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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 ating temperature [5]. Most of the attempts are towards the use
of ZnO nanoparticles to improve the sensitivity or with addi-
Historically, zinc oxide (ZnO) is one of the first materials tives for selective sensing of H2 , H2 S or NH3 gas. These are
studied as a gas sensor. This is primarily due to the high mobil- mostly based on thin films, which require specific instrumenta-
ity of conduction electrons in the material and good chemical and tion as well as high temperature treatment. On the other hand,
thermal stability under operating conditions [1,2]. It is a direct thick film sensors are more versatile and amenable for large-
band gap wurtzite-type semiconductor with band gap energy scale production. There are some reports on thick film sensors
of 3.37 eV at room temperature, and a very large exciton bind- with highly calcined samples [6,7] and a few on the sensing of
ing energy of about 60 meV. ZnO presents interesting electrical, ethanol (EtOH) at an operating temperature of 332 C [8]. There
optical, acoustic and chemical properties, which find wide appli- is hardly any report on liquefied petroleum gas (LPG) sensors
cations in acoustic and short wavelength optical devices [3,4]. based on ZnO. With the aim of developing a sensor to detect
Although ZnO is one of the earliest materials developed as a LPG at comparatively low temperature, an attempt is made to
gas sensing material, because of high operating temperature synthesize nanoparticles of ZnO and study their gas sensing
(around 400 C to 500 C) and poor selectivity, until recently characteristics.
it has been less popular compared to SnO2 . In recent years, sev- In the present paper we report a very simple method to syn-
eral studies are going on to improve the performance of ZnO thesize highly crystalline ZnO nanoparticles via hydrothermal
sensors in order to increase the selectivity and to lower the oper- 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-
Corresponding author. Tel.: +91 27160123/2386; fax: +91 40 27160921. perature for maximum sensitivity decreased nearly by 100 C
E-mail address: manorama@iict.res.in (S.V. Manorama). 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 at the rate of 5 C/min in air to ascertain the stability, weight loss
and phase changes during the heat treatment.
2.1. Chemicals
2.7. Electrical conductivity studies
All the chemicals used for synthesis are procured from s. d.
fine-chem. limited and are used without further purification. Keithley 236 Source Measure Unit attached with an indige-
nously designed and fabricated sample holder was used to study
2.2. Synthesis procedure the DC characteristics of the ZnO nanoparticles in the range
35050 C with a step of 10 C. The samples were used in the
Two grams of Zn(NO3 )2 4H2 O was dissolved in 200 ml dou- form of circular pellets of diameter 0.8 cm and 0.4 cm thick-
bly distilled water. The pH of the solution was brought to 7.5 ness. The pellets were sandwiched between two spring loaded
by drop wise addition of ammonium hydroxide solution (25%). platinum electrodes.
The reaction mixture was then stirred for 1 h at room temperature AC impedance studies were carried out at temperatures from
and transferred to a Teflon lined steel autoclave and maintained 350 C to 50 C in a frequency range 505 MHz in a HIOKI
at 120 C for different time periods ranging from 6 h to 24 h. LCR meter with a temperature interval of 10 C. The samples
The autoclave was then allowed to cool to room temperature. are made in the form of pellets of diameter 0.8 cm. Complex
The product was then washed several times with doubly dis- impedance plot and frequency dependent dielectric loss charac-
tilled water, filtered and dried at 80 C overnight. The reaction teristics were studied.
can be scaled up without any change in phase and morphology
of the samples. 2.8. Gas sensing characteristics

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

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


was carried out to know the possible changes occurring when
X-ray diffraction studies confirmed that the synthesized the materials were subjected to heat treatment. Fig. 3 shows
materials were ZnO of the wurtzite phase and all the crystal the corresponding TG-DTA trace for the as-synthesized ZnO
structures agreed with the reported JCPDS data (Card No. 5- nanoparticles. From the TG-DTA studies it is seen that the trace
664). Fig. 1a shows the powder XRD pattern of the sample 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 679

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


Fig. 5. Arrhenius plot for ZnO nanoparticles in the temperature range 350 C to
peak could not be associated with any phase change, as the cor- room temperature, showing typical semiconducting behavior.
responding XRD pattern (Fig. 1b) also did not show any change
in the phase of the material synthesized. At the most, the peak 3.5. DC conductivity
can be attributed to complete crystallization of the sample. The
mass loss associated with the heating process was only 2.17% Fig. 5 shows the log versus 1/T Arrhenius plot for the ZnO
as observed from the TGA trace. nanoparticles. As seen from the figure, the conductivity of the
sample increased with an increase in temperature, following a
3.4. Uitra-violet diffuse reectance spectroscopy linear dependence, as expected for a typical semiconducting
material. The activation energy calculated from the reciprocal
UV-DRS studies were carried out to estimate the optical band of slope was about 0.1 eV.
gap of the synthesized nanoparticles. Fig. 4 shows the plot for
the optical absorbance () as a function of band gap energy 3.6. AC conductivity
(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 As is well known for nanostructured materials, the electrical
sample has a band gap of 3.18 eV that is slightly lower than and most physical properties are dictated by the grain boundaries
that of bulk ZnO (3.37 eV). This red shift may be attributed to rather than the grains. To categorize and assign the contribution
the agglomeration occurring in the samples. This argument is of the conductivities due to these two phenomena in these mate-
supported by the TEM micrographs in Fig. 2. 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. 4. Optical absorbance () vs. band gap energy (h) plot for the ZnO nanopar- Fig. 6. Complex impedance (Z vs. Z ) plot for the ZnO nanoparticles at 200 C.
ticles synthesized via hydrothermal route at 120 C for 6 h. 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- the sensitivity to these gases was very low compared to LPG and
stants for the conduction process through the grain cores and EtOH.
across the grain boundaries are identical or the conduction pro- It is now well known that the sensing mechanism of semicon-
cess is similar to each other [10]. ductor gas sensor materials is a surface controlled process. The
adsorption of test gases, which depends on both the type of test
3.7. Gas sensing experiments gas and the sensor material, might affect both the response char-
acteristics and response time. Better response would be expected
Fig. 7a shows the sensor response (S) versus operating tem- for larger concentration of the test gas adsorbed, because the
perature plot for the as-synthesized ZnO nanoparticles towards reaction between the adsorbed reducing gas and oxygen species
reducing gases LPG and EtOH. These nanoparticles showed a becomes more favorable. When the sensor element is maintained
typical n-type conductivity behavior, as observed by a drop in at equilibrium at the operating temperature, oxygen in the form
voltage across the sensor element, indicating a reduction in elec- of oxide species like O , O2 , O2 , etc., localize mobile elec-
trical resistance when exposed to the reducing gases. The sensor trons from the n-type semiconducting oxide in air, creating a
characteristics show that response towards both gases is almost depletion layer at the surface of the individual particles and
similar, although slightly higher response was observed to EtOH inter-granular regions. Thereafter, the reaction of reducing test
at the same operating temperatures. Both gases have a maxi- gas with the charged oxygen species destroys the electron local-
mum response at an operating temperature around 250 C. These ization process [10] and is observed as a change in conductivity.
studies were repeated several times and the response values Fig. 7b shows the sensor response (S) versus operating tem-
obtained were within 2% of the values in Fig. 7a. The exper- perature plot for the 0.1% Pd incorporated ZnO nanoparticles
iments were carried out to study the response of the sensor to towards LPG and EtOH. From the plot it is clearly evident that
other interfering gases like H2 , NH3 , etc., but it is observed 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 681

temperature for maximum response by more than 100 C. The (i) We synthesized ZnO nanopowders by a very simple
operating temperature for the maximum response is observed hydrothermal process at low temperature in large quanti-
around 150 C. ties (up to 100 g scale under our laboratory conditions).
Fig. 7c shows the plot for sensor response (S) as a function of (ii) The materials were found to have very good sensitivity
logarithmic gas concentration of the Pd incorporated nanoparti- towards LPG and EtOH in comparison to other reducing
cles at 170 C (also called the calibration curve). The response gases at lower operating temperatures.
of the nanoparticles for 100 ppm gas (both LPG and EtOH) was (iii) Pd incorporation lowered the operating temperature by
almost 20%, showing the suitability of the material as a good more than 100 C.
sensor for very low concentrations of gases at low operating (iv) The material was a promising candidate as a sensor for
temperature. detecting both LPG and EtOH. The response to EtOH was
Fig. 7d shows the response characteristics for the Pd incor- better in terms of its response time. With slight modifi-
porated nanoparticles to 200 ppm LPG and EtOH at 170 C. The cations the material could be tailored to develop selective
response and recovery times for LPG were found to be 100 s and sensors for LPG and EtOH.
80 s, while for EtOH they were 60 s and 10 s, respectively. From
this observation we can infer that the material responds more Acknowledgement
efficiently to EtOH than LPG.
The observations from the above studies can be elucidated on B.B. is thankful to CSIR, India for SRF fellowship.
the basis of our earlier work [11] where we were able to throw
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Biographies
4. Summary and conclusions
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 following are the major conclusions from the above the field of nanomaterials especially for gas sensing and catalytic applications
study: 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.