Gas Sensing Application of Nanocrystalline Zinc Oxide Thin Films Prepared by Spray Pyrolysis
Gas Sensing Application of Nanocrystalline Zinc Oxide Thin Films Prepared by Spray Pyrolysis
Gas Sensing Application of Nanocrystalline Zinc Oxide Thin Films Prepared by Spray Pyrolysis
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Abstract. Nanocrystalline oxygen-deficient ZnO thinfilm sensors were prepared by spray pyrolysis technique using
zinc acetate dissolved in propanol and water as precursor. Response of the sensor to target gases NO2 and H2 S
is studied. At optimum temperature of 200 C, the sensors have a response of 3.32 to 7 ppm NO2 and 1.4 to 18
ppm of H2 S gas. The analytical characterizations of the prepared sensors were performed using X-ray diffrac-
tion measurement, scanning electron microscopy, energy-dispersive X-ray spectroscopy and Raman spectroscopy.
Dynamic response of sensors to different concentrations of NO2 and H2 S gas was tested at optimum temperature.
Experimental data revealed the sensors to be more selective to NO2 gas with satisfactory response and recovery time.
583
584 Nisha R et al
2.1 Film preparation The gas sensing measurements of the thin film sensor were
carried out on custom-built static gas characterization sys-
Zinc oxide thin films were prepared on soda lime glass sub- tem. The schematic representation of test system is shown
strate using CSP technique. Zinc acetate solution (0.3 M) in figure 1. The test system consists of a stainless steel
was prepared in a mixture of propanol and water, taken in the chamber of diameter 7.5 and 6.35 cm height. The effective
volume ratio 1:1. This precursor was selected due to its high volume of the chamber is 280 ml. An inlet is provided for
vapour pressure at low temperature. Addition of few drops inserting the desired concentration of the gas to the cham-
of acetic acid prohibits the precipitation of zinc hydrox- ber. The gas is injected into the test chamber with a syringe
ide, thereby making the spray solution clear and produc- through the inlet provided with septum. Electrical connec-
ing films of better optical transmittance. Quantity of acetic tions from the sensor are taken with the help of two thin copper
acid added to the solution is also a key parameter in the wires, bonded to the sensor with silver paint. The distance
film deposition process. Compressed air was used as the between the two electrodes is adjusted to 5 mm. The sensing
carrier gas (pressure 0.34 bar) and temperature of sub- capability of the sensor is characterized at different operat-
strate was kept at 450 5 C. Now keeping the molarity of ing temperatures with a precisely controlled heater (0.5 C)
zinc acetate (Zn(CH3 CO2 )2H2 O) at 0.3 M and spray rate inside the system, to find out the optimum working temper-
at 7 ml min1 , deposition was done using automated spray ature. Resistance change of the sensor on introduction of
machine in which the spray rate, deposition time and move- the test gas into the chamber is measured using computer-
ment of the spray head were controlled by a microprocessor. controlled Keithley 195A digital multimeter. Gas concentra-
After the deposition, samples were quickly removed from tion is measured by taking required amount of gas from the
the substrate heater.45 ZnO films were deposited with 550 nm
obtained precalibrated cylinder (Chemtron Science Labora-
thickness over 30 cm2 area. ZnO films for gas sens-
tories) in a syringe and then injecting it into the chamber
ing application were selected after optimizing the various
pre-filled with air at atmospheric pressure. The response of
parameters like spray rate, molarity, oxygen stoichiometry
the sensor was studied at different operating temperatures in
and thickness.4648 Prior to gas sensing measurements, the
the range 100225 C for various concentrations of NO2 and
films were annealed at an approximate temperature 600 C
H2 S gas ranging from 1.5 to 30 ppm and 5 to 60 ppm in air,
overnight (Actual temperature at the sample was within a
respectively.
range of 5% of this set temperature.) to remove any possi-
ble organic residue remained from the precursor solution and
also to improve the crystallinity and to sinter the layer. High 2.3 Characterization of the ZnO film
temperature annealing also helps in avoiding posterior insta-
bilities, as these sensors are to be operated at elevated tem- The crystalline structure and particle size of annealed thin
peratures. For the purpose of gas sensing investigations, the film sensor were examined by X-ray diffraction measure-
films were cut into small pieces with an approximate area of ment (XRD, Bruker AXS D8 Advance). Surface morphology
1 cm2 . of the prepared sensors were analysed using scanning
Response of the sensor to target gases NO2 and H2 S 585
Figure 2. XRD pattern of annealed ZnO thin film sensor. Figure 3. SEM images of annealed ZnO thin film sensor.
3.1 XRD
elements only. The XPS analysis performed on the ZnO film 3.4 Gas sensing investigations
is reported elsewhere.45
The gas sensing properties of thin film ZnO sensor was
studied in a static gas sensing test system with an effective
volume of 280 ml. Sensitivity of the active layer upon
3.3 Raman spectroscopy
oxidizing NO2 gas exposure is measured in terms of the
Raman spectrum of annealed thin film sensor is shown in ratio S = Rgas /Rair and for reducing gas (H2 S), S is given
figure 5. Raman spectroscopy gives information on vibra- as Rair /Rgas , where Rgas is resistance of sensor in presence
tional properties of ZnO.51 It is known for wurtzite-type ZnO of gas and Rair is resistance of sensor before introduction of
(space group p63 mc) that optical phonons at the point of gas. The temperature-dependent sensitivity of sensors was
the Brillouin zone belong to the following irreducible repre- studied in the range of 100225 C. Below the sensor
sentation: = A1 + E1 + 2E2 + 2B1 , where A1 and E1 temperature of 100 C, it was difficult to measure gas sens-
modes are both Raman and infrared active, E2 modes are ing characteristics due to the sluggish recovery kinetics.
Raman active only and B1 modes are both Raman and Relatively low concentration 7 ppm of NO2 and 18 ppm
infrared inactive (silent modes).13,5254 Nonpolar E2 phonon H2 S gas investigation is presented in detail. Similar results
modes have two frequencies; the low were obtained for higher concentration studied. Figure 6a
low frequency
E2 mode
and b represents temperature-dependent sensitivity of sensor
high
E2 and high frequency E2 mode E2 . The E2 modes
to a concentration of 7 ppm NO2 gas and 18 ppm H2 S gas
at low and high frequencies are at 101 and 437 cm1 , studied.
respectively. The low frequency E2 mode E2low is associ- NO2 response of sensor to 7 ppm presents a maximum
ated with vibration
of the Zn sublattice, while the high fre- sensitivity at 200 C as the temperature increases from 100
quency E2 mode E2
high
is related to the vibration of oxygen to 225 C, the sensor sensitivity increasing from 1.22 to 3.32,
high which is the maximum. Increasing the temperature above
atoms.55,56 E2 of ZnO is the strongest mode in the wurtzite
crystal structure. The strong E2 (high) mode indicates a good
crystallinity.57 Peak at 556 cm1 is a contribution of the E1
(LO) mode of ZnO in the case of oxygen deficiency.58,59
Such a strong intensity of 556 cm1 E1 mode demonstrates
that ZnO thin film sensor is oxygen deficient. These oxygen-
deficient sites can enhance the gas sensing properties of thin
film sensor. An additional peak is obtained at 330 cm1 .
Peak at the same position was reported earlier in literature
by various researchers.6062 This peak is assigned to possi-
ble multiple-phonon-scattering. The above presented results
confirmed the ZnO hexagonal wurtzite structure, which is in
good agreement with the obtained XRD results.
200 C decreases sensor sensitivity, achieving 1.29 at 225 C. optimum operating temperature of 200 C. Figure 9 repre-
Concerning the 18 ppm H2 S sensor response, sensitivity sents the dynamic response of the sensor to H2 S gas at 200 C
increases with increase of temperature in the studied range, to various concentrations.
attaining a maximum 1.4 at 200 C. Increasing the tempera- Chemoresistivity is the basis of sensing mechanism for
ture more than 200 C, the sensitivity decreases and attains metal oxides, which consists of a variation of intergranu-
1.15 at 225 C. Considering the temperature-dependent sen- lar and intragranular barriers with subsequent conductance
sitivity studies, optimal operating temperature of 200 C was change, as a response to surface chemical reactions with
chosen to further examine the characteristics of the gas sen- environmental gases. ZnO-based gas elements prepared in
sor to NO2 and H2 S gas. Comparing the maximum sensitiv- nanocrystalline form have large numbers of grain bound-
ity values (3.32 for 7 ppm NO2 and 1.4 for 18 ppm H2 S), aries and necks. The adsorbed oxygen on the grain surface
ZnO sensor is more sensitive to NO2 at lower concentration extracts the conduction electrons from near-surface region of
and operating temperature. Figure 7a and b shows response the grain, leading to the grain-boundary barriers and the neck
of sensor to 7 ppm NO2 and 18 ppm H2 S gas at 200 C, barriers.63 The neck barrier controls the electron conduct-
respectively. ing channel through the neck and the electron density in the
The maximum sensitivity of ZnO being obtained at 200 C, space charge layer at the neck.64 Therefore the neck barrier
the dynamic responses of ZnO thin film gas sensor at 200 C
were tested with different NO2 concentrations at 1.5, 3.5
and 30 ppm, respectively. Figure 8 represents the dynamic
response of sensor to different NO2 gas concentration
studied. Dynamic responses of the sensor to 5, 10, 30 and
60 ppm concentration of H2 S gas were performed at the
Figure 7. Response of ZnO thin film sensor to (a) 7 ppm NO2 gas Figure 9. Dynamic response of thin film sensor to different H2 S
and (b) 18 ppm H2 S gas at 200 C. gas concentrations studied.
588 Nisha R et al
determines the neck resistance. At the same time, the grain- sensor, because the O 2 ions tend to assist the adsorbed NO
2
boundary barrier determines the grain-boundary resistance. ions in taking the electrons from the ZnO thin films.
Ma et al63 studied the effect of grain size on gas sensitivity The optimum operating temperature for pure and doped
on ZnO.65 This group described the total sensitivity in ZnO- sensors was found to be 200 C for NO2 gas. At lower tem-
based nanocrystalline sensors is the effect of both neck and perature the sensitivity was low; also the recovery time kept
the neckgrain boundary resistance. Gupta et al65 studied the on increasing, which indicates a longer time taken by the sen-
sensitivity of ZnO-based gas sensors to NO and H2 S gas. sor to revert back to its base-line properties for the next oper-
The results demonstrate that response of ZnO sensors to H2 S ation. At low operating temperature sensitivity of the films
arises from grain boundary only, whereas both grain bound- to NO2 is restricted by the speed of the chemical reaction,
aries and intra-grain resistances contribute towards response because the electrons do not have enough thermal energy to
to NO. As XRD studies confirmed the nanocrystalline nature, react with the surface adsorbed oxygen species. In fact, dur-
a similar effect is expected in our sensors to NO2 and H2 S ing adsorption of atmospheric oxygen on the film surface, a
gases. However, detailed investigations like impedance spec- potential barrier to charge transport is developed. As operat-
troscopy measurements are to be carried out to confirm these ing temperature increases the thermal energy obtained is high
findings. enough to overcome the potential barrier and thus electron
Oxygen vacancies and defects in lattice act as adsorption concentration increases significantly, which in turn leads to
sites for oxygen and test gases. As the detection of gases orig- an increase in sensitivity of sensor films. At optimum operat-
inates from interaction of these adsorbed oxygen atomswith ing temperature the sensitivity is maximum. This is attributed
gases, maximum (minimum) defect density in (polycrys- to the availability of sufficient adsorbed ionic species of oxy-
talline material) yields maximum (minimum) response.65 gen on film surface, which react most effectively with NO2
Raman spectroscopy performed on our sensors revealed that molecules at this particular temperature. The results obtained
the thin film sensors prepared are oxygen deficient. These for NO2 gas sensing is comparable with earlier published
oxygen vacancies in the sensors act as additional sites for gas results.68,69
adsorption, there by enhancing the sensitivity. A reverse effect is observed when the sensor films are
Earlier research works conclude, oxygen adsorbed on exposed to H2 S gas, a decrease of the ZnO film resistance
the surface of oxide gas sensors undergoes the following under H2 S exposure, which can be explained by its reac-
reactions given by66 eqs (25). tion with chemisorbed oxygen (eqs (9 and 11)), inducing
the release of electrons in the conduction band.70 The gas
O2 (gas) O2 (ads) , (2) response by MOS, in general, can be described as
the sensitivity of ZnO to H2 S gas in the temperature range of baseline conductance. Response time of a sensor can vary
100450 C and reported the sulphuration of ZnO surface on from seconds to minutes, but a good sensor is the one that
exposure to H2 S gas. When the sensor was exposed to H2 S shows a short response and recovery time. In our work,
gas, the transformation of highly resistive ZnO into well- response time of sensor was defined as time required for sen-
conducting ZnS led to the decrease of electrical resistance. sor resistance to reach 90% of maximum resistance. Recov-
The reactions in the response and recovery processes can be ery time was defined as time necessary for the sensor to
represented as follows: return to 10% of its original resistance (before introduc-
tion of gas). Response and recovery time of ZnO sensor to
ZnO(s) + H2 S(g) ZnS(s) + H2 O(g), (11) 7 ppm NO2 and 18 ppm H2 S gas at the temperature range of
100225 C was recorded and is shown in figure 10a and b.
2ZnS(s) + 3O2 (g) 2ZnO(s) + 2SO2 (g). (12)
At optimum temperature of 200 C, the response time of
The Gibbs free energy, enthalpy and entropy for both sulphu- ZnO sensor was 6 and 10 s to NO2 and H2 S gases, respec-
ration and desulphuration were calculated by the group and tively. The recovery time recorded was 2.3 and 7 min to NO2
the results showed that both reactions are spontaneous. We and H2 S gases respectively. The response and recovery time
expect the same kind of sulphuration process in our ZnO thin obtained for ZnO sensor to NO2 gas is comparable with earlier
film H2 S sensors along with the reaction of H2 S with oxy- published results.44,68,79,80 Compared to NO2 measurements
gen adsorbates, thereby decreasing sensor resistance in the it is seen that the recovery characteristics are very slow for H2 S
presence of H2 S gas. measurements. This may be due to slow desulphuration process
Response and recovery times are important parameters for on the surface of sensors resulting in larger recovery time.
designing sensors for desired application. Response/recovery
times are defined as the time required for absorption and
4. Conclusion
desorption of the oxygen on, or from the sensor surface to
reach the saturation or to reduce the conductivity back to the
ZnO thin film sensors were fabricated by spray pyrolysis
technique. The prepared films were annealed at 600 C
overnight prior to gas sensing measurements. The XRD analysis
confirmed the nanocrystalline nature of the annealed sensor.
The average particle size was found to be 38 nm. The crys-
talline structure was found to be hexagonal wruzite in nature.
Surface morphological studies performed with SEM revealed
closely packed arrangement of crystallites. Elemental anal-
ysis were performed using EDS. Raman spectroscopy stud-
ies confirmed the ZnO hexagonal wurtzite structure. Raman
studies established the oxygen deficient nature of thin film
sensor, which has an added advantage for gas sensing pur-
poses. Gas sensing investigation of the prepared sensors was
characterized with NO2 and H2 S gases. Thin film sensors
were found to be more selective to NO2 gas at an optimum
temperature of 200 C. For a 7 ppm concentration, the sensor
sensitivity was 3.32 with a response and recovery time of 6 s
and 2.26 min, respectively. It is expected that the response to
H2 S arises due to changes in grain boundary resistance, while
that to NO2 arises due to changes in both intra-grain and
grain boundary resistances. Oxygen vacancies in the lattice,
as were also seen, enhance the sensor response. However, the
exact details of these complicated surface reactions are yet
to be fully understood. More detailed experimentation would
be necessary to substantiate the suggestions speculated here.
The results indicate that spray pyrolysis technique is a reli-
able method for the preparation of nanocrystalline zinc oxide
films for gas sensor applications.
Acknowledgements
Figure 10. Response and recovery time of ZnO thin film sensor We wish to acknowledge Dr M K Jayaraj, Nanophotonic &
to (a) 7 ppm NO2 gas (b) 18 ppm H2 S gas at different temperature. Optoelectronic Devices Laboratory, Department of Physics
590 Nisha R et al
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