 500 550 600 650 700 2.236 9 106 X. In this experiment, a known amount
Wavelength (nm) of gas was inserted into the chamber, which was
initially filled with air. Upon exposure to CO2 (an
oxidizing gas), the resistance of the FLG chemire-
sistor increased. However, the resistance of the
chemiresistor decreased when it was exposed to
LPG (a reducing gas). This confirms that FLG
exhibits n-type characteristics.30 The sensing
response of the chemiresistor was found to vary
linearly with the concentration of CO2 gas. This
IUV IDL IUV/IDL linear relationship between the response and the
CO2 gas concentration suggests that the chemire-
28.20 1.5 18.8 sistor response exhibits a good dependence on the
31.38 1.53 20.50 gas concentration. Saturation was observed for LPG
36.66 1.56 23.5 above 75 ppm. This may indicate the optimum
42.30 1.63 25.95
detection limit for LPG.
51.35 1.67 30.74
To determine the interaction between oxygen-
adsorbed FLG and CO2 or LPG gas, Raman spec-
troscopy was performed. Figure 9 depicts the
Raman spectra of FLG in CO2 and LPG environ-
ments, acquired after testing the sensing response
of FLG towards CO2 and LPG at room temperature.
The intensities of almost all the peaks shown in the
Raman spectrum were significantly affected. Among
these bands, the D band is strongly affected. This
may be due to gas molecules forming surface species
such as surface carbonate and water, which affect
the one-phonon lattice vibration process.
This observation can also be explained based on
the surface reaction between adsorbed oxygen ions
and the gas molecules. Oxygen may be either
adsorbed as uncharged molecules or chemisorbed as
charged species on the film surface.31 For adsorbed
oxygen ions, the interactions are
O2 ðgasÞ ! O2 ðadsÞ
O2 ðadsÞ þ e ! O2 ðadsÞ
O  
2 ðadsÞ þ e ! 2O ðadsÞ
A great number of oxygen ions on the surface
creates a higher potential barrier; therefore, the
resistance of the chemiresistor increases.32 The CO2
gas detection mechanism of the FLG chemiresistor
is based on the reaction that occurs between
adsorbed oxygen and CO2 gas molecules. CO2 is a
strong oxidizer gas with electron-withdrawing
power. When the chemiresistor is exposed to CO2
 Author's personal copy
2862 Nemade and Waghuley

105 6
740 K
100 DTA

95 4
Mass change=15.32 %

DTA (uV/mg)
90
% TGA 85 2
TGA Mass change=10.15 %
80

75 0

70

65 342 K -2

60
350 400 450 500 550 600 650 700 750
Temperature (K)
Fig. 7. TG–DTA curves of FLG.

5 1000
FLG in air
Carbon dioxide 900 FLG in CO2
4 LPG FLG in LPG
800
Sensing response

700
Intensity

3
600

2 500
400
1 300
200
0
0 50 100 150 200 1000 1500 2000 2500 3000
-1
Gas concentration (ppm) Raman shift (cm )
Fig. 8. Sensing response of the chemiresistor towards CO2 and Fig. 9. Raman spectra of FLG in CO2 and LPG environments.
LPG at room temperature.

gas, the gas is chemisorbed onto bridging oxygen Figure 10 shows the variation of the gas-sensing
atoms with the formation of a surface carbonate and responses of the FLG chemiresistor and the IUV/IDL
increase in the resistance of the chemiresistor.33 ratio (obtained from fluorescence measurements) as
The interactions between CO2 and adsorbed oxygen a function of temperature for constant concentra-
ions are tion of CO2 (30 ppm, 40 ppm, and 50 ppm). It is
noticeable that excellent correlation exists between
CO2 þ 2O ðadsÞ ! CO2 the IUV/IDL ratio and the gas-sensing response with
3
temperature.
CO2 þ O ðadsÞ ! CO
3 Figure 11 shows the variation of the gas-sensing
responses and IUV/IDL ratio as a function of tem-
perature for constant concentration of LPG
LPG is composed of CH4, C3H8, C4H10, etc., and
(30 ppm, 40 ppm, and 50 ppm). Here also, excellent
these molecules are reducing species. When the
correlation is observed between the IUV/IDL ratio
chemiresistor is exposed to LPG, the LPG interacts
and the gas-sensing response with temperature.
with adsorbed oxygen ions to form H2O and CO2.
The highest value of the sensing response was
The interactions between LPG and adsorbed oxygen
found at 423 K for CO2 and 398 K for LPG for
ions are34
30 ppm, 40 ppm, and 50 ppm. Therefore, for CO2
gas detection, the operating temperature of the
Cn H2nþ2 þ 2O ðadsÞ ! H2 O þ Cn H2n : O þ e chemiresistor can be 423 K, and 398 K for LPG.
Cn H2n : O þ O ðadsÞ ! CO2 þ H2 O þ e This strong sensing response can be attributed to an
 Author's personal copy
Chemiresistive Gas Sensing by Few-Layered Graphene 2863

(a) 32 1.5
30 ppm
30
1.4

CO2 sensing response

28
1.3

IUV / I DL
26

24 1.2

22
1.1

20
1.0
320 340 360 380 400 420 440 460 480
Temperature (K)

32 1.9
(b) 40 ppm

30 1.8

CO2 sensing response

28
1.7
IUV / I DL

26
1.6
24

1.5
22

20 1.4

320 340 360 380 400 420 440 460 480

Temperature (K)

(c) 32 50 ppm 2.1

30
2.0
CO2 sensing response

28 1.9
IUV / I DL

1.8
26

1.7
24
1.6
22
1.5

20 1.4

320 340 360 380 400 420 440 460 480

Temperature (K)
Fig. 10. Variation of the IUV/IDL ratio and CO2 sensing response as a function of temperature for (a) 30 ppm, (b) 40 ppm, and (c) 50 ppm.

increase in the concentration of defects. The most
probable defects in graphene are hexagonal defects
in the form of oxygen vacancies.35,36 As the tem-
perature increases, the defect concentration also
increases and emerges onto the surface of the
chemiresistor. These defects in the form of vacant
sites are available for chemisorption of atmospheric
oxygen.37 The greater the number of defects, the
more oxygen will be chemisorbed. This results in
enhancement of the sensing response. However, in
 Author's personal copy
2864 Nemade and Waghuley

(a) 32 1.0
30 ppm

30
0.9

LPG sensing response

28

IUV / I DL 26 0.8

24
0.7

22

0.6
20

320 340 360 380 400 420 440 460 480

Temperature (K)

(b) 32 1.3
40 ppm

30
1.2

LPG sensing response

28
1.1
IUV / I DL

26

24 1.0

22
0.9

20
0.8
320 340 360 380 400 420 440 460 480
Temperature (K)

(c) 32 50 ppm
1.9
30
LPG sensing response

28
1.8
IUV / I DL

26

24 1.7

22

1.6
20

320 340 360 380 400 420 440 460 480

Temperature (K)
Fig. 11. Variation of the IUV/IDL ratio and LPG sensing response as a function of temperature for (a) 30 ppm, (b) 40 ppm, and (c) 50 ppm.

both cases, the response decreases above certain of the response at high temperatures. This result is
higher temperatures, as the absorbed oxygen is well consistent with observations by Kapase et al.31
desorbed from the surface of the chemiresistor. This Figure 12a shows the transient response charac-
is one of the possible explanations for the lowering teristics of the chemiresistor for CO2 and LPG,
 Author's personal copy
Chemiresistive Gas Sensing by Few-Layered Graphene 2865

(a) 1 Carbon dioxide

(b) 2.5 Carbon dioxide
LPG LPG
0.8

Sensing response
2

Sensing response
0.6
1.5
0.4

1
0.2

0 0.5
0 10 20 30 0 10 20 30
Time (s) Time (Days)
Fig. 12. (a) Transient and (b) stability response characteristics of FLG to 100 ppm CO2 gas and LPG at room temperature.

measured to determine the response and recovery

times at room temperature for 100 ppm. The Table II. Resolution limit of the chemiresistor for
CO2 gas
response time of the chemiresistor can be defined as
the time required for its resistance to change from Concentration of Resistance of
its initial value to 90% of its highest value, whereas CO2 Gas (ppm) Chemiresistor (X)
the recovery time of the chemiresistor can be
defined as the time taken for its resistance to reduce 0 (air) 2.236 9 106
by 90% from its highest value. In this measurement, 1 2.236 9 106
gas was inserted into the chamber and the resis- 2 2.236 9 106
3 2.417 9 106
tance of the chemiresistor was measured. The
response time was found to be 11 s for CO2 gas and
5 s for LPG. To measure the recovery time, the
sample was exposed to air. The recovery time was
found to be 14 s for CO2 gas and 18 s for LPG. This Table III. Resolution limit of the chemiresistor for
fast response characteristic may be attributed to the LPG
fast interaction of gas molecules with the FLG sur- Concentration Resistance of
face, whereas the slow recovery can be attributed to of LPG (ppm) Chemiresistor (X)
strong bonding of the gas molecules to the absorbed
oxygen, requiring a longer time for the annihilation 0 (air) 2.236 9 106
process. To check the stability of the chemiresistor, 1 2.236 9 106
its response towards 100 ppm of CO2 and LPG at 2 2.236 9 106
room temperature was measured for 30 days at 3 2.236 9 106
4 2.317 9 106
intervals of 5 days after the first measurement. The
results are illustrated in Fig. 12b. The chemiresis-
tor showed a nearly constant response to CO2 gas
and LPG, indicating good stability of the chemire- concentrations (ppm) of gas could change the resis-
sistor. This shows that the graphene chemiresistor tance of the chemiresistor.
possesses good stability. In the present case, the strongest sensing
The resolution limit is the lowest concentration response was found to be on the order of 3.83 for
difference that can be distinguished by the che- CO2 at 200 ppm, which is better than reported in
miresistor.38 The resistance of the chemiresistor in Refs. 3,39. The operating temperature for CO2 gas
air was 2.236 9 106 X. The resolution limit charac- detection is 423 K, which is also much lower than in
teristic was measured by injecting a known volume Ref. 40. The low operating temperature (398 K) and
of gas into the chamber. A sharp change from the infinitesimal resolution limit (4 ppm) for LPG
resistance value in air for a particular gas concen- sensing are the most attractive features of the
tration was considered to indicate the resolution present work, as operation of LPG chemiresistors at
limit of the chemiresistor. The resolution limit high temperatures is difficult due to the explosive
results are presented in Tables II and III for CO2 nature of the gas. The good sensing response (0.92),
and LPG, respectively. lower operating temperature (398 K), fast response
The resolution limit value was found to be 3 ppm time (5 s) and recovery time (18 s), and lower reso-
and 4 ppm for CO2 and LPG, respectively. It lution limit (4 ppm) are adequate for use as a prac-
was observed that absorption of even minute tical LPG sensor. The low operating temperatures for
 Author's personal copy
2866
both investigated gases significantly reduce the
operating cost.
CONCLUSIONS
We have demonstrated a chemiresistive gas-sensing
application of FLG synthesized by electrochemical
exfoliation using silver as a cathodic electrode. The
phase composition as analyzed by XRD showed the
formation of FLG. Raman spectroscopy results con-
firmed that the FLG surface possesses fewer defects
and a layered structure. The layered structure was
also confirmed by AFM and HR-TEM. The FLG che-
miresistor exhibited a good sensing response for CO2
and LPG gases at room temperature as well as at
relatively low operating temperatures. The sensing
response showed a good dependence on the concen-
tration of defects. The chemiresistor realized detec-
tion of CO2 and LPG with rapid response and
recovery. The chemiresistor was found to exhibit
good stability for CO2 and LPG sensing. The
chemiresistor exhibited low resolution limit values
for both investigated gases. Such detection of lower
concentrations can be useful for practical applica-
tions. The described FLG chemiresistor may be
a good candidate for practical use in CO2 and
LPG detection based on the good characteristics
mentioned.
ACKNOWLEDGEMENTS
The authors are very grateful to the Head of the
Department of Physics, Sant Gadge Baba Amravati
University, Amravati, India and the Head of the
Department of Chemical Science, North Maha-
rashtra University, Jalgaon, India for providing
necessary facilities.
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Journal of Materials Science and Engineering B 3 (5) (2013) 310-313
D DAVID PUBLISHING

Gas Sensing Mechanism of Metal Oxide Doped PANi

Composites

Kailash R. Nemade and Sandeep A. Waghuley

Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India

Received: December 03, 2012 / Accepted: January 06, 2013 / Published: May 25, 2013.

Abstract: Novel hybrid gas-sensitive materials were made-up by means of metal oxide (MOX) doped organopolymers. The hybrid
gas-sensitive materials were prepared by varying molar concentration of Bi2O3 and Y2O3 MOX in conducting polymer PANi. The
hybrid materials have tested upon exposure to LPG gas. The sensitivity of both composites materials was studied at room
temperature. The gas sensing mechanism explained on the basis of chemisorbed/adsorbed oxygen. The materials were characterized
by FTIR and SEM analysis.

Key words: Gas sensing, metal oxide, PANi.

Nomenclature metal oxides have been synthesized and investigated

PANi: Polyaniline
1. Introduction
Polymer-metal or metal oxide nanocomposite is a
new class of material that combines the advantages of
both organic polymer material and inorganic metal or
semiconductor oxide and shows improved optical,
electrical and mechanical properties for gas sensor
applications. The gas sensing properties of films
depend not only upon the individual components used
but also on the morphology and the interfacial
characteristics. The composite films that combine
materials with synergetic behaviours possess unique
physical, chemical, optical, mechanical, magnetic and
electrical properties unavailable from that of the
component materials and have attracted much
attention for a wide range of device applications such
as gas sensors. Recently, various nanocomposite films
consisting of either metal-metal oxide, mixed metal
oxides, polymers mixed with metals or metal oxides,
or carbon nanotubes mixed with polymers, metals or
Corresponding author: Sandeep A. Waghuley, Ph.D.,
professor, research fields: sensors, conducting glasses. E-mail:
sandeepwaghuley@sgbau.ac.in.
for their application as active materials for gas sensors.
Design of the nanocomposite films for gas sensor
applications needs the considerations of many factors,
such as the surface area, interfacial characteristics,
electrical conductivity, nanocrystallite size, surface
and interfacial energy, stress and strain, etc. which
depend significantly on the material selection,
deposition methods and deposition process parameters.
The conducting polymers have shown great promise is
in sensory applications. The localized electronic states
combined with the restriction on the extent of
delocalization makes most of the conductive polymers
behave like p-type semiconductors. As these polymers
are redox-active, their conductivity can be changed by
means of doping/dedoping. A great number of sensing
applications are designed by exploiting nature of
conducting polymers [1]. Cioffi, et al. investigated
polymer films embedded with Pd or Au nanoparticles
for detecting vapours of organic solvents [2].
The importance of environmental gas monitoring is
well understood and much research has been focused
on the development of suitable gas sensitive materials.
Recently, there has been considerable interest in
exploiting organic substances such as porphyrin,
 Gas Sensing Mechanism of Metal Oxide Doped PANi Composites 311

phthalocyanines and doped conductive polymers for
this purpose. The conducting polymers are good
candidates for the elaboration of chemical or
electrochemical sensors. Among the conducting
polymers, polyaniline (PANi) is a promising sensing
material and can be synthesized by chemical,
electrochemical or plasma methods, and in each case,
the composition, morphology and physical properties
of the resulting polymer are strongly dependent on the
detailed reaction conditions [3].
In present work, two different composites were
synthesised by chemical route. The PANi/Bi2O3 and
PANi/Y2O3 composites were prepared by varying
molar concentration of MOX. The prepared samples
were characterized by FTIR analysis on shimadzu
(model: 8400s). The morphology of powders was
investigated by using JEOL-JSM (Model-6063) SEM
instrument.
absorptions at 1,590, 1,508, 1,304, 1,210, 1,145 and
831 cm-1. The peaks at 1,590 cm-1 and 1,508 cm-1 are
assigned to C-C ring stretching vibrations. The peaks
at 1,304-1,310 cm-1 correspond to N-H bending. The
bands at 1,145 and 831 cm-1 can be attributed to the in
plane and out-of-plane C-H bending modes,
respectively. The corresponding peaks for the PANi
salt appear at 1,560, 1,482, 1,306, 1,245.9, 1,148 and
814 cm-1, respectively. The peak at 2,390 cm-1 could
be attributed as due to NH stretching mode and the
1,653 cm-1 bond to the NH bending vibration [4]. The
several peaks from 400 to 600 cm-1 attributed to
vibration of Bi-O bonds displayed in Fig. 1,
confirming the formation of Bi2O3 [5]. The peak
observed in Fig. 2 at 415 cm-1 which may be attributed
to the presence of Y-O bond in Y2O3 [6].

2. Experiments
AR grade (SD fine, india) chemicals were used for
this work. The composites PANi/Bi2O3 and PANi/
Y2O3 were prepared by chemical route. The
ammonium persulphate was used as oxidant for
polymerisation of PANi. The samples of Bi2O3/PANi
composites were prepared of 0.5 M and 1 M tested for
LPG gas whereas Y2O3/PANi composites prepared by
varying molar concentration from 0.4-2 M. The thick Fig. 1 FTIR spectra of (a) PANi; (b) 0.5 M; (c) 1 M and
films of prepared samples were fabricated by (d) Bi2O3.

screen-printing method on SiO2 substrate. The silver

electrodes were coated on the films for electrical
contact purpose. The electrical resistance of the film
was measured by using a voltage drop method.

3. Results and Discussion

3.1 FTIR Analysis

The FTIR spectra of the PANi/Bi2O3 and PANi/

Y2O3 composites powder samples were recorded in
the range 4,000-400 cm-1 to confirm polymerisation
shown in Figs. 1 and 2, respectively. The FTIR Fig. 2 FTIR spectra of (a) Y2O3; (b) 0.4 M; (c) 0.8M; (d)
spectrum of the PANi base shows six principal 1.2 M; (e) 1.6 M and (f) 2M.
312 Gas Sensing Mechanism of Metal Oxide Doped PANi Composites

3.2 SEM Analysis

The SEM analysis examined the surface topography

of prepared samples and the representative images are
shown in Figs. 3 and 4. The SEM reveals an
agglomerated powder with a fluffy appearance. This
process yields highly agglomerated composite
material with fluffy morphology, which play vital role
in capturing the gas molecules. This type of
morphology highly functional in gas sensing action.

3.3 Sensing Response Fig. 4 SEM micrograph of Y2O3 (0.4 M) doped PANi.

The PANi/Bi2O3 composites thin films were tested

towards LPG gas at room temperature. The sensor
response is defined as in Eq. (1) [7].
S = (Rg – Ra)/Ra (1)
where, Ra is the resistance of sensor in air and Rg is
the resistance in gas, respectively. The resistance of
the films was found to be decrease with concentration
of LPG. Sensing response of the films was measured
for different concentration of LPG gas at room
temperature Fig. 3. The gas chamber having volume 5
L attached to sensing system for sensors testing. Gas
was introduced in chamber with the help of injection.
Each injection has capacity to inlet 38 mg LPG. Fig. 4 Sensing response of and PANi/Bi2O3 composites.
The sensing responses of PANi/Y2O3 composites
films were also tested toward LPG gas shown in Fig. 4.
The sensor response is defined as Eq. (1). The
resistance of the films was found to be decrease with
concentration of LPG gas.

Fig. 5 Sensing response of PANi/Y2O3 composites.

The sensing mechanisms for prepared materials

were described on the basis of chemisorptions reaction.
The chemisorptions reaction play different role for
oxidising gas and reducing gas. The sensing
Fig. 3 SEM micrograph of Bi2O3(0.5 M) doped PANi. mechanism for both composites explained from
 Gas Sensing Mechanism of Metal Oxide Doped PANi Composites 313

reaction on the sensor surface, resulting in a Acknowledgments

change in concentration of adsorbed oxygen. This
Authors are very much thankful to Head, Department
reaction may be represented as Eq. (2) and Eq. (3) as
of Physics Sant Gadge Baba Amravati University,
follows
Amravati for providing necessary facilities.
O2 (gas) ↔ O2 (ads) (2)
O2 (ads) + e− ↔ O2− (ads) (3)
References
The free electron shown in Eq. (3) on left hand side
[1] S.C. Hernandez, D. Chaudhari, W. Chen, N. Myung, A.
affected by the nature of gas. The oxidising gases
Mulchandani, Single polypyrrole nanowire ammonia gas
inject electrons from material surface, where as the sensor, Inter Science 19 (2007) 2125-2130.
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composites at room temperature, whereas the (0.4 M) Kosalge, G.T. Bhalerao, G.G. Muley, et al., Sensitivity
and dynamic response of Zinc oxide thin films to carbon
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response. 133-135.
 DOI 10.1515/revce-2012-0021      Rev Chem Eng 2013; x(x): xxx–xxx
Q1:
Editorial
Ashok S. Rahate, Kailash Rambhau Nemade and Sandeep A. Waghuley*
assistance
has been Polyphenylene sulfide (PPS): state of the art and
given to
improve the
clarity of
applications
this article.
Please check
to ensure Abstract: Polyphenylene sulfide (PPS) is a versatile mate-
that none rial that gives extruded and molded components the
of your
meaning has
ability to meet exceptionally demanding criteria. This
been lost or semicrystalline engineering thermoplastic has outstand-
misconstrued ing thermal stability, superior toughness, inherent flame
resistance, and excellent chemical resistance. It also has
high mechanical strength, impact resistance, and dimen-
sional stability as well as good electrical properties. The
present review outlines the synthesis methods, charac-
terizations, and electrical and dielectric properties of
PPS composite. Its structural and morphological charac-
teristics, studied for advanced applications such as pho-
tovoltaic cells, gas sensors, and supercapacitors, are in
prospect. In the composite phase, the electric and dielec-
tric properties of PPS are found to be improved.
Keywords: polyphenylene sulfide; synthetic metal;
transport properties.
*Corresponding author: Sandeep A. Waghuley, Department of
Physics, Sant Gadge Baba Amravati University, Amravati 444 602,
India, e-mail: sandeepwaghuley@sgbau.ac.in
Ashok S. Rahate: Department of Applied Physics, Babashaeb Naik
College of Engineering, Pusad 445 215, India
Kailash Rambhau Nemade: Department of Physics, Sant Gadge
Baba Amravati University, Amravati 444 602, India
Q2:
Please 1 Introduction
check the
numbering A field is still remaining where polymers have to enter, and
of headings
that is in electrical conductivity in which metals still have
an upper hand. These polymers have to be made inherently
conductive. This can be achieved by modifying the basic
chemical structure or by doping at the molecular level.
Most of the conducting polymers produced so far by elec-
trochemical technique exhibit poor mechanical strength,
which unfortunately forbids their usage in commercial
products. It has been experimentally demonstrated that
copolymerization is one of the most effective methods to
impart mechanical strength to the known brittle polymers.
In this regard, copolymerization of polyheterocycles with
poly(p-phenylene sulfide) (PPS) would be highly desirable
because PPS can be expected to give better mechanical
strength. It has less pronounced O2 sensitivity, and PPS can
be conveniently doped to get high conductivity.
Charles Friedel and James Mason Crafts discovered
PPS in 1888. Regular PPS is an off-white, linear poly-
meric material of modest molecular weight (18,000) and
mechanical strength. The melt viscosity of this material is
low, of the order of 3–5 Pa·s. The polymer exhibits a glass
transition temperature (Tg) of approximately 85°C and
approximate melting temperature (Tm) of 285°C. When
heated above Tg, the material crystallizes rapidly. PPS is
basically divided into three types:
1. Cured PPS: Cured PPS results from heating of regular
PPS in the presence of oxygen. Generally, the property
changes that occur are a result of molecular chain
extension and formation of some molecular chain
branches that increases the molecular weight and
results in some thermoset-like properties.
2. Linear PPS: The molecular weight of this polymer is
nearly double that of regular PPS. This characteristic
is achieved directly by polymerization. The increased
molecular chain length results in higher tenacity,
elongation, and impact strength.
3. Branched PPS: It has a higher molecular weight than
regular PPS; however, the backbone of the extended
molecule has additional polymer chains branched
from it. This attribute improves some mechanical
properties as well as tenacity and ductility.
PPS possesses high temperature resistance combined with
good mechanical properties, exceptional chemical and
solvent resistance, high dimensional stability, and easy
processing. It has, however, a lower elongation to break
and a higher cost and is rather brittle. In order to improve
these adverse effects, some researchers have blended both
materials and obtained a polymer alloy with outstanding
properties (Akhtar and White 1992). PPS has been increas-
ingly used owing to its excellent chemical, thermal, and
mechanical properties (Ehlers et  al. 1969, Brandy 1981,
Shacklette et al. 1981, Elsenbaumer et al. 1982, Kispert et al.
1983, Bertinelli et al. 1986). A commercially important prep-
aration procedure of PPS involves the polycondensation of
1,4-dichlorobenzene and sodium sulfide in polar solvent,
such as N-methylpyrrolidone, at high temperature and
2      A.S. Rahate et al.: Polyphenylene sulfide
pressure (Edmonds and Hill 1968, Cambell and Edmonds
1977, Koch and Heitz 1983). Much effort has been con-
sumed in the modification of the synthetic route for PPS.
It has also been reported that PPS can also be prepared by
the polycondensation of metal p-halobenzenethiolate at
350°C (Macallum 1949, Lenze et  al. 1959, Lenz and Hand-
lovits 1960, Lenz et  al. 1962, Smith and Handovit 1962,
Handlovit 1968). High-temperature conditions are required
to increase the reactivity of the monomer in the formation
of high molecular weight PPS. However, the polycondensa-
tion of alkyl-substituted monomer does not provide PPS
with high molecular weight, even at high temperature. Few
papers have reported on the preparation of substituted PPS
(Tsunawaki and Prince 1964, Port and Still 1979). Yamamoto
et al. (1989) reported that diphenyl disulfide as a monomer
reacts with Lewis acid to cleave its S-S bonds and is easily
polymerized to linear PPS at room temperature and atmos-
pheric pressure (Tsuchida et al. 1987, 1990).
PPS has been widely used as a material for nonwoven
bag filters because of its good mechanical properties as well
as resistance to high temperature. The relation between
deterioration and crystallinity is based on two things:
Strength is dominated by crystallinity, and strength is
dependent on the defects in amorphous regions and some
parts of crystalline regions. An increase in NO concentra-
tion has a potential to increase the deterioration rates of
amorphous and crystalline phases, but the crystallization
process is unaffected. An increase in O2 concentration
leads to enhancement of both crystallization and dete-
rioration (Tanthapanichakoon et al. 2006). Manufacturers
often rely on PPS to meet demanding conditions. Not only
is this high-performance thermoplastic extremely strong,
rigid, and tough, but it also retains these attributes at tem-
peratures well above 200°C. PPS is perfectly suited for
parts that have to withstand high mechanical and thermal
requirements because the semicrystalline thermoplastic
polymer offers a high melting point range between 280°C
and 290°C; inherent flame resistance; excellent resistance
to chemicals, oils, and fluids; alternatives to conventional
materials such as thermosetting polymers and metals;
high hardness and stiffness and superb long-term creep
under load properties; weight reduction combined with
high dimensional stability; and easy flexibility to injection
mold, blow mold, and machine (Favaloro 2012). The physi-
cal properties of PPS are listed in Table 1.
2 Uses of PPS
PPS is primarily used in injection molding, preci-
sion mechanical parts, electrical components, and
Table 1 Physical properties of PPS.
Physical properties Values
Density (ρ) 1350 kg m-3
Melting temperature (Tm) 280°C
Dielectric strength 22–28 kV mm-1
Coefficient of thermal expansion ( × 10-6/°C) 51.6 ( < Tg), 97.9 ( > Tg)
Thermal conductivity (k) 0.22 W (m·K)-1
Electrical conductivity (S cm-1) 1.5 × 10-16 S cm-1
Vickers microhardness (kg mm-2) 24
components for use in harsh environments. Manufactured
parts from PPS are engine components, valves, high-pres-
sure nozzles, fuel manifolds exterior light reflectors, coil
bobbins, and flow measuring units for hot and cold water
(Garbassi and Po 2005).
Regular PPS is primarily used in coatings due to its
thermal and chemical stability. Cured PPS gives good
results in coatings and injection molding compounds,
whereas linear PPS is ideal for fibers and tougher injec-
tion molding compounds due to the increased molecu-
lar chain length resulting in higher tenacity, elongation,
and impact strength. Due to some improved mechanical
properties as well as tenacity and ductility, branched PPS
is suitable for films and injection molding compounds
(Geibel and Leland 1996).
The preparation of PPS composites with short glass or
carbon fibers provides a cost-effective method for enhanc-
ing mechanical properties. Although many applications of
PPS depend on its electrical insulating behavior, it can be
made electrically conductive by doping with arsenic pen-
tafluoride. PPS is the only commercial polymer that can
be made conductive in this manner and is the only melt-
processable resin (Hill 1979a, Brady et al. 1984, Brochure
and Phillips 2008). Selective doping of the amorphous
or crystalline regions of PPS has been reported (Brady
1985, O’Connor et  al. 1986). This technique has been
extended to metal plating (Chem Eng News 1980). Proton-
Q3:
conducting membranes of sulfonated films composed of Pat et al.
poly(phenylene) sulfide, an organic polymer, and an elas- (2006) was
tomer have been reported. Filler and Dobulis (2006) first changed to
reported the PEM fuel cell application of PPS (Filler and Filler and
Dobulis
Dobulis 2006). The photovoltaic application of PPS was
(2006).
reviewed by Gurunathan et  al. (1999) due to its strong Please
optical absorption in the solar region (1–2.5 eV). confirm
3 Characteristics of PPS
The most important characteristic of PPS is its ability
to change upon heating in the presence of oxygen. This
 A.S. Rahate et al.: Polyphenylene sulfide      3

change generally represents alterations in properties Table 2 Effect of chemical environments on PPS.a
and characteristics as a result of increasing molecular
weight and has been associated with several descriptive Chemical environment Temperature (°C) Rating

terms such as curing, cross-linking, and chain extension. Aromatic hydrocarbons 25 1

Although much is known about this change, the phenom- 93 2
ena are complex in nature and the complete chemistry Aliphatic hydrocarbons 25 1
93 1
is not fully understood. Investigations employing model
Halogenated solvents 25 1
systems indicate that varying degrees of oxidation, cross- 93 2
linking, and chain extension are involved. In this article, Esters and ketones 25 1
this change is referred to as curing. 93 1
As curing occurs, molecular weight and melt viscos- Alcohols 25 1
93 1
ity increase in a gradual manner. The curing of PPS below
Amines 25 –
the melting point (175–280°C) gives a lightly cured and
93 1–3
slightly darkened product, whereas heating above its Weak bases 25 1
melting point (315–425°C) results in gel formation and 93 1
eventual conversion to an infusible black solid. Both the Strong bases 25 1
processes of curing are shown in Figure 1. 93 1
Strong acids 25 1
PPS is almost totally insoluble in organic solvents
93 1
below 200°C. Because of this characteristic, PPS mold- Strong oxidants 25 1
ings are resistant to a variety of different chemical envi- 93 3
ronments as shown in Table 2. Critical analysis of Table 2 24-h water absorption (%) < 0.05
shows that PPS is affected only by high-temperature expo- a
Rating: 1, no effect or inert; 2, slight effect; 3, mild effect (Plast
sure to a few organic solvents, strong mineral acids, and World 1977, Hill 1979b).
strong oxidizing environments.
Because of its chemical structure and its ability to char present review, the discussion regarding the synthesis of
when exposed to a flame, PPS is inherently flame resistant. PPS is confined to chemical route and electrolysis.
A low radiant-panel flame-spread index for PPS is 44 in
oxygen environment. The autoignition temperature of PPS
is 540°C. Oxidizing agents oxidize the sulfide bond to sul- 4.1 Chemical route
foxide or sulfone groups. The aromatic ring can be halogen-
ated, nitrated, and sulfonated to synthesize functionalized The polymerization of diphenyl disulfide with oxidative
PPS. The electrical properties of PPS compounds with polymerization approach is a very easy and convenient
40 wt% glass and glass filled with mineral are listed in Table 3. method. The polymerization route of diphenyl disulfide
with Lewis acid is a convenient procedure for the prepa-
ration of PPS. Polymerization with various Lewis acids
4 Synthesis such as SbCl5, MoCl5, and TiCl4 was reported (Lenz and
Handlovits 1960). The selection of Lewis acid/oxidant
The synthesis of PPS through chemical route and electrol-
ysis is reported in the literature of polymer science. In the
Table 3 Electrical properties of PPS compounds.

>285°C Heat
S Fluid melt Darkening, Property 40 wt% Glass-mineral Test
x thickening, gelation glass-filled filled method

Dielectric strength (kV/mm) 17.7 13.4–15.7 D149

Dielectric constant (25°C)
 1 kHz 3.9 4.6–6.6 D150
<5 h 175-280°C Heat  1 MHz 3.8 4.3–6.1 D150
Dissipation factor (25°C)
 1 kHz 0.0014 0.01–0.08 D150
Slightly darkened powder Infusible black solid  1 MHz 0.0014 0.01–0.02 D150
(lightly cross-linked) (cross-linked)
Volume resistivity (Ω cm) 4.5 × 1016 1–3 × 1015 D257
Arc resistance (Ω) 34 116–182 D495
Figure 1 Curing of PPS.
4      A.S. Rahate et al.: Polyphenylene sulfide

ratio strongly affected the structure, morphology, and 100

transport properties (Lenz et  al. 1962). The tuning of
optimum PPS yield is dependent on the Lewis acid-to-
monomer ratio in the chemical route. The yield of PPS
is temperature dependent; it decreases with increase in

Polymer yield / wt%

temperature (Son et al. 2001). The conventional method
for manufacturing of PPS is by reacting halogenated 50
aromatic compounds, such as p-dichlorobenzene and
sodium sulfide (Na2S·9H2O), in an aprotic organic solvent
under nitrogen atmosphere. Diphenyl disulfide was
allowed to react with aluminum trichloride at room tem-
perature in nitromethane. The polymer was formed as a
white powder having an empirical formula of C6H4S and
0 5 10 15 20
was soluble in hot N-methylpyrrolidone. The PPS yield
[Lewis acid] / [Monomer]
remained at about 50% for the polymerization of diphe-
nyl disulfide and decreased with an increase in the tem- Figure 2 Effect of the concentration of Lewis acid on the polymeri-
perature. The yield and melting point of PPS in various zation of diphenyl disulfide. AlCl3 (•) and SbCl5 (o).
solvents and Lewis acids are listed in Table 4 (Yamamoto
et al. 1989).
because of the electron-donating substitutents. The
The optimum concentration of SbCl5, MoCl5, and FeCl3
results also supported the cationic mechanism.
is two times equimolar of diphenyl disulfide in the polym-
erization. In contrast AlCl3, TiCl4, and BF3O(C2H5)2 required
more than 10 times equimolar of the monomer for an effi-
4.2 Electrolysis
cient formation of PPS. The dependence of PPS yield on
the Lewis acid/monomer ratio is depicted in Figure 2.
Yamamoto et al. (1989) reported the electrolysis synthesis
The melting point, which corresponds to the mole-
method for PPS. A pair of platinum plates was placed in
cular weight of the polymer, increased after the polymer
the cell with 1-cm spacing as the working electrode and
yield becomes constant. The formed polymer or oligom-
auxiliary electrodes. The reference electrode was Ag/AgCl.
ers reacted with Lewis acid to form PPS. This means that
A nitromethane solution of thiophenol (0.1–1 mol) con-
the polymerization proceeds in a stepwise fashion to
tained Lewis acid and was kept at 20°C under a nitrogen
yield PPS. It is considered that the cations electrophili-
atmosphere. The preparative electrolysis was carried out
cally react with dipheynyl disulfide to form the trimer. The
under a controlled potential.
polymerization mechanism of diphenyl disulfide is illus-
trated in Figure 3.
Poly(methyl-substituted phenylene) was rapidly
Lewis acid
formed on the polymerization in comparison with PPS S S S S

Table 4 The yield and melting point of PPS in various solvents and
Lewis acids.

S S S S
Solvent Al2O3 TiCl4 FeCl3 MoCl5 SbCl5 BF3O(C2H5)2 SnCl4 n
S
C6H5NO2
 Yield (wt%) 31 96 60 29 28 0 0
 Mp (°C) 180 183 150 207 194 – –
CH3NO2
Electrophilic
 Yield (wt%) 50 67 93 9 89 59 0 reaction
 Mp (°C) 135 139 139 108 191 119 – S S S S
n+1
(CHCl2)2
 Yield (wt%) 36 0 42 60 67 0 0
Figure 3 Polymerization mechanism of diphenyl disulfide
 Mp (°C) 124 – 104 115 140 – –
monomer.
 A.S. Rahate et al.: Polyphenylene sulfide      5

5 Characterizations of PPS
5.1 Structure
The crystalline structure of PPS is orthorhombic and its
intramolecular repeating unit reflects an extended back-
bone in which the sulfide group defines a planar zigzag
conformation, as shown in Figure 4. The unit cell dimen-
sions of PPS consist of a = 0.867 nm, b = 0.561, c = 1.026 nm,
confirming the original work of Tabor (1971) showing
the Pbcn cell symmetry with four molecules per unit cell
(Lovinger and Davis 1985). The phenyl rings are inclined
in an alternating manner to the backbone plane, the angle
of inclination being assumed to lie in 40–45° ranges.
An S-S separation along the chain is 0.627  nm and the
C S C bond angle is 110°. X-ray diffraction (XRD) analysis
reflects that there is a conjugation between adjacent pairs
of phenylene rings and the π electrons on the sulfur atom.
It is well known that thermal transition for this polymer
occurs exceptionally at high temperatures, in compari-
son to aliphatic polymer, due to restricted mobility of the
chain imposed by the phenyl group on the backbone.
The properties of semicrystalline polymer, such as PPS,
depend on the degree of crystallinity and morphology of
0.516 nm
the polymer structure. Figure 5 shows the XRD pattern
of the crystalline and amorphous nature (dotted line) of Q4:
PPS. The average crystallite size of the crystalline phase Reference
“Tabor
of PPS determined using Debye-Scherrer formula was (1971) [40]
found to be 8.7505 nm. The amorphous hallow for PPS in has been
XRD is shown by a dotted line. The PPS is a polymer that changed
to “Tabor
crystallizes slowly when compared to other conventional
(1971) and
polymers without aromatic groups, with crystallinity com-
Lovinger and
monly near 50% (Lenz and Handlovits 1960). Tabor (1971) Davis (1985)
and Lovinger and Davis (1985) reported the crystalline to matched
with refer-
density of 1.43 g cm-3 with four chain segments per unit
ence list.
cell. The amorphous density was measured as 1.32 g cm-3.
Please check
The structure of PPS has attracted considerable and confirm
interest as an engineering polymer because of its high
modulus, tensile strength, and good dimensional stabil-
ity. The structural literature available with PPS is still in
a predicament. Hay and Luck (2001) reported the crystal-
line structure of PPS, whereas Gaure and Varma (2007)
explored the semicrystalline behavior of PPS. XRD analy-
sis was used to measure a crystallinity index:
Acryst
C i= × 100
Acryst + Aamorph
where A is the area under the diffraction curve. Curing and
branching reduce the final degree of crystallinity. In fact,
excessive branching and cross-linking produce amor-
phous resins.

5.2 Morphology

The morphology of PPS studied by Chen et  al. (2004)

S S reflects the fluffy nature of the surface, which is typi-
cally required for various applications such as photovol-
taic cells, gas sensors, and ultra capacitors. Anagreha
1.026 nm

70
(110)
S S
60

50
Intensity

40 (002)

30
S S 20

10

0
26 24 22 20 18 16 14 12
2θ Position

Figure 5 X-ray diffraction patterns of PPS. — Crystalline;

Figure 4 Chain structure of PPS. --- amorphous.
6      A.S. Rahate et al.: Polyphenylene sulfide
et  al. (2007) reported the surface modification of PPS
with plasma treatment in various gas atmospheres for
adhesive bonding. The adhesive bonding characteristic
is very useful for chemical stability, oxidation resistance,
and dimensional stability. Adhesive bonding of PPS parts
with aluminum plates is modified by using low-pressure
plasma.
Oxygen plasma pretreatment, independent of the
adhesive, enables a clearly better adhesion to the PPS
surface than argon plasma. The higher bonding strength
after treatment with oxygen plasma is caused by the
higher polar surface energy and the increase of surface
roughness. The surface energy and polar components
hardly rise with increasing pretreatment time. Oxygen
plasma treatment leads to surface tracks, which increase
with treatment time.
5.3 FTIR analysis
The oxidative polymerization of diphenyl disulfide
monomer with various Lewis acids gives PPS. The confor-
mation of polymerization is done through Fourier trans-
form infrared (FTIR) analysis of samples. The principal
bonding in PPS explained with the help of FTIR spectra
is displayed in Figure 6 and mentioned in Table 5 (Piaggio
et al. 1989).
Piaggio et al. (1989) studied the characteristic bands;
the 1093  cm-1 crystalline-related band, and the 1073  cm-1
120
110 PPS
100
% Transmittance
PPS debris
90
80
70
60
1600 1400 1200
Wavenumbers (cm-1)
Figure 6 FTIR spectrum of PPS composite (reproduced with kind permission from (Qixian et al. 1995)).
Table 5 Principal bonding in PPS.
Bondings in PPS Wavenumber (cm-1)
C H (deformation vibration) 818
C C (stretching vibration) 1470
C S 1010–1100
amorphous band have been found most suitable to rep-
resent the crystalline or amorphous structural feature at
the molecular level owing to their sensitive symmetric
and symmetric stretching of the S-phenylene ring group.
Yu et al. (2000) also show the presence of crystalline and
amorphous phases in PPS through FTIR analysis; peak
values are listed in Table 6.
Rahate et al. (2012) have made an attempt to elaborate
the FTIR analysis for amorphous and crystalline phases
of PPS composite using Al2O3 as Lewis acid (Figure 7). The
peak values for crystalline and amorphous phases are
listed in Table 7.
Yu et  al. (2000) reported the intensity or shape of
FTIR bands at 1472, 1389, 1093, 820, 555, and 482 cm-1 for
the crystalline phase of PPS, whereas the intensity of
the FTIR bands at 1573, 1180, 1073, 742, and 707  cm-1 are
attributed to the amorphous content of the sample. The
1093  cm-1 crystalline-related band is composed of contri-
butions of both the crystal and the amorphous fraction
that cannot be separated precisely. Therefore, there is a
tendency to use the 1073 cm-1 amorphous band as a probe
1000 800 600
 A.S. Rahate et al.: Polyphenylene sulfide      7

Table 6 FTIR peak values for crystalline phase and amorphous Table 7 FTIR peak values for crystalline phase and amorphous
phase (Yu et al. 2000). phase (Rahate et al. 2012).

Crystalline phase (cm-1) Amorphous phase (cm-1) Crystalline phase (cm-1) Amorphous phase (cm-1)

1472 1573 1464.02 1558

1389 1180 1369.50 1170.83
1093 1073 1013.14 1105
820 742 511.15 746
555 707

that any deviation from 90° of the angle between adjacent

rings would result in the corresponding variation in the
for characterizing the crystallization behavior of the PPS
electronic intramolecular coupling, which results in a
sample. Piaggio et  al. (1989) studied the characteristic
significant spectroscopic change. This is the main mecha-
bands; the 1093 cm-1 crystalline-related band and 1073 cm-1
nism for the difference in the spectra between the crystal-
amorphous band have been found most suitable to rep-
line and the amorphous PPS samples.
resent the crystalline or amorphous structural feature at
the molecular level owing to their sensitive symmetric and
symmetric stretching of the S-phenylene ring group. The
5.4 Thermal analysis
large descending baseline in the spectral region of 4000–
2000  cm-1 was attributed to conduction free electrons in
The differential thermal analysis (DTA) of molded PPS
the composite (Steijkal and Gilbert 2002). The shift in
compares the increasing temperature of a test material to
standard peak values may be attributed to doping of AlCl3
that of a reference material when both are heated at the
as Lewis acid. The FTIR technique has been verified as a
same constant rate. Any change in the rate of temperature
powerful means for studying polymerization processes for
increase indicates some other change in heat energy of the
it can be used to trace monomer structural changes during
material. For example, low-crystallinity PPS exhibits glass
crystallization, being much more sensitive and precise
transition, recrystallization and melting at the tempera-
than other measurements. Generally, PPS crystallizes in
tures noted on the thermogram shown in Figure 8. Highly
an orthorhombic lattice with the formation of two parallel
crystalline PPS does not show the same recrystallization
chains in the unit cell. The sulfur atoms from each chain
exotherm, but annealed material can exhibit a small endo-
lie on the same plane in a zigzag-like arrangement, and
thermic peak slightly above the annealing temperature. In
the phenylene rings alternatively form an angle of ± 45°
addition, highly crystalline PPS exhibits slightly higher Tg
to this plane (Tabor 1971). Therefore, it may be expected
and Tm with a more sharply defined melting range.
Crystallinity has such an important effect on the
balance of PPS properties that many processors use DTA
as a quality control test. Even without quantitative evalu-
ation, the DTA thermogram can provide a qualitative indi-
cation of whether the part is fully crystallized or not.
The thermal gravimetric analysis (TGA) curves of
LCMO/PPS composite samples are shown in Figure 9
(Gaure and Varma 2007). It is found that the decomposi-
%T

tion of pure PPS and composite starts at about 450°C and

465°C, respectively. In both cases, the dissociation tem-
peratures are above the sintering temperature (400°C) of
the composite.
The effect of thermal treatment on polymer morphol-
ogy can be studied by differential scanning calorimetry
(DSC), shown in Figure 10. In semicrystalline polymers,
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
the DSC scans show the glass transition temperature (Tg)
Wavenumber (cm-1)
and crystalline melting point (Tm). The heating of a sem-
Figure 7 FTIR spectrum of PPS composite (reproduced with kind icrystalline polymer above its Tm will melt the polymer,
permission from (Rahate et al. 2012)). and the cooling process will solidify the polymer in an
8      A.S. Rahate et al.: Polyphenylene sulfide

EXO

Recrystallization, Tc=260°F

Tg=190°F Melting, Tm=545°F

Amorphous PPS
(cold mold)
∆T

Crystalline PPS

Tg=200°F

Annealing endotherm
ENDO

Increasing temperature

Figure 8 TG-DTA of PPS.

1.00 450°C
temperature (Tc). If the sample is heated up to Tm and
PPS
0.95 quenched below the Tg, it becomes solid. However, the
0.90
0.85 polymeric chains will not have time to organize and to
0.80 form crystalline regions, i.e., the sample is in amorphous
Weight (%)

0.75
0.70 solid state despite its tendency to crystallize (Lucas et al.
1.0 465°C
LCMO-PPS
2001, Longo et al. 2011).
0.8 The area above the basis line that is the area under
0.6
the endothermic peak is directly related with the energy
0.4
0.2 absorbed in the polymer crystalline region melting. A
0.0 higher quantity of heat is absorbed during the melting
0 100 200 300 400 500 600 700 800
when the sample chains present are arranged (more crys-
T (°C)
talline regions or higher degree of crystallinity). Also, the
Figure 9 TG-DTA of PPS and LCMO-PPS. opposite is valid; low degree of crystallinity demands a
low quantity of heat.

organized manner, restoring its crystalline arrangement.

The crystal formation is identified by the appearance of
an exothermic peak corresponding to the crystallization
6 Electric and dielectric properties
38
of PPS
Tpeak=285.4°C Q5:
36
Electromagnetic interference (EMI), which is an unwanted Please
disturbance to the electronic devices, may interrupt, confirm
Heat flow (mW) endo up

34
expansion
degrade, or limit the effective performance of the elec- of MWCNT
32
tronic devices. The protection of the devices and circuits
delta H=43.1 J.g-1 against EMI with shielding materials has become an
30
essential issue ( Joo and Epstein 2004, Yang and Dudley
28
2007, Zhang et  al. 2007). The shielding material must
26 Tonset=277.1°C possess good electrical conductivity and dielectric con-
stant. Metals are well suited for many EMI shielding
24
applications. However, metals have their own short-
22 comings like heavy weight, susceptibility to corrosion,
30 60 90 120 150 180 210 240 270 300 330
wear, physical rigidity, etc. The conductive particle-filled
Temperature (°C)
polymer-matrix composites score over these materials with
Figure 10 Differential scanning calorimetry of PPS. advantages like low weight, resistance to corrosion, ease
 A.S. Rahate et al.: Polyphenylene sulfide      9

of processing, and tailored coefficient of thermal expan- 1.E+01

sion (Ishigure et al. 1999, Sandler et al. 1999, Ramasubra- 1.E-01

Electrical conductivity (S/cm)

maniam et al. 2003). 1.E-03
1.E-05

1.E-07
6.1 Electrical properties of PPS 1.E-09
1.E-11
Surface electrical properties of PPS/multiwalled carbon 1.E-13
nanotube (MWCNT) composites were studied by Han
1.E-15
et  al. (2009). PPS/MWCNT composites were prepared by
1.E-17
melt mixing using a twin-screw extruder. Melt mixing is 0 5 10 15 20 25
the preferred method of composite preparation because Wt% GF in PPS matrix

aggregate formation can be minimized by appropriate

application of shear during melt mixing. The surface
electrical conductivity was measured for the in-plane of
polymer/MWCNT composites. To measure the electri-
cal conductivity, four-probe method was used to reduce
contact resistance between the probe and sample surface.
The electrical conductivity of the PPS/MWCNT composite
is shown in Figure 11; it is shown that the electrical con-
ductivity of the PPS/MWCNT composite is increased with
the increase in MWCNT content. For the PPS/MWCNT com-
posite, it appears that the electrical percolation threshold
from the electrical conductivity measurements is about
3 wt% MWCNT.
Goyal and Kadam (2010) explored the electrical prop-
erties of PPS/graphite flake (GF) composites, which were
prepared by mixing PPS and GF in ethanol medium fol-
lowed by hot pressing technique (Goyal and Kadam 2010).
Significant improvement in electrical properties shown
in Figure 12 may be useful for EMI shielding particularly
at high-temperature applications. Composites exhibited
an electrical conductivity percolation threshold of 5 wt%.
The conductivity of 8 and 20 wt% composite is 12 orders of
Figure 12 Weight percent GF in PPS matrix vs. electrical conductiv-
ity (S/cm).
magnitude and 14 orders of magnitude higher than that of
pure PPS, respectively.
The electrical conductivity is imparted to the com-
posite due to the formation of three-dimensional (3D)
conducting paths of GF fillers within the matrix. The
minimum loading of conducting particles at and above
which 3D network is formed within the matrix is called a
percolation threshold (Sandler et  al. 1999). The percola-
tion threshold depends on the aspect ratio, inherent elec-
trical conductivity, and degree of dispersion of filler in the
matrix, nature of interface, and interaction between the
filler and matrix.
Goyal et al. (2011) reported the various compositions
of composites based on PPS and Cu, which were prepared
using mechanical mixing followed by hot pressing (Goyal
et al. 2011). The vol% Cu-dependent conductivity in PPS
composite is displayed in Figure 13. The electrical proper-
ties of high-performance PPS composites reinforced up to

1
PPS/MWCNT 1.E-05
0
1.E-07
Electrical conductivity (S/cm)

Conductivity (S/cm)

-1
1.E-09

-2 1.E-11

-3 1.E-13

1.E-15
-4

1.E-17
-5 0 10 20 30
0 5 10 15 20 25 30 35 Volume % Cu in PPS matrix
Content of MWCNT (wt%)
Figure 13 Volume percent Cu in PPS matrix vs. electrical conductiv-
Figure 11 Content of MWCNT (wt%) vs. electrical conductivity (S/cm). ity (S/cm).
 10      A.S. Rahate et al.: Polyphenylene sulfide
31 vol% Cu particles were investigated to be used as mate-
rials for electronic applications. The significant improve-
ment in conductivity results in conductive cluster in the
matrix, and thus, the composite becomes conductive.
However, on further increasing the Cu content the conduc-
tivity decreased, which may be attributed to the presence
of porosities (Elias 2003) that are the scattering centers
for electrons, and hence, electron mobility is decreased.
Q6: The measured conductivities of about 10-8–10-7  S cm-1 for
The fol- these samples are useful for electrostatic discharge or EMI
lowing
shielding applications.
references
“Ana et al. The temperature dependence of the electrical con-
2012, Yu ductivity for PPS/single-walled CNT (SWCNT) buckypaper
et al. 2007, (BP) composites was reported by Ana et al. (2012) (Díez-
XiaoChun
Pascual et al. 2012b) and is shown in Figure 14. The bucky-
et al. 2007”
are not listed paper-reinforced composite laminates were manufactured
in reference as a sandwich-like assembly of a BP sheet between two
list. Please PPS polymer layers via hot-press processing (Diez-Pascual
supply refer-
et  al. 2012a). The weight fraction of polymer matrix was
ence details
or delete about 80% for PPS-based composites, and their average
them from void content was calculated to be 2.6%. The laminates
text were cut into test specimens with a cutter knife to be used
Figure 14 Temperature dependence of the electrical conductivity of
PPS/single-walled carbon nanotube buckypaper.
for the different characterizations. At room temperature,
the randomly oriented SWCNT-BP possesses a higher
value of electrical conductivity (σ) than PPS-SWCNT-BP.
The discrepancies are attributed to the different degree
of porosity and thickness of the BP sheets (Fisher et  al.
2003, Pham et al. 2008, Park et al. 2009); because thinner
networks are found to exhibit lower intertube contact
resistance, σ rises with increasing temperature, indicat-
ing typical semiconducting behavior (Park et  al. 2009).
The polymer wrapping of the SWCNTs strongly modifies
the electrical conduction mechanism; conductivity in
the composites seems to be hindered by potential barri-
ers between neighboring nanotube bundles due to the
polymer coating. As the concentration of CNT increases,
the samples become more conductive. The electrical prop-
erties of thermoplastic polymers with SWCNT-BP can be
improved for practical applications.
The electrical conductivities of pure PPS and its com-
posites at room temperature are listed in Table 8.
6.2 Nanocomposites of PPS
Kanade et  al. (2005) synthesized the nanocomposites of
CdS nanoparticles in cyclized PPS matrix as shown in
Figure 15. The CdS nanopartcles added into the polymer
matrix through in situ approach.
The sulfur moiety of the polymer forms a bond with
Cd2+ of cadmium salt. This effect, ultimately leading to gen-
eration of nano-CdS which automatically gets entrapped
in thermally formed cyclized PPS matrix.
Zhao et al. (2007) prepared the nanocomposites based
on PPS and expanded graphite (EG) or ultrasonicated EG
(S-EG) were prepared by melt blending and studied its elec-
trically conductive behavior. EG was obtained by heating
the expandable graphite in a muffle furnace at 950°C for
30 s. The variation of the electrical conductivity of PPS/EG
and PPS/S-EG composites is shown in Figure 16.
Table 8 Electrical conductivities in PPS and PPS composites at
room temperature.
Material Composition Conductivity
(S/cm)
PPS – 1.5 × 10-16
Cu in PPS matrix Cu = 18.5 vol%, 4.2 × 10-7
PPS = 60 wt%
Graphite flake in PPS 20 wt% of graphite 1.25 × 10-2
matrix flake
PPS/MWCNT 3 wt% of MWCNT 6.51 × 10-2
PPS/SWCNT-BP 80 wt% PPS 1.8
 A.S. Rahate et al.: Polyphenylene sulfide      11

∆
S Cdl2 S
285°C
n n
Cd2+

Cd2+

n
CdS

Figure 15 Scheme for formation of CdS nanocrystallites in cyclized PPS matrix.

The introduction of EG significantly improved the
conductivity of PPS with a sharp transition from an elec-
trical insulator to an electrical semiconductor. PPS/S-EG
nanocomposites had higher conductivity than PPS/EG
nanocomposites. The PPS/S-EG nanocomposites exhib-
ited higher conductivity due to the small particle size of
S-EG. The conductivity reached 10-2, 10-3 S/cm for both
PPS/S-EG and PPS/EG nanocomposites containing 10%
EG. The notable improvement of electrical conductivity
of composites resulted from the formation of the conduc-
tive network of EG within PPS matrix. According to the
percolation theory (Tsuchida et al. 1987), the percolation
threshold corresponds to the onset of transition from
an insulator to a semiconductor. For PPS/S-EG, PPS/EG
nanocomposites, the percolation threshold values were 1
and 2 wt%, respectively.
Yu et  al. (2007) synthesized the CNT-reinforced PPS
nanocomposites and studied its resistivity behavior with
CNT concentration and as a function of temperature (Yu
et al. 2000). The volume resistivity of the nanocomposites
as a function of CNT concentrations is shown in Figure 17.
The electrical resistance decreases with CNT fraction
and exhibits a percolation. The percolation threshold,
a critical concentration of CNT filler where the resistiv-
ity starts to reduce abruptly, lies between 1 and 2 wt% for
PPS composites. Comparing the electrical behavior of CNT-
reinforced nanocomposites to conventional carbon-black-
filled composites, there are three obvious differences: (1)
The percolation threshold of the CNT-filled polymer is much
lower compared to carbon-black-filled composites – the low
percolation threshold results from the homogeneous dis-
persion of CNTs in polymer matrix and high aspect ratio of
CNT filler; (2) the conducting network formed in CNT-filled
polymer is robust and less segregated; and (3) the percola-
tion curve of CNT-filled polymer is not so steep. It is thus
easier to precisely control the level of electrical resistance for
the material. The temperature dependency of volume resis-
tivity of the PPS/CNT nanocomposites is shown in Figure 18.

0.1

1016
1E-3
Volume resistivity (ohm cm)

1014
Electrical conductivity (S/cm)

1E-5
1012

1010
1E-7
108
PPS/EG nanocomposites
1E-9 PPS/S-EG nanocomposites 106

1E-11 104

102
1E-13
0% 1% 2% 4% 6% 8% 10% -1 0 1 2 3 4 5 6 7 8
EG content CNT concentration (wt%)

Figure 16 Electrical conductivities of PPS/EG composites vs. EG Figure 17 Resistivity of the nanocomposites as a function of CNT
content. concentrations.
12      A.S. Rahate et al.: Polyphenylene sulfide

106 20
H=3kOe
18

16
Volume resistivity (ohm cm)

2 wt% of CNT
14
104
12

MR (%)
10

5 wt% of CNT 8
102
6

7 wt% of CNT 4 x=0

x=0.10
2
x=0.20
100 x=0.30
0
0 20 40 60 80 100 120 140 160 180 200 220
Temperature (°C) -2
75 100 125 150 175 200 225 250 275 300
Figure 18 Temperature dependency of resistivity of the PPS/CNT T (K)
nanocomposites.
Figure 19 Temperature dependence of magnetoresistance (MR) in a
field of 3 kOe of (LCMO)1-x (PPS)x composite samples.

For PPS/CNT composites, their resistance is almost

temperature independent in the temperature range from boundaries and increases the anisotropy in the interfacial
20°C to 200°C. The minimal change in the electrical con- regions and misalignment of the magnetic moments of
ductivity measured shows that the electrical property of the neighboring ferromagnetic domains (De Andres et al.
PPS/CNT nanocomposites is thermally stable and the 1999). Therefore, despite the nonmagnetic character of
composite can be used in electronic devices without any PPS, it is expected to increase the magnetic disorder by
compromise in its electrical properties when temperature disrupting the Mn-O-Mn bonds in the interfacial regions
changes. and hence suppression of the long-range ferromagnetic
Gaure and Varma (2007) prepared polymer-embed- order.
Q7:
ded, La0.7Ca0.3MnO3/PPS (LCMO)1-x/(PPS)x (with x = 0, 0.10, XiaoChun et  al. (2007) studied the electrical bista-
Please
0.20, and 0.30; x is the weight fraction of PPS) compos- ble characteristics of PPS thin film deposited by thermal supply the
ites prepared and their magnetotransport properties were evaporation in vacuum. The PPS (Acros) thin film was manu-
investigated. It has been observed that the incorporation thermally deposited onto the surface of ITO at a rate of 0.2 facturer’s
name, city,
of PPS phase into the LCMO matrix sharply increases the nm/s in a vacuum of 10-3 Pa. Its thickness was about 300
and country
resistivity and lowers the metal-insulator transition tem- nm. Then, Au thin film with a thickness of 20 nm was also for any
perature (TIM). Magnetic measurement reveals that the thermally deposited onto the PPS film. I-V curves and the devices,
ferromagnetic order of LCMO is suppressed by the addi- writeread-erase-read cycles were performed using a pro- equipment,
or software
tion of nonmagnetic PPS. The significant enhancement in grammable Keithley 4200 Semiconductor Characteriza-
mentioned
magnetoresistance (MR) is observed at low temperature tion System is shown in Figure 20. in the
below 175 K for the composites with x = 0.10 and 0.20 with In Figure 20, curve 1 is the same curve of the inset article. For
respect to pure LCMO at magnetic field H = 3 kOe, as shown figure. After the first sweep from 0 to 100 V, a voltage pulse American
manu-
in Figure 19. The enhancement in MR may be due to spin (80 V, 5 s) was applied to the thin film, and then a second
facturers
disorder caused through enhanced spin-polarized tun- sweep from 0 to 76 V was carried out. As shown by curve 2, provide the
neling at the grain boundaries in the composite samples. the thin film showed a higher electrical conductance state state as a
This discrepancy in magnetization (M) leads us to in comparison with curve 1, which corresponds to an ON two-letter
take into account the extra magnetic disorder caused by state (low-resistance state). Then, a 100-V (V min) voltage abbreviation

PPS in the composites. This extra magnetic spin disorder
is induced by grain boundaries in the composites and
suggests the suppression of double exchange mechanism
resulting in suppression of the ferromagnetic alignment
of Mn ions, because the PPS is not incorporated into the
LCMO lattice and it segregates into the grain boundaries
or interfacial regions, which blocks the Mn spins at grain
pulse (5 s) was applied to the thin film and a third voltage
sweep from 0 to 76 V was carried out. As shown by curve 3,
the thin film showed a lower electrical conductance state
in comparison with curve 2 from 0 to 40 V. Referring to
curve 2, this state corresponds to an OFF state.
Band structure calculations on PPS show that the
highest occupied π band has contributions from the sulfur
 A.S. Rahate et al.: Polyphenylene sulfide      13

2.0 high-temperature resistance, makes the PPS resin one of

8.0
Current (A)
6.0
the ideal choices for the composite bipolar plates (Huang
1.6 4.0
et  al. 2005). It can be seen from Figure 21 that the con-
2.0 ductivity of the composite decreases with increase in PPS
resin content. The electrical conductivity of the composite
Current (A)

1.2 0.0
0 20 40 60 80 100
Voltage (V) can reach its maximum value (168.8 Scm-1) when the PPS
0.8
resin content is 20%. The electrical conductivity can be
explained by two mechanisms: interparticle conductivity
and intraparticle conductivity. The interparticle conduc-
0.4
tivity is related to the connectivity by direct contact among
graphite particles. The intraparticle conductivity is pro-
0.0
portional to the conductive path length of the inside of a
0 10 20 30 40 50 60 70 unit particle, or to particle size (Heo et al. 2006).
Voltage (V)

Figure 20 I-V characteristics of the device. Inset: just after the

device was fabricated. 1, The same curve of the inset; 2, after apply- 6.3 Dielectric properties
ing an 80-V pulse; 3, after applying a 100-V pulse; 4, after applying
a 0.92-V pulse. Goyal and Kadam (2010) explored the dielectric proper-
ties of PPS/graphite flake (GF) composites. The dielec-
tric constants for pure PPS and 5 wt% GF composites are
3pz and adjacent carbon 2pz orbits, antibonding in char- almost frequency independent (Goyal and Kadam, 2010).
acter (Cambell and Edmonds 1977). So we believe, after However, the dielectric constant for composites with more
PPS undergoing high electrical field, that migration of than 5 wt% GF content decreased gradually with increas-
electrons from S to C atoms will influence the highest occu- ing frequencies. The significantly higher dielectric con-
pied π band and then influence the electrical conductance stants at lower frequencies are believed to be due to the
of PPS thin film. After the electron transfer, better conju- Maxwell-Wagner polarization originating in the interfaces
gation between S atom and phenyl ring is achieved. The between the GF particles and the matrix (Panwar et  al.
C-S-C angle may become larger, and the overlapping of S 2010, Singh et al. 2010). Dielectric constants for compos-
orbits with phenyl orbits are improved as a result. There- ites as a function of (A) frequency and (B) GF content in
fore, better conductivity is observed. The conversion of the matrix is shown in Figure 22.
PPS from low- to high-conductance state may be due to
the increase of electron density on the phenyl ring result-
ing from electron transfer from S to C.
Xia et al. (2008) reported the PPS/graphite composite
for bipolar plate prepared by simple hot pressing tech-
nique. Graphite and PPS resin powders with different
mixture ratios were first mixed thoroughly in a planetary
high-energy ball miller for 2 h at the speed of 380 rpm and
then hot-pressure molded at different temperatures under
a pressure of 30 MPa for different times to obtain the com-
posite samples. Bipolar plates are important components
in polymer electrolyte membrane fuel cells, which account
for approximately 80% of the fuel cell volume, 70% of the
fuel cell weight, and as much as 60% of the entire stack
cost (Davies et al. 2000).
As most polymer resins intrinsically have low electri-
cal conductivity, higher loading fillers must be added in
order to improve the conductivity and meet the require-
ments of the bipolar plate ( > 100 S cm-1) (Wu et al. 2005).
The superior chemical resistance, coupled with excel- Figure 21 Effect of PPS resin content on conductivity of the
lent mechanical properties, dimensional stability, and composite.
14      A.S. Rahate et al.: Polyphenylene sulfide

A 1.E+09 1.E+04
0.1 MHz
1.E+08 0% 1.E+03
1 MHz
1.E+07

Dissipation factor
1.E+02
Dielectric constant

5% 10 MHz
1.E+06
1.E+01 15 MHz
1.E+05 8%
1.E+04 1.E+00
10%
1.E+03 1.E-01
1.E+02
20%
1.E-02
1.E+01
1.E-03
1.E+00
0 5 10 15 20 25
1.E+05 1.E+06 1.E+07 1.E+08 Wt% GF in PPS matrix
Frequency (Hz)
B 1.E+09 Figure 23 Dissipation factor for composites as a function of GF
0.1 MHz content in the matrix.
1.E+08

1.E+07 1 MHz
Dielectric constant

1.E+06
10 MHz
1.E+05 constants are primarily due to the polarization associated
15 MHz
1.E+04 with the charges induced on Cu particle surfaces and at
the interfaces. Higher dielectric constant for PPS/Cu com-
1.E+03
posites may also be attributed to the presence of a thin
1.E+02
oxide layer on Cu particles. A high dielectric constant
1.E+01 would be beneficial for flexible capacitors and EMI shield-
1.E+00 ing applications (Chung 2001).
0 5 10 15 20 25
Figure 26 shows the dissipation factor of PPS and its
Wt% GF in PPS matrix
composites measured at frequencies varying from 100 KHz
Figure 22 Dielectric constants for composites as a function of (A) to 15 MHz. The dissipation factors of composites except
frequency and (B) GF content in the matrix. C-30 decreased gradually with increasing frequency up to
10 MHz. However, there is not much difference in dissipa-
tion factor measured at 10 and 15 MHz. Figure 27 shows
Figure 23 shows the dissipation factors (tan δ) for the dissipation factor of composites vs. vol% Cu. The dis-
the pure PPS and its composites measured at frequen- sipation factor increased with increased Cu content in the
cies varying from 100 KHz to 15 MHz as a function of EG PPS matrix. The dissipation factor of pure PPS measured
content. The tan δ for pure PPS measured at 1  MHz is at 1 MHz is 0.004. The high dissipation factor is good for
0.005. The tan δ for 0 and 5 wt% composites increases EMI shielding applications.
steadily with increasing frequency but it is lower than 0.1
at all frequencies. The high tan δ is good for EMI shielding
applications. 50
C-0
Goyal et  al. (2011) reported the dielectric properties
C-30
of PPS/Cu composites. Figure 24 shows the dielectric 40
C-45
constants for the pure PPS and its composites measured
Dielectric constant

C-60
at frequencies varying from 100 kHz to 15 MHz. Figure 25 30
C-75
shows the dielectric constant of composites vs. vol% Cu.
The dielectric constants for C-0, C-30, and C-45 compos- 20
ites are almost frequency independent. However, the die-
lectric constants of C-60 and C-75 composites decreased 10
gradually with increasing frequency up to 1 MHz, and
thereafter their dependence seems to be insignificant on 0
100 1000 10,000 100,000
frequencies. The dielectric constant of PPS (1 MHz) is 3.25.
Frequency (in KHz), Lag scale
It can be seen that the dielectric constants of composites
increased with increasing Cu content. Increased dielectric Figure 24 Dielectric constant of composites vs. frequencies.
 A.S. Rahate et al.: Polyphenylene sulfide      15

25 6.4 Conduction mechanism

20 Polyacetylene was prepared as a silvery film by Shirakawa

and coworkers from acetylene, using a Ziegler-Natta cata-
Dielectric constant

15 lyst, in 1974. Despite its metallic appearance, it was not a

conductor. In 1977, however, Shirakawa, MacDiarmid, and
Heeger discovered that oxidation with chlorine, bromine,
10
or iodine vapor made polyacetylene films 109 times more
conductive than they were originally (Shirakawa et  al.,
5
1977). Organic chemistry shows that conjugated double
bonds behave differently from isolated double bonds. As
0 the word indicates, conjugated double bonds act collec-
0 5 10 15 20 25 30 35
tively, knowing that the next-nearest bond is also double.
Volume % Cu in PPS matrix
Huckel theory and other simple theories predict that π
Figure 25 Dielectric constant of composites vs. vol% Cu. electrons are delocalized over the entire chain and that
the band gap becomes vanishingly small for a long enough
chain. One reason for this prediction is the character of the
π molecular orbital, including the p orbital of all carbon
0.8 atoms along the chain of conjugated double bonds. When
0.7 C-0 looking at the distribution of electron density, to which
0.6 C-30 all filled molecular orbitals contribute, the electrons are
Dissipation factor

C-45 predicted to be spaced out rather evenly along the entire

0.5
C-60 chain. In other words, all bonds are predicted to be equal.
0.4
C-75
The role of the dopant is either to remove or to add elec-
0.3 trons to the polymer. For example, iodine (I2) will abstract
0.2 an electron under formation of an (I3-) ion. If an electron
0.1 is removed from the top of the valence band of a semi-
conductive polymer, such as polymer or polypyrrole, the
0
100 1000 10,000 100,000 vacancy (hole) so created does not delocalize completely,
Frequency (KHz), Log scale as would be expected from classical band theory. If one
imagines that when an electron is removed locally from
Figure 26 Dissipation factor of composites vs. frequencies.
one carbon atom, then a radical cation would be obtained.
The radical cation (also called a “polaron”) is localized,
as shown in Figure 28, partly because of Coulomb attrac-
tion to its counterion (I3-), which has normally a very low
0.4
mobility, partly because of a local change in the equilib-
rium geometry of the radical cation relative to the neutral
molecule.
0.3
If a second electron is removed from an already
Dissipation factor

oxidized section of the polymer, either a second inde-

0.2
pendent polaron may be created or, if it is the unpaired
electron of the first polaron that is removed, a bipolaron
is formed. The two positive charges of the bipolaron are
0.1 not independent, but move as a pair, like the Cooper pair
in the theory of superconductivity. Whereas a polaron,
being a radical cation, has a spin of 1/2, the spins of the
0 bipolarons sum to S = 0. Polymer chain defects important
0 5 10 15 20 25 30 35
for conductivity in the polymer are solitary wave defects
Volume % Cu in PPS matrix
known as “solitons”. A soliton is created by isomerization
Figure 27 Dissipation factor of composites vs. vol% Cu measured of the polymer chain and moves by pairing to an adja-
at 1 MHz. cent electron, as shown in Figure 29. However, generally
 16      A.S. Rahate et al.: Polyphenylene sulfide

C Figure 30 Intersoliton hopping: charged solitons (bottom) are

trapped by dopant counterions, while neutral solitons (top) are free
to move. A neutral soliton on a chain close to one with a charged
soliton can interact: the electron hops from one defect to the other.
D

Q8: to that operating in most conducting polymers somewhere

E
Please con- in between the metallic state at high doping and the semi-
firm change conducting state at very low doping. All conjugated poly-
from “undec-
mers do not carry solitons, but polarons can be found in
ahexaene” to Figure 28 Radical cation (polaron) formed by removal of one elec-
“undecahex- tron from the fifth carbon atom of an undecahexane chain (A→B).
most of them. Charge transport in polaron-doped polymers
ane The polaron migration shown in (C→E). occurs via electron transfer between localized states being
formed by charge injection on the chain.
Two aspects remained to be stressed. First, in poly-
solitons made by doping are more important than “bond
meric materials, the charge carriers have not only to move
alternation defects”.
along the chains but also to jump from chain to chain.
Bulk conductivity in the polymer material is limited
The latter process is likely to be the rate-limiting step,
by the need for the electrons to jump from one chain to
which determines the conductivity observed macroscopi-
the next, that is, in molecular terms, an intermolecular
cally. Interchain interactions are thus of prime impor-
charge transfer reaction. It is also limited by macroscopic
tance (Wegner 1984) Models for the interchain hopping
factors such as bad contacts between different crystalline
of solitons or bipolarons have been proposed (Chance
domains in the material. One mechanism proposed to
et al. 1984). Second, these materials are rather amorphous
account for conductivity by charge hopping between dif-
and inhomogeneous. Disorder effects (the importance of
ferent polymer chains is “intersoliton hopping”. Here an
which can be determined from resonant Raman scatter-
electron is jumping between localized states on adjacent
ing experiments) (Vardeny et  al. 1985) need therefore to
polymer chains, as shown in Figure 30; the role of the
be properly taken into account. Many efforts are currently
soliton is to move around and to exchange an electron with
devoted toward developing organic polymers that would
a closely located charged soliton, which is localized. The
be intrinsically better conductors, i.e., which would have
mechanism at work in intersoliton hopping is very similar
smaller band gap. The band gap of polymer is found to
be half that of the parent polymer upon doping. The com-
plete elucidation of the transport mechanism remains
A
one of the major goals to be pursued in the field of con-
ducting polymers. The electrical conductivity can also be
explained by two mechanisms: interparticle conductivity
and intraparticle conductivity. Interparticle conductivity
B
is related to the connectivity by direct contact among filler
particles. Intraparticle conductivity is proportional to the
C conductive path length of the inside of a unit particle, or
to particle size (Heo et al. 2006).
D

E 7 Conclusions
Figure 29 A soliton is created by isomerization of cis-polyacetylene The complete elucidation of the electrical and dielectric
(A→B) and moves by pairing to an adjacent electron (B→E). mechanism remains one of the major goals to be pursued
 A.S. Rahate et al.: Polyphenylene sulfide      17

in the field of conducting polymers. The synthesis of PPS and thermal stability were found to be improved in com-
through the chemical route is the simplest method. The posite form. The electrical conductivity was found to be
structural, morphological, electrical, and dielectric prop- decreased significantly due to addition of SWCNT-BP in
erties of PPS are monomer-to-Lewis acid/oxidant ratio PPS composite.
dependent. The XRD study reveals the crystalline and
amorphous phases in PPS. The adhesive bonding in PPS Acknowledgments: The authors are very grateful to the
for metal contact is found to be improved with surface head of the Department of Physics at Sant Gadge Baba
modification by plasma treatment. The FTIR technique Amravati University, Amravati, India, for providing the
has been verified as a powerful means for studying polym- necessary facilities. A.S. Rahate is very grateful to the
erization processes and also for the analysis of phases. principal, Babasaheb Naik College of Engineering, Pusad.
The TG-DTA technique has been a proficient tool for the
Q9:
As per
analysis of phases of the composite and to determine the
journal style Tg and Tc. The electrical conductivity, dielectric constant, Received November 8, 2012; accepted August 9, 2013
“numbered”
refer-
ences have
changed
to “name References
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Ashok S. Rahate received his MSc degree in Physics from Rashtras-
ant Tukadoji Maharaj Nagpur University, India, in 1983. He worked
as Associate Professor and head in the Department of Applied
Physics in Babasaheb Naik College of Engineering, Pusad, India.
He is currently pursuing a PhD in Physics at the Sant Gadge Baba
Amravati University, Amravati, India under the direction of Dr. S. A.
Waghuley. His current research is on conducting polymers.
Kailash Rambhau Nemade received an MSc degree in physics from
Sant Gadge Baba Amravati University, Amravati, India, in 2011. He
had qualified to take the PAT eligibility tests required for research
fellowship and has received an M.N. Kale Scholarship. He is cur-
rently pursuing a PhD in physics (materials science) at the Sant
Gadge Baba Amravati University under the direction of Dr. S.A.
Waghuley. His current research topics are graphene composites,
quantum dots, and gas sensors.
A.S. Rahate et al.: Polyphenylene sulfide      19
nanostructure-filled polymer composites in the Ku-band
frequency. Micro Nano Lett 2007; 2: 85–89.
Yu J, Asai S, Sumita M. Time-resolved FTIR study of crystallization
behavior of melt-crystallized poly(phenylene sulfide).
J Macromol Sci Part B: Phys 2000; 39: 279–296.
Zhang CS, Ni Q, Fu S, Kurashiki K. Electromagnetic interference
shielding effect of nanocomposites with carbon nanotube
and shape memory polymer. Compos Sci Technol 2007; 67:
2973–2980.
Zhao YF, Xiao M, Wang SJ, Ge XC, Meng YZ. Preparation and
properties of electrically conductive PPS/expanded graphite
nanocomposites. Compos Sci Technol 2007; 67: 2528–2534.
Zheng W, Wong S-C. Electrical conductivity and dielectric properties
of PMMA/expanded graphite composites. Compos Sci Technol
2003; 63: 225–230.
Sandeep Anandrao Waghuley received a PhD in Physics from
Sant Gadge Baba Amravati University, Amravati, India, in 2008.
He worked as Assistant Professor in Physics in the Department of
Physics, Sant Gadge Baba Amravati University. He has been actively
engaged in research since 2002. He is a member of many national/
international professional bodies. Since 2012, he has been coordi-
nator of the Fabrication Laboratory (FABLAB) of the same university.
He has published more than 85 refereed journal articles and book
chapters in the fields of Physics, Chemistry, and Materials Science.
His current research interests include conducting polymers, nano-
composites, sensors, conducting glasses, thin films, quantum dots,
carbon-based materials, and acoustical properties of nanofluids.
 Results in Physics 3 (2013) 52–54

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Results in Physics
journal homepage: www.journals.elsevier.com/results-in-physics

UV–VIS spectroscopic study of one pot synthesized strontium oxide

quantum dots q
K.R. Nemade, S.A. Waghuley ⇑
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India

a r t i c l e i n f o a b s t r a c t

Article history: The properties of drastically change when matter makes transition from 1D, 2D, 3D, to 0D. The quantum
Received 28 December 2012 dots (QDs) of strontium oxide (SrO) were synthesized by one pot chemical precipitation method using
Accepted 4 March 2013 hexamethylenetetramine (HMT). The radius of SrO QDs was calculated from hyperbolic band model
Available online 13 March 2013
(HBM). The direct and indirect band gaps of SrO QDs were estimated from UV–VIS analysis. The particle
size was found to be 2.48 nm. The quantum confinement effect in SrO QDs is discussed through exciton
Keywords: Bohr radius. The particle size from UV–VIS analysis is in excellent agreement with fluorescence and TEM.
Strontium oxide
Ó 2013 The Author. Published by Elsevier B.V. All rights reserved.
Quantum dots
UV–VIS analysis

1. Introduction and stable systems with well-defined crystallographic structures.

The optical and electronic properties of materials change dras-
tically due to the quantum confinement of the charge carriers
within the particle. SrO, an important wide band gap metal oxide
(MOX) has attracted much attention. Jose et al. [1] reported the
glass system of SrO for new broadband Raman gain media. Due
to the inherent high-energy phonons in silicate-based glasses,
usable rare-earth ions, which are optically active for optical ampli-
fication, are limited in silicate-based fibers. Because fluoride and
heavy metal oxide glasses have low energy phonons and many
rare-earth ions are optically active in them, these glasses have been
studied as rare-earth hosts to expand amplification bandwidth in
wavelength division multiplexing (WDM) systems [2]. There has
been several method for the synthesis of MOX by low-temperature
routes to obtain relatively homogeneous and small-sized grains.
These methods include chemical precipitation, hydrothermal reac-
tion and the sol gel method. Here we discuss chemical precipita-
tion method for the synthesis of SrO QDs [3].
MOX nanoparticles can exhibit unique physical and chemical
properties due to their limited size and a high density of corner
or edge surface sites. Particle size is expected to influence three
important groups of basic properties in any material. The first
one comprises the structural characteristics, namely the lattice
symmetry and cell parameters [4]. Bulk oxides are usually robust
q
This is an open-access article distributed under the terms of the Creative
Commons Attribution License, which permits unrestricted use, distribution, and
reproduction in any medium, provided the original author and source are credited.
⇑ Corresponding author. Tel.: +91 9423124882; fax: +91 07212662135.
E-mail address: sandeepwaghuley@sgbau.ac.in (S.A. Waghuley).
However, the growing importance of surface free energy and stress
with decreasing particle size must be considered: changes in ther-
modynamic stability associated with size can induce modification
of cell parameters and/or structural transformations [5] and in ex-
treme cases the nanoparticle can disappear due to interactions
with its surrounding environment and a high surface free energy
[6]. Although, SrO is a dangerously radioactive isotope, it is a useful
by-product of nuclear reactors from which spent fuel is extracted.
Its high-energy radiation can be used to generate an electric cur-
rent, and for this reason it can be used in space vehicles, remote
weather stations and navigation buoys [7].
The optical conduction is one of the fundamental properties of
metal oxides and can be experimentally obtained from reflectivity
and absorption measurements. Due to quantum-size confinement,
absorption of light becomes both discrete-like and size-dependent.
In nano-crystalline semiconductors, both linear (one exciton per
particle) and non-linear optical (multiple excitons) properties arise
as a result of transitions between electron and hole discrete or
quantized electronic levels. In the first case, depending on the rela-
tionship between the radius of the nanoparticle (R) and the Bohr
radius (RB) of the bulk exciton, the quantum confinement effect
can be divided into three categories; weak, intermediate and
strong confinement regimes, which correspond to R  RB, R  RB,
and R  RB, respectively [8]. The effective mass theory (EMA) is
the most elegant and general theory to explain the size depen-
dence of the optical properties of nanometer semiconductors.
In the present work, SrO QDs are synthesized by one pot chem-
ical precipitation method. The direct and indirect band gaps of QDs
are determined through UV–VIS analysis. The quantum dot radius
is computed from hyperbolic band model (HBM) using UV–VIS

2211-3797/$ - see front matter Ó 2013 The Author. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.rinp.2013.03.001
 K.R. Nemade, S.A. Waghuley / Results in Physics 3 (2013) 52–54 53

analysis. The effective mass approximation is used to find out the

particle size in case of fluorescence spectroscopy. The confirmation
is done through TEM.

2. Experimental

The AR grade (SD Fine, India) chemicals were used in this work.
The SrO QD was arrested by one pot chemical route approach. The
reaction is shown below.
SrðNO3 Þ2 þ C6 H12 N4 ! SrO þ C6 N6 þ 6H2 O
The 1 M HMT was dissolved in 5 ml double distilled water sep-
arately. After rigorous stirring, 1 M strontium nitrate was added in
the solution. The HMT is used as a nitrate remover (precursor re-
mover). The reaction was stood for 2 h at room temperature. The
precipitate so obtained was vacuum filtered and filtrate was first
dried at room temperature for 24 h and sintered at 100 °C for
3 h. The SrO QDs prepared in this way were characterized by Fig. 2. Direct band gap of SrO QDs.
UV–VIS analysis on a Perkin Elmer Spectrophotometer. The TEM
analysis is used to know the particle size of SrO QDs. The fluores-
cence analysis was done on a FL Spectrophotometer (Model: HIT- of direct and indirect bands are determined by extrapolating the
ACHI, F-7000). The slit width was adjusted to 5 nm. The sample straight-line portion of (ahm) versus hm graph to the hm axis. The
for TEM analysis was prepared by carbon-coated copper TEM grids. band gap of bulk SrO is 1.8 eV [9].
The measurements were performed on a JEOL Model 1200EX Fig. 2 shows the direct band gap of SrO QDs which is found to be
instrument operated at an accelerating voltage of 120 kV. at 6.14 eV (Enano). This confirms the nanophase of material. It is
also reflected from HBM analysis.
3. Results and discussion By considering absorption edge at 203 nm, the QDs radius was
estimated by using the HBM (Eq. (2)) [10].
The analysis of UV–VIS spectra of SrO QDs shown in Fig. 1 was vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
carried out with a view to explore their optical properties. u 2p2 h2 Ebulk
R¼ t ð2Þ
Fig. 1 shows that the% transmission is higher on lower wave- m ðE2nano  E2bulk Þ
length side. It was seen that the strongest absorption appears at
wavelength 203 nm. At lower wavelengths edge absorption rep-
where Ebulk is bulk band gap, Enano is band gap of nanomaterial, m⁄
resents the quantum confinement effect present in the synthesized
is effective mass of electron in bulk SrO. (m⁄ = 0.24 m0). The QDs ra-
SrO QDs. Many applications of the materials depend upon its direct
dius was found to be 1.24 nm. Hence the particle size estimated as
and indirect band gap values. The relation between absorption
2R is 2.48 nm.
coefficient (a) and incident photon energy (hm) can be expressed
Fig. 3 shows the indirect band gap of SrO QDs. It is found to be
as Eq. (1).
6.1 eV by substituting the exponent value n = 2 in Eq. (1). The shift-
Aðhv  Eg Þn ing of band gap from 6.14 to 6.1 eV confirms the presence of indi-
a¼ ð1Þ
hv rect band gap. The difference 0.04 eV may represent the energy of
lattice phonon. The highest energy phonons correspond to intra-
where A is constant and Eg is the band gap of the material. The
cellular vibrations, in our case found to be 0.04 eV that should
exponent n depends on the type of the transition, its value is 1
not have seriously affected the size of the QDs [11]. There may
for direct band gap and 2 for indirect band gap. The exact values
be some effect of phonon energy but not strapping which affects
the UV–Visible spectra. Thus the SrO QDs are defect free. The de-
fects may not exist around the QDs’ surface.

Fig. 1. UV–VIS Spectra of SrO QDs. Fig. 3. Indirect band gap of SrO QDs.
54 K.R. Nemade, S.A. Waghuley / Results in Physics 3 (2013) 52–54
Fig. 4. Emission spectrum of SrO QDs under 254 nm excitation.
The exciton Bohr radius of SrO QDs was estimated as in refer-
ence [8]. In this study it was found to be 1.983 nm. This value is
greater than the quantum dot radius. This is in agreement with
R  RB, which shows the presence of strong quantum confinement
regime in SrO QDs.
In order to calculate the particle size, fluorescence measure-
ments were made at an excitation wavelength of 254 nm and fluo-
rescence observed from 320 to 500 nm, displayed in Fig. 4. The
fluorescence is the exciton recombination, which directly probe
the optical band gap of the particles. This emission frequency is
perceived as fluorescence and depends on the size of the band
gap, which can be altered by changing the size of the QD as well
as changing the surface chemistry. It is important to note that
the smaller the QD, the higher the band gap energy. This size tun-
able absorption and emission property of QDs is extremely valu-
able for quantum dot analysis. QDs are fluorescent
semiconductor nanocrystals, range in size from 2 to 25 nm in
diameter and contain approximately 200–10,000 atoms leading
to the effects of quantum confinement [12].
The particle size was calculated using the effective mass
approximation (EMA) assuming exciton confinement in particle
with. The optical band gap and particle size are correlated with
Eq. (3) [13].
2   2
h 1 1 e
Eg ¼ Ebulk þ þ 
8r 2 me mh 4pe0 er ce
where r is the radius of the particle, ce is the Bohr exciton radius and
Ebulk is the band gap of bulk SrO, er is relative dielectric constant, e0
is dielectric constant of air. me effective mass of electron in SrO, mh
is effective mass of hole. These calculations resulted in the radius of
particle of SrO QDs. r is found to be 1.33 nm, 2r = 2.67 nm gives the
particle size.
The TEM image of SrO QDs is shown in Fig. 5. This shows that
the QDs are spherical in shape. The small amount of agglomeration
of QDs is observed in the micrograph. The average particle size is
observed to be 3 nm. The average particle size estimated from
UV–VIS analysis and fluorescence spectroscopy is in good agree-
ment with the TEM investigation. Micic et al. [14] reported the
EMA break down at a lower particle size. This observation is not
evidenced in the present case. Imaging a small dot through
Fig. 5. TEM image of SrO QDs.
electron microscopy technique is not enough to say it is in a quan-
tum dot state [15]. The optical absorption is a technique that al-
lows one to directly probe the band gap of QDs. The band gap
edge of a material should be blue shifted if the material is confined.
This blue-shifted spectrum confirmed the formation of QDs. In our
case, the intense absorption is observed at 203 nm.
4. Conclusions
The nanosize SrO QDs were successfully synthesized by chemi-
cal route. The direct and indirect band gap values for SrO QDs were
found to be 6.14 eV and 6.1 eV, respectively. The radius of SrO QDs
was computed by HBM and found to be 1.24 nm. Thus the particle
size was 2.48 nm. The energy of lattice phonon may be observed as
0.04 eV. The exciton Bohr radius of SrO QDs was estimated to be
1.983 nm. This value is greater than the quantum dot radius. This
is in agreement with R  RB. This indicates the presence of strong
quantum confinement regime in SrO QDs. The average particle size
from TEM analysis was observed to be 3 nm. This agrees with
UV–VIS analysis and fluorescence spectroscopy.
Acknowledgement
Authors are very much thankful to the Head, Department of
Physics Sant Gadge Baba Amravati University, Amravati for provid-
ð3Þ ing necessary facilities.
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 Solid State Sciences 22 (2013) 27e32

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Solid State Sciences

journal homepage: www.elsevier.com/locate/ssscie

LPG sensing application of graphene/Bi2O3 quantum dots composites

K.R. Nemade, S.A. Waghuley*
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444 602, India

a r t i c l e i n f o a b s t r a c t

Article history: Liquid petroleum gas (LPG) sensing characteristics of graphene/Bi2O3 quantum dots (QDs) composites
Received 16 April 2013 have been studied. The prepared materials were characterized through X-ray diffraction, atomic force
Received in revised form microscopy, Raman, high resolution-transmission electron microscopy along with selected area electron
7 May 2013
diffraction, ultravioletevisible spectroscopy, fluorescence spectroscopy and thermo gravimetric-
Accepted 9 May 2013
differential thermal analysis. The X-ray diffraction pattern of Bi2O3 showed broad peaks and intense
Available online 24 May 2013
absorption at 362 nm in UVeVIS spectrum confirms that chemically synthesized Bi2O3 particles are
quantum dots. The composites show significant better performance towards the LPG. The defects
Keywords:
Graphene
chemistry was employed to analyse the increasing gas sensing properties with an increasing wt.% of
Bi2O3 graphene. Also, excellent correlation observed between the defects concentration (IUV/IDL) and sensing
LPG response as a function of wt.% of graphene.
Ó 2013 Elsevier Masson SAS. All rights reserved.

1. Introduction
LPG is a very competent energy source that burns in a clean way,
but due to extremely flammable nature this gas is hazards to
humans [1]. LPG is invisible and has no natural smell, so a unique
smell is added to make possible any leaks to be detected. Due to its
highly explosive nature, even for low concentration (ppm) creates
serious problem [2]. Hence, it is important to detect it at its lower
concentration very efficiently. Metal oxide based LPG sensors en-
ables to detect lower concentration of LPG presence, but suffer from
lack of selectivity and high operation temperature [3]. The detec-
tion of LPG at higher temperature increases power consumption
and risk [4]. For this, many efforts are made by researchers to
investigate novel LPG sensing materials. Gurav et al. reported the
LPG sensing using Pd-sensitized vertically aligned ZnO nanorods
[5] with operating temperature 573 K. Hence, the present work is a
bold attempt to resolve high temperature operation disadvantage
using novel material graphene/Bi2O3 composite.
As a potential candidate in material science, graphene has
excellent gas sensing properties due to its high surface to volume
ratio [6]. Schedin et al. reported graphene based FET (field-effect
transistors) to detect the absorption of a single gas molecule [7].
The Bi2O3 is much more known transition metal oxide semi-
conductor. It has been extensively investigated for various appli-
cations as photocatalyst [8], ion conducting solid electrolyte [9],
* Corresponding author. Tel.: þ91 9423124882.
E-mail address: sandeepwaghuley@sgbau.ac.in (S.A. Waghuley).
optical and electrical material in solid oxide fuel cells [10] and
oxygen sensors [11], and selective sensing material for NO detec-
tion [12]. In the last decade, Bi2O3 has been reported with various
morphologies, such as nanorods [13], nanotubes [14], nanowires
[15] and nanofibers [16]. Due to such morphology, Bi2O3 has found
numerous modern applications in electronics and electro-optics
[17e20], catalysis [21] and gas sensors [11].
In the present work, for the first time, we explored the LPG
sensing properties of graphene/Bi2O3 composite. Much effort has
been put to reduce operating temperature in order to reduce
operation cost and risk. The structural, morphological, optical and
thermal properties of graphene/Bi2O3 composite were investigated
using X-ray diffraction (XRD), atomic force microscopy (AFM),
Raman, high resolution-transmission electron microscopy (HR-
TEM)-selected area diffraction pattern (TEM-SAED), ultraviolete
visible (UVeVIS) spectroscopy, fluorescence spectroscopy and
thermo gravimetric-differential thermal analysis (TG-DTA).
2. Experimental
The Bi2O3 QDs were obtained through chemical route. In a
typical experiment, precursors bismuth nitrate (1 M) and hexa-
methylenetetramine (HMT) (1 M) were dissolved in 30 ml double
distilled water separately. The solutions were mixed thoroughly by
addition of HMT drop-by-drop under magnetic stirring for 2 h at
room temperature. Subsequently, the product was kept for a
centrifuge operating at 3000 rpm for 30 min. This centrifuged
precipitate was collected through cellulose nitrate filter paper. The

1293-2558/$ e see front matter Ó 2013 Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.solidstatesciences.2013.05.008
28 K.R. Nemade, S.A. Waghuley / Solid State Sciences 22 (2013) 27e32

filtrate was dried at room temperature for over night in vacuum

chamber and then sintered at 373 K for 3 h.
The electrochemical exfoliation method was used to synthesize
graphene; during the process silver was used as a cathode and
graphite flake as anode. The electrodes were inserted into the ionic
solution with separation of 5 cm. The ionic solution was prepared
by taking 4.8 g of sulphuric acid diluted in 100 ml of double distilled
water [22]. Exfoliation process was carried out by DC bias
arrangement (10 V) at room temperature. The prepared graphene
was collected through cellulose nitrate filter paper and washed
with double distilled water several times. The obtained sample was
dried at 373 K for 2 h.
The graphene/Bi2O3 QDs composites were prepared by mixing
graphene in constant 1 g Bi2O3 QDs, where acetone used as organic
media. The solution was thoroughly mixed by magnetic stirrer for
30 min at room temperature. The resultant solution was kept for over
night for evaporation of acetone. In this manner, prepared composite
was sintered at 373 K for 1 h. During this stage, complete evaporation
of acetone takes place. Same method was employed to prepare
composite with varying wt.% of graphene from 20 to 80 wt.%.
The X-ray diffraction (XRD) patterns of samples were recorded
on an XRD Philips PW 1830 using CuKa radiation (l ¼ 1.54  A) in the
range 1060 . The morphology of the samples was studied using
imaging techniques, high resolution-transmission electron micro-
scopy (HR-TEM)- selected area electron diffraction (SAED) (Philips
Tecnai F-30107). The surface topography and thickness distribution
of graphene was observed by AFM on Bruker Webinar Series.
Raman spectra was acquired on a BRUKER RFS 27: Raman Spec-
trometer using Nd: YAG laser source of excitation 514 nm. The
optical transmission was measured by a UVeVIS spectrophotom-
eter (Perkin Elmer) for the conformation of quantum confinement.
The fluorescence analysis was done on FL Spectrophotometer
(Model: HITACHI, F-7000) to know the defects density. The thermal
stability of material analysed through thermo gravimetric-
differential thermal analysis (TG-DTA) on Shimadzu DTG-60h
Fig. 1. XRD patterns of (a) graphene, (b) Bi2O3 QDs and (c) 20 wt.%, (d) 40 wt.%, (e)
thermal analyser under nitrogen atmosphere. 60 wt.% and (f) 80 wt.% graphene/Bi2O3 QDs composites.
The chemiresistor films for LPG sensing were prepared by
screen-printing on glass substrate of size 25 mm  25 mm and then pattern shown in Fig. 1 (a), indicates the formation of graphene.
dried at room temperature for 24 h [23]. The heating treatment was There are two prominent peaks (002) and (100) which are char-
given to the film at 373 K for 3 h. For surface resistance measure- acteristic peaks of graphene [24]. Fig. 1(b) shows the structural
ment, the electrodes of silver were deposited on adjacent sides of purity of Bi2O3 QDs. There are seven prominent peaks observed in
the film and then it was kept to heating at 353 K for 15 min for the XRD pattern, (102), (122), (212), (014), (302), (304), and (323)
drying the silver paint. The sensing response was determined from which are characteristic peaks of Bi2O3 QDs. All the peaks exactly
resistance change of chemiresistor. The electrical resistance was match with JCPDS Data Card No. 41-1449. The XRD pattern of
measured by using a voltage drop method adopted by Waghuley composites shows in Fig. 1 (c)e(f) displays broad hump peak, which
et al. [23]. The gas sensing response of chemiresistor is defined as implies that the composites are nanocrystalline or loose the crys-
 tallites [25]. This loose crystallites may be due addition of graphene
DR R g  R a j
S ¼ ¼ (1)
Ra Ra
where Ra is the resistance of chemiresistor in air and Rg is the
resistance chemiresistor in gas. The response time was determined
by injecting known amount of gas in the chamber. The time taken
by chemiresistor to achieve 90% of its highest value was considered
as response time. While, the recovery time of the chemiresistor was
defined as the time taken for its resistance to be reduced by 90%
from its highest value. The experiment was carried out 5 times for
reproducibility of chemiresistors.
3. Results and discussion
3.1. Materials characterization
Fig. 1(a)e(f) depicts the XRD patterns of graphene and Bi2O3 QDs
along with (20e80 wt.%) graphene/Bi2O3 QDs composites. The XRD
in Bi2O3 induce disorder/defects in the structure [26,27]. The
crystallite size decreases with an increase in the wt.% of graphene.
DebyeeScherrer formula was used to calculate the crystallite size.
The average crystallite size of Bi2O3 QDs was found to be 4.63 nm
and for composites, it was found to be ranges between the 5.23 and
5.68 nm. The smallest crystallite size was found to be 5.23 nm for
80 wt.% graphene/Bi2O3 QDs composite. The crystallite size of
composites does not show significant difference.
Fig. 2(a) shows AFM image and thickness profile of graphene.
The thickness distribution of graphene was 1.77 nm, indicated the
few layered structure of graphene possesses 5e6 layers. The Raman
spectrum of graphene is shown in Fig. 2(b). The prominent Raman
features of FLG are D-band (w1300 cme1), G-band (w1580 cme1)
and 2D-band (w2700 cme1). The D-band is known as the defect
concentration band. The intensity of the D-band is directly pro-
portional to the concentration of defects. The G-band assigned to
in-plane vibration of sp2 carbon atoms [28]. The 2D-band originates
from a two-phonon double resonance process [29].
 K.R. Nemade, S.A. Waghuley / Solid State Sciences 22 (2013) 27e32 29

Fig. 2. (a) AFM image with thickness distribution of graphene and (b) Raman spectrum of graphene.

image of graphene shows a wrinkled sheet like structure at the

edges. Inset of Fig. 4(a) shows the SAED image of graphene. The
planes appeared in SAED image are agreed with the results ob-
tained from XRD analysis. The SAED image is clearly visible, and the
bright diffraction spots reflect the hexagonal symmetry [30].
Fig. 4(b) presents the TEM image of Bi2O3 QDs. TEM image shows
the small amount of aggregation of Bi2O3 QDs. The average crys-
tallite size of Bi2O3 QDs estimated from XRD analysis agrees with

Fig. 3. UVeVIS spectra of the Bi2O3 QDs dispersed in distilled water. Inset shows the
optical photograph.

Fig. 3 shows UVeVIS spectrum of Bi2O3 QDs. The plots show

intense absorption at 362 nm. This absorption in UV region con-
firms the presence of quantum confinement.
The morphology of as-prepared graphene was examined
through TEM; representative image is shown in Fig. 4(a). The TEM Fig. 5. TEM and SAED image of 80 wt.% graphene/Bi2O3 QDs composite.

Fig. 4. (a) TEM image of graphene and inset shows the SAED image. (b) TEM image of Bi2O3 QDs shows the aggregation of particles and inset shows the SAED image.
30 K.R. Nemade, S.A. Waghuley / Solid State Sciences 22 (2013) 27e32
Fig. 6. TGeDTA curves of 80 wt.% graphene/Bi2O3 QDs composites.
TEM investigation. The inset image shows the SAED image, which is
consistent with the diffraction planes obtained from XRD analysis.
The HR-TEM image of the 80 wt.% graphene/Bi2O3 QDs com-
posite provided in Fig. 5. This image shows hybridised structure of
graphene and Bi2O3 QDs. The inset of Fig. 5 shows the SAED image
of composite; reflects composite possesses less crystalline or
amorphous structure. This result is consistent with XRD analysis.
Fig. 6 demonstrates the TG-DTA of 80 wt.% graphene/Bi2O3 QDs
composites, in order to study the changes occurred regarding the
phase transition during heat treatment to the sample. The TG-DTA
analysis was carried out from room temperature to 775 K in ni-
trogen atmosphere.
According to the % TGA curve, the sample shows sharp weight
loss upto 373 K and DTA shows an endothermic pick at 346 K
corresponding to the evaporation of absorbed water. The total mass
loss from room temperature to 453 K was about 7.0339%. The DTA
curve shows another peak at 551 K, corresponds to the evaporation
of the constitution water in Bi2O3 QDs. The weak peak at 578 K
assigned to the oxidation of amorphous carbon present on the
surface of graphene [31]. The exothermic peak appears at 759 K,
which may be associated with the phase transition from a-Bi2O3 /
d-Bi2O3 in composite [32]. The thermal study of sample shows the
stability of composite material in the vicinity of operating tem-
perature of 80 wt.% graphene/Bi2O3 QDs composites chemiresistor.
The sensing characteristics are significantly influence by defects
concentration on the sensing surface [33,34]. Thus, the fluores-
cence spectroscopy is straightforward approach of measurements
of defects density. Fig. 7 shows the fluorescence spectrum of (20e
Fig. 7. Fluorescence spectrum of (20e80 wt.%) graphene/Bi2O3 QDs composites.
Fig. 8. Response of chemiresistors towards CO2 (30 ppm) and LPG (30 ppm) at 398 K.
80 wt.%) graphene/Bi2O3 QDs composites. From plots, it is observed
that the intensity value of ultraviolet (IUV) enhanced with an in-
crease in wt.% of graphene. This shows that the graphene surface
becomes defects rich in the presence of Bi2O3 QDs. The intensities
ratio of the ultraviolet (IUV) to visible leep levels (IDL) is measure of
defect concentration [34].
3.2. LPG sensing characteristics
The capability of a chemiresistor to respond to a definite gas is
known as selectivity. The selectivity response of chemiresistors was
checked towards to 30 ppm CO2 and LPG at 398 K. The results are
shows in Fig. 8. The composites are more selective towards the LPG,
than CO2. It is clearly observable that 80 wt.% graphene/Bi2O3
composites chemiresistor is highly selective.
As the composite chemiresistors are more selective towards the
LPG, the sensing response of chemiresistors was measured as a
function of concentration of LPG at room temperature (303 K). The
results are presented in Fig. 9. The chemiresistors shows an in-
crease in response as a function of LPG concentration upto
100 ppm. Beyond 100 ppm, response of chemiresistors decline
from linearness. This suggested the saturation effect of chemir-
esistors. From the plots, it is observed that 80 wt.% graphene/Bi2O3
composite highly responsive even at room temperature. This may
be due the smaller crystallite size, which provides a larger surface
Fig. 9. Chemiresistor response as a function of concentration of LPG.
 K.R. Nemade, S.A. Waghuley / Solid State Sciences 22 (2013) 27e32
Fig. 10. The variation of defects density (IUV/IDL) ratio and LPG sensing response with
the wt.% of graphene.
to volume ratio for gasesolid interaction [35]. An additional reason
for increase in response with wt.% of graphene attributed to an
increase in defects concentration. Fig. 10 shows the variation of
defects density (IUV/IDL) ratio and LPG sensing response as a func-
tion of wt.% graphene. From the plots, it is analysed that LPG
response increases linearly with defects concentration and wt.%
graphene. This result is consistent well with the [34].
Gas sensing action basically depends on electron transfer re-
actions, which are redox reactions. The free energy that drives the
reaction is the difference in reduction potentials between donor
and acceptor [36]. As mentioned above, gas sensing related to de-
fects, that is oxygen vacancies can act as adsorption sites for gas
molecules. The reactions for adsorbed oxygen ions are as follows
(Eqs. (2)e(4)) [37].
O2 ðgasÞ/O2 ðadsÞ (2)
O2 ðadsÞ þ e /O
2 ðadsÞ (3)
O  
2 ðadsÞ þ e /2O ðadsÞ (4)
It is well known that LPG is composition of CH4, C3H8, C4H10, etc.,
and these molecules having tendency to donate electron to the
surface. When the chemiresistor is exposed to LPG, it interacts with
Fig. 11. Chemiresistor response as a function of operating temperature to 50 ppm LPG.
31
the adsorbed oxygen ions and formed H2O and CO2. The reaction
between LPG and adsorbed oxygen ions are as follows (Eqs. (5) and
(6)) [35].
Cn H2nþ2 þ 2O ðadsÞ/H2 O þ Cn H2n : O þ e (5)
Cn H2n : O þ O ðadsÞ/CO2 þ H2 O þ e (6)
The response of chemiresistors towards the 50 ppm LPG as a
function of operating temperature is shown in Fig. 11. All curves
shows a highest sensing response values corresponding to tem-
perature. From the plot, it is examined that all composites possess
low operating temperature at 398 K. The 80 wt.% graphene/Bi2O3
composites exhibited the optimum value of sensing response. This
is the most important accomplishment of present investigation,
which reduced the operation cost. Besides that, sensing of LPG at
elevated temperature is tricky due to its explosive nature. This
problem resolved up to some extent by present study. The response
value start to decreases from certain temperature, this may be due
to desorption of oxygen ions from sensing surface [37].
The primary sensing mechanism is applicable to pure graphene
and Bi2O3 QDs, which is based on charge transfer between adsor-
bed gas molecules and sensing surface, leading to change in its
resistance. It is known that a certain amount of oxygen from air is
adsorbed on the surface of the chemiresistors. The graphene and
Bi2O3 QDs interact simply with the oxygen, by transferring the
electrons from the conduction band to adsorbed oxygen atoms.
Therefore, the adsorption of LPG molecules on the sensing surface
is the dominant sensing mechanism [38e40]. Careful analysis of
sensing mechanism in case of composites shows that Bi2O3 QDs act
as active sensing sites by damaging the graphene surface, which
may create vacancies or dangling bonds on graphene surface and
subsequently, enhance defects density [28].
In order to check the stability of 80 wt.% graphene/Bi2O3 com-
posites, its responses to 100 ppm LPG was measured for 30 days at
an interval of 5 days at room temperature. The results are illus-
trated in Fig. 12. The chemiresistors have nearly constant response
to LPG indicating the good stability. The transient response char-
acteristic of 80 wt.% graphene/Bi2O3 composite chemiresistor to
100 ppm LPG were studied at room temperature and displayed in
inset of Fig. 12. In this measurement, gas inserted in the chamber
and resistance of chemiresistor was measured in air and in
Fig. 12. Stability and transient response (inset) characteristics of 80 wt.% graphene/
Bi2O3 QDs chemiresistor to 100 ppm LPG.
32 K.R. Nemade, S.A. Waghuley / Solid State Sciences 22 (2013) 27e32
presence of gas. The 80 wt.% chemiresistor shows fast response
time towards the LPG of the order 16 s. For measuring the recovery
time, chemiresistor was exposed to air. The chemiresistor achieve
fast recovery in 20 s. The results indicate that the chemiresistor can
meet the practical application for detection of LPG.
On the basis of above discussion, it can be hypothesized that, as
a general, increasing the graphene content in Bi2O3 enhances the
sensing response to LPG. Obviously, a more detailed investigation is
necessary to validate this hypothesis. Further work on enhance-
ment of sensing response is currently under way.
4. Conclusions
The addition effect of graphene on LPG sensing properties of
graphene/Bi2O3 QDs composites was successfully investigated. It
was found that the addition of graphene into Bi2O3 QDs, makes
graphene surface defective. This directly and simply confirmed
using fluorescence spectroscopy. Simultaneously, provide strong
support to improvement in LPG sensing properties based on defect
density. The 80 wt.% graphene/Bi2O3 composite possesses high
sensing response; low operating temperature, fast response and
recovery time along with good stability are adequate to be a
practical LPG sensor. Low operating temperature feature of 80 wt.%
graphene/Bi2O3 composite chemiresistor reduced the operation
cost as well as risk.
Acknowledgments
Authors are very much thankful to Head, Department of Physics
Sant Gadge Baba Amravati University, Amravati, India for providing
necessary facilities.
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