Sensors and Actuators B 119 (2006) 676682

Hydrothermal synthesis of highly crystalline ZnO nanoparticles:

A competitive sensor for LPG and EtOH
Babita Baruwati, D. Kishore Kumar,
Sunkara V. Manorama
Nanomaterials Laboratory, Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology,
Hyderabad 500007, India
Received 7 October 2005; received in revised form 13 January 2006; accepted 16 January 2006
Available online 20 February 2006

Abstract
Highly crystalline zinc oxide (ZnO) nanoparticles have been synthesized by hydrothermal route at 120 C over a range of different time periods.
The synthesized nanoparticles are characterized for their phase and morphology by X-ray diffraction (XRD) and transmission electron microscopy
(TEM). Thermogravimetric-differential thermal analysis (TG-DTA) follows the thermal changes accompanying the heat treatment and ultra-violet
diffuse reflectance spectroscopic studies (UV-DRS) give a measure of the optical properties. Electrical properties of the synthesized nanoparticles
are studied by AC impedance and DC conductivity measurement. The gas sensing properties were studied towards reducing gases like liquefied
petroleum gas (LPG), ammonia, hydrogen, ethanol (EtOH), etc., and it is observed that the nanoparticles show high sensitivity to LPG and ethanol
at relatively low operating temperatures. Pd incorporation results in a decrease in operating temperature by more than 100 C, and improves the
sensing characteristics in terms of response and recovery times.
2006 Elsevier B.V. All rights reserved.

Keywords: ZnO nanoparticles; Pd incorporation; Sensor response

1. Introduction
Historically, zinc oxide (ZnO) is one of the first materials
studied as a gas sensor. This is primarily due to the high mobil-
ity of conduction electrons in the material and good chemical and
thermal stability under operating conditions [1,2]. It is a direct
band gap wurtzite-type semiconductor with band gap energy
of 3.37 eV at room temperature, and a very large exciton bind-
ing energy of about 60 meV. ZnO presents interesting electrical,
optical, acoustic and chemical properties, which find wide appli-
cations in acoustic and short wavelength optical devices [3,4].
Although ZnO is one of the earliest materials developed as a
gas sensing material, because of high operating temperature
(around 400 C to 500 C) and poor selectivity, until recently
it has been less popular compared to SnO2 . In recent years, sev-
eral studies are going on to improve the performance of ZnO
sensors in order to increase the selectivity and to lower the oper-
Corresponding author. Tel.: +91 27160123/2386; fax: +91 40 27160921.
E-mail address: manorama@iict.res.in (S.V. Manorama).
ating temperature [5]. Most of the attempts are towards the use
of ZnO nanoparticles to improve the sensitivity or with addi-
tives for selective sensing of H2 , H2 S or NH3 gas. These are
mostly based on thin films, which require specific instrumenta-
tion as well as high temperature treatment. On the other hand,
thick film sensors are more versatile and amenable for large-
scale production. There are some reports on thick film sensors
with highly calcined samples [6,7] and a few on the sensing of
ethanol (EtOH) at an operating temperature of 332 C [8]. There
is hardly any report on liquefied petroleum gas (LPG) sensors
based on ZnO. With the aim of developing a sensor to detect
LPG at comparatively low temperature, an attempt is made to
synthesize nanoparticles of ZnO and study their gas sensing
characteristics.
In the present paper we report a very simple method to syn-
thesize highly crystalline ZnO nanoparticles via hydrothermal
route at 120 C with high sensitivity towards LPG and EtOH at
lower operating temperatures. The response and recovery times
were around 100 s. After Pd incorporation, the operating tem-
perature for maximum sensitivity decreased nearly by 100 C
and the response time decreased to few seconds.

0925-4005/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.01.028
 B. Baruwati et al. / Sensors and Actuators B 119 (2006) 676682 677

2. Experimental
2.1. Chemicals
All the chemicals used for synthesis are procured from s. d.
fine-chem. limited and are used without further purification.
2.2. Synthesis procedure
Two grams of Zn(NO3 )2 4H2 O was dissolved in 200 ml dou-
bly distilled water. The pH of the solution was brought to 7.5
by drop wise addition of ammonium hydroxide solution (25%).
The reaction mixture was then stirred for 1 h at room temperature
and transferred to a Teflon lined steel autoclave and maintained
at 120 C for different time periods ranging from 6 h to 24 h.
The autoclave was then allowed to cool to room temperature.
The product was then washed several times with doubly dis-
tilled water, filtered and dried at 80 C overnight. The reaction
can be scaled up without any change in phase and morphology
of the samples.
at the rate of 5 C/min in air to ascertain the stability, weight loss
and phase changes during the heat treatment.
2.7. Electrical conductivity studies
Keithley 236 Source Measure Unit attached with an indige-
nously designed and fabricated sample holder was used to study
the DC characteristics of the ZnO nanoparticles in the range
35050 C with a step of 10 C. The samples were used in the
form of circular pellets of diameter 0.8 cm and 0.4 cm thick-
ness. The pellets were sandwiched between two spring loaded
platinum electrodes.
AC impedance studies were carried out at temperatures from
350 C to 50 C in a frequency range 505 MHz in a HIOKI
LCR meter with a temperature interval of 10 C. The samples
are made in the form of pellets of diameter 0.8 cm. Complex
impedance plot and frequency dependent dielectric loss charac-
teristics were studied.
2.8. Gas sensing characteristics

2.3. Palladium incorporation in ZnO
0.1 wt.% Pd was incorporated into the as-synthesized sample
by dissolving PdCl2 in water along with the sample and then
calcining at 250 C for 2 h to decompose the PdCl2 .
2.4. Structure and morphology studies
For the gas sensing measurements ZnO nanoparticles were
coated over a cylindrical alumina tube of length 15 mm and
diameter 5 mm. A heating coil was inserted inside the alumina
tube and a pair of electrodes was fixed at the two ends of the
tube for electrical contacts. The schematic sensor assembly and
the circuitry for the sensor characteristics measurement were

The synthesized samples were characterized for their struc-

ture and morphology by powder X-ray diffraction (XRD;
Siemens D5000 XRD) and transmission electron microscopy
(TEM; Phillips Tecnai G2 FEI F12). The X-ray diffraction
data were recorded by using Cu K radiation (1.5406 A). The
intensity data were collected over a 2 range of 260 by
using a counting time of 0.5 s per 0.045 . The average crys-
tallite size of the samples was estimated with the help of
Scherer equation using the diffraction intensity of all promi-
nent lines. For TEM studies the samples were dispersed in
ethanol by ultrasonication and then loaded over formvar coated
copper grids. The grids were air dried before recording the
micrographs.

2.5. Optical band gap studies

The optical band gap Eg was estimated from ultra-

violet diffuse reflectance spectroscopic studies (UV-DRS; Cin-
tra UVvis spectrophotometer) in a wavelength range from
200 nm to 800 nm. The samples for this study were used
in the form of pellets with KBr and also pure KBr as the
reference.

2.6. Thermal analysis

Thermogravimetric-differential thermal analysis (TG-DTA;

Mettler Toledo, Stare system) of the as-synthesized ZnO Fig. 1. XRD patterns of (a) the as-synthesized sample (hydrothermal at 120 C
nanoparticles were carried out from room temperature to 800 C for 6 h) and (b) the sample calcined at 300 C for 2 h.
678 B. Baruwati et al. / Sensors and Actuators B 119 (2006) 676682

described in our earlier publication [9]. The sensor surface was
stabilized by heating the sensor element at 200 C for 2 h in
air. The electrical resistance of the sensor element in dry air
was measured by means of a conventional circuitry in which it
was connected to a standard resistor in series and the voltage
drop across the standard resistor at a circuit voltage of 10 V was
used to calculate the electrical resistance of the sensor element.
The values of the resistance were obtained by monitoring the
voltage drop across the sensor element. The electrical resistance
was measured both in the presence and absence of a test gas. The
sensor response (S) is defined as the ratio R/Ra , i.e. change in
resistance of the sensor (Ra ) in air and in the gas (Rg ), normalized
to the sensor resistance in air.
R |Ra Rg |
S= = TEM pattern shows that the particles are agglomerated up to
Ra Ra
synthesized at 120 C for 6 h as a representation of all samples.
A definite line broadening of the diffraction peaks is an indica-
tion that the synthesized materials are in nanometer range. The
crystallite size was calculated from Scherrer formula applied to
the major peaks and was found to be around 17 nm. The lattice
parameters calculated were also in accordance with the reported
value. We calcined the samples at 300 C for 2 h but no sig-
nificant grain growth was observed from XRD. Fig. 1b shows
the XRD pattern of the sample calcined at 300 C for 2 h. The
crystallite size calculated in this case was also 17 nm.
3.2. Transmission electron microscopy
Fig. 2 gives the TEM micrographs of the ZnO nanoparticles.
some extent.

3. Results and discussion 3.3. Thermogravimetric-differential thermal analysis

3.1. X-ray diffraction Thermal analysis of the as-synthesized ZnO nanoparticles

X-ray diffraction studies confirmed that the synthesized
materials were ZnO of the wurtzite phase and all the crystal
structures agreed with the reported JCPDS data (Card No. 5-
664). Fig. 1a shows the powder XRD pattern of the sample
was carried out to know the possible changes occurring when
the materials were subjected to heat treatment. Fig. 3 shows
the corresponding TG-DTA trace for the as-synthesized ZnO
nanoparticles. From the TG-DTA studies it is seen that the trace
for the hydrothermally synthesized ZnO is almost featureless

Fig. 2. TEM micrographs of the as-synthesized ZnO nanoparticles.

 B. Baruwati et al. / Sensors and Actuators B 119 (2006) 676682
Fig. 3. TG-DTA trace for the ZnO nanoparticles synthesized via hydrothermal
route at 120 C for 6 h.
except for a small endothermic peak at around 300 C. This
peak could not be associated with any phase change, as the cor-
responding XRD pattern (Fig. 1b) also did not show any change
in the phase of the material synthesized. At the most, the peak
can be attributed to complete crystallization of the sample. The
mass loss associated with the heating process was only 2.17%
as observed from the TGA trace.
3.4. Uitra-violet diffuse reectance spectroscopy
UV-DRS studies were carried out to estimate the optical band
gap of the synthesized nanoparticles. Fig. 4 shows the plot for
the optical absorbance () as a function of band gap energy
(h) of the nanoparticles synthesized via hydrothermal route at
120 C over a period of 6 h. From the figure it is seen that the
sample has a band gap of 3.18 eV that is slightly lower than
that of bulk ZnO (3.37 eV). This red shift may be attributed to
the agglomeration occurring in the samples. This argument is
supported by the TEM micrographs in Fig. 2.
Fig. 4. Optical absorbance () vs. band gap energy (h) plot for the ZnO nanopar-
ticles synthesized via hydrothermal route at 120 C for 6 h.
679
Fig. 5. Arrhenius plot for ZnO nanoparticles in the temperature range 350 C to
room temperature, showing typical semiconducting behavior.
3.5. DC conductivity
Fig. 5 shows the log versus 1/T Arrhenius plot for the ZnO
nanoparticles. As seen from the figure, the conductivity of the
sample increased with an increase in temperature, following a
linear dependence, as expected for a typical semiconducting
material. The activation energy calculated from the reciprocal
of slope was about 0.1 eV.
3.6. AC conductivity
As is well known for nanostructured materials, the electrical
and most physical properties are dictated by the grain boundaries
rather than the grains. To categorize and assign the contribution
of the conductivities due to these two phenomena in these mate-
rials, AC impedance studies were carried out in a temperature
range from 350 C to 50 C (during cooling) in the frequency
range 505 MHz. Fig. 6 is a typical complex impedance (Z
versus Z ) plot for the sample synthesized at 120 C for 6 h. The
plot shows only one semicircular arc for all the temperatures
showing that the conduction process is dominated by a single
Fig. 6. Complex impedance (Z vs. Z ) plot for the ZnO nanoparticles at 200 C.
The dotted line shows the simulated curve.
680 B. Baruwati et al. / Sensors and Actuators B 119 (2006) 676682

phenomenon. This observation also implies that the time con-
stants for the conduction process through the grain cores and
across the grain boundaries are identical or the conduction pro-
cess is similar to each other [10].
3.7. Gas sensing experiments
Fig. 7a shows the sensor response (S) versus operating tem-
perature plot for the as-synthesized ZnO nanoparticles towards
reducing gases LPG and EtOH. These nanoparticles showed a
typical n-type conductivity behavior, as observed by a drop in
voltage across the sensor element, indicating a reduction in elec-
trical resistance when exposed to the reducing gases. The sensor
characteristics show that response towards both gases is almost
similar, although slightly higher response was observed to EtOH
at the same operating temperatures. Both gases have a maxi-
mum response at an operating temperature around 250 C. These
studies were repeated several times and the response values
obtained were within 2% of the values in Fig. 7a. The exper-
iments were carried out to study the response of the sensor to
other interfering gases like H2 , NH3 , etc., but it is observed that
the sensitivity to these gases was very low compared to LPG and
EtOH.
It is now well known that the sensing mechanism of semicon-
ductor gas sensor materials is a surface controlled process. The
adsorption of test gases, which depends on both the type of test
gas and the sensor material, might affect both the response char-
acteristics and response time. Better response would be expected
for larger concentration of the test gas adsorbed, because the
reaction between the adsorbed reducing gas and oxygen species
becomes more favorable. When the sensor element is maintained
at equilibrium at the operating temperature, oxygen in the form
of oxide species like O , O2 , O2 , etc., localize mobile elec-
trons from the n-type semiconducting oxide in air, creating a
depletion layer at the surface of the individual particles and
inter-granular regions. Thereafter, the reaction of reducing test
gas with the charged oxygen species destroys the electron local-
ization process [10] and is observed as a change in conductivity.
Fig. 7b shows the sensor response (S) versus operating tem-
perature plot for the 0.1% Pd incorporated ZnO nanoparticles
towards LPG and EtOH. From the plot it is clearly evident that
incorporation of Pd results in a drastic decrease in the operating

Fig. 7. (a) Sensor response (S) vs. operating temperature plot of the ZnO nanoparticles towards 10% LPG and EtOH; (b) sensor response (S) vs. operating temperature
plot of the ZnO nanoparticles towards 10% LPG and EtOH after 0.1% Pd incorporation; (c) sensor response (S) vs. logarithmic gas concentration plot of the Pd
incorporated ZnO nanoparticles at 170 C. Error bar indicates the standard deviation; and (d) response characteristics of the Pd incorporated ZnO nanoparticles to
200 ppm LPG and EtOH at 170 C.
 B. Baruwati et al. / Sensors and Actuators B 119 (2006) 676682
temperature for maximum response by more than 100 C. The
operating temperature for the maximum response is observed
around 150 C.
Fig. 7c shows the plot for sensor response (S) as a function of
logarithmic gas concentration of the Pd incorporated nanoparti-
cles at 170 C (also called the calibration curve). The response
of the nanoparticles for 100 ppm gas (both LPG and EtOH) was
almost 20%, showing the suitability of the material as a good
sensor for very low concentrations of gases at low operating
temperature.
Fig. 7d shows the response characteristics for the Pd incor-
porated nanoparticles to 200 ppm LPG and EtOH at 170 C. The
response and recovery times for LPG were found to be 100 s and
80 s, while for EtOH they were 60 s and 10 s, respectively. From
this observation we can infer that the material responds more
efficiently to EtOH than LPG.
The observations from the above studies can be elucidated on
the basis of our earlier work [11] where we were able to throw
light on the increase in gas response of ZnGa2 O4 as a function
of noble metal additives on the basis of a simple work function
model. This can be elaborated by considering the role of different
contributions individually to the sensing phenomenon.
(a) When the metal-semiconductor (PdZnO) contact is formed
a barrier is formed at the interface that is fully characterized
by the electron affinity of the semiconductor, the work func-
tion (i.e. the minimum energy required to take out electron
from the metal surface) of the metal and the surface state
density of the semiconductor inside the energy gap. In equi-
librium and in the absence of any gas, if the metal work
function is large, a depletion layer will be developed in the
semiconductor. For those metals with high work function,
this depletion region of electrons is much more pronounced,
which gives rise to a larger barrier height. This manifests a
larger electrical resistance of the sensor material (semicon-
ductor and metal) in air. When exposed to a reducing gas,
the change in resistance, because of the decrease in junc-
tion barrier height becomes more significant and in effect
this increases the value of the gas response [12,13]. This
argument holds true even in the present case.
(b) Nanostructuring of the base semiconducting oxide also con-
tributes to the improvement in the gas response by larger
surface area because here the complete particle contributes
to the gas sensing phenomenon (D 2L, where D is the
particle diameter and L is the Debye length). The larger sur-
face area of the materials synthesized also facilitates the gas
detection at much lower temperatures [13].
(c) In addition, palladium is known to have a catalytic effect due
to its excellent oxidation capability to convert hydrocarbons
at lower temperatures [14] making the sensor selective to
hydrocarbons.
4. Summary and conclusions
The following are the major conclusions from the above
study:
681
(i) We synthesized ZnO nanopowders by a very simple
hydrothermal process at low temperature in large quanti-
ties (up to 100 g scale under our laboratory conditions).
(ii) The materials were found to have very good sensitivity
towards LPG and EtOH in comparison to other reducing
gases at lower operating temperatures.
(iii) Pd incorporation lowered the operating temperature by
more than 100 C.
(iv) The material was a promising candidate as a sensor for
detecting both LPG and EtOH. The response to EtOH was
better in terms of its response time. With slight modifi-
cations the material could be tailored to develop selective
sensors for LPG and EtOH.
Acknowledgement
B.B. is thankful to CSIR, India for SRF fellowship.
References
[1] T. Seiyama, A. Kato, K. Fujiishi, M. Nagatani, A new detector for gaseous
components using semiconductive thin films, Anal. Chem. 34 (1962)
15021503.
[2] N. Yamazoe, G. Sakai, K. Shimanoe, Oxide semiconductor gas sensors,
Catal. Surveys Asia 1 (2003) 6375.
[3] F.C.M. Van De Pol, Thin-film ZnO-properties and applications, Am.
Ceram. Soc. Bull. 69 (1990) 19591965.
[4] C.F. Klingshirm, Semiconductor Optics, Springer, Berlin, 1995, p. 309.
[5] T. Kwon, S. Park, J. Ryu, H. Choi, Zinc oxide thin film doped with Al2 O3 ,
TiO2 and V2 O5 as sensitive sensor for trimethylamine gas, Sens. Actuators
B: Chem. 46 (1998) 7579.
[6] S. Basu, A. Dutta, Room-temperature hydrogen sensors based on ZnO,
Mater. Chem. Phys. 47 (1997) 9397.
[7] G. Rao, D. Rao, Gas sensitivity of ZnO based thick film sensor to NH3 at
room temperature, Sens. Actuators B: Chem. 55 (1999) 166169.
[8] Xu Jiaquing, Chen Yuping, Li Yadong, Shen Jianiah, Gas sensing properties
of ZnO nanorods prepared by hydrothermal method, J. Mater. Sci. 40 (2005)
29192921.
[9] S.V. Manorama, G. Sarala Devi, J. Rao, Hydrogen sulfide sensor based
on tin oxide deposited by spray pyrolysis and microwave plasma chemical
vapor deposition, Appl. Phys. Lett. 64 (1994) 31633165.
[10] J. Jose, A. Khadar, Impedance spectroscopic analysis of AC response of
nanophase ZnO and ZnOAl2 O3 nanocomposites, Nanostruct. Mater. 11
(1999) 10911099.
[11] L. Satyanarayana, C.V. Gopal Reddy, S.V. Manorama, V.J. Rao,
Liquidpetroleumgas sensor based on a spinel semiconductor, ZnGa2 O4 ,
Sens. Actuators B: Chem. 46 (1998) 17.
[12] S.C. Tsang, C.D.A. Bulpitt, P.C.H. Mitchell, A.J. Ramirez-Cuesta, Some
new insights into the sensing mechanism of palladium promoted tin(IV)
oxide sensor, J. Phys. Chem. B 105 (2001) 57375742.
[13] L. Satyanarayana, K. Madhusudan Reddy, S.V. Manorama, Nanosized
spinel NiFe2 O4 : a novel material for the detection of liquefied petroleum
gas in air, Mater. Chem. Phys. 82 (2003) 2126.
[14] M. Fernandez-Garcia, A. Martinez Arias, A. Iglesisa-Juez, A.B. Hungria,
J.A. Anderson, J.C. Conesa, J. Soria, New strategies for the improvement
of automobile catalysts, Int. J. Mol. Sci. 2 (2001) 251262.
Biographies
Babita Baruwati did her masters in physics (nuclear and high energy physics)
from Gauhati University, Assam, India, in 2002. She is pursuing her PhD in
the field of nanomaterials especially for gas sensing and catalytic applications
at the Indian Institute of Chemical Technology, Hyderabad. Her other areas of
682 B. Baruwati et al. / Sensors and Actuators B 119 (2006) 676682

interest include designing novel materials towards applications in electronic and Sunkara V. Manorama did her PhD in physics, from Department of Physics,
magnetic devices, sensors and catalysis. University of Pune, Maharashtra, India, in 1990. After a brief postdoctoral
experience at UWCC, Cardiff, UK, she joined Indian Institute of Chemical
D. Kishore Kumar completed his masters in chemistry from Vellore Institute
Technology, Hyderabad. She is presently working as a scientist in the Nano-
of Technology, Tamil Nadu, India, in 2005. For his masters dissertation he
materials Laboratory, Indian Institute of Chemical Technology, Hyderabad. Her
worked on the synthesis of well dispersed zinc oxide nanoparticles that he used
fields of interest are synthesis of new functional nanomaterials for applications
for gas sensing and catalytic applications. He is presently pursuing his research
in the field of sensors, catalysis, etc.
at IGCAR, Kalpakkam, Tamilnadu.