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Sensors and Actuators B 207 (2015) 375382

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical


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

Origin and role of elasticity in the enhanced DMMP detection by


ZnO/SAW sensor
V. Bhasker Raj a , Harpreet Singh b , A.T. Nimal b , Monika Tomar c , M.U. Sharma b ,
Vinay Gupta a,
a

Electronic Materials and Devices Laboratory, Department of Physics and Astrophysics, University of Delhi, Delhi 110007, India
Solid State Physics Laboratory (DRDO), Lucknow Road, Timarpur, Delhi 110054, India
c
Physics Department, Miranda House College, University of Delhi, Delhi 110007, India
b

a r t i c l e

i n f o

Article history:
Received 4 August 2014
Received in revised form
27 September 2014
Accepted 2 October 2014
Available online 23 October 2014
Keywords:
SAW
DMMP
ZnO
Mechanism
Sensor

a b s t r a c t
ZnO/Quartz based surface acoustic wave (SAW) sensors have been fabricated for the detection of DMMP
(di-methyl methyl phosphonate) at room temperature. The as-deposited ZnO thin lms are c-axis oriented. The sensitivity of the sensor toward DMMP vapors increases with increase in the thickness of ZnO
thin lms. A change in elasticity of ZnO lms with exposure to DMMP vapors is the dominant sensing
mechanism. Various properties of ZnO thin lms (roughness, porosity, crystallite size, bond strength etc.)
responsible for elastic changes are analyzed by depositing the lms under different processing conditions.
The ZnO/SAW sensor is also highly selective toward DMMP vapors as compared to other interferants. The
results throw light into the elasticity mechanism for SAW sensing along with the possibility of utilizing
ZnO/SAW sensor for DMMP detection.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Chemical warfare agents (CWA) constitute a fatal class of chemicals developed for military personnel on the battleeld. However
they also pose a civilian threat in public places and laboratories.
Thus development of suitable devices for their fast and reliable
detection with high sensitivity and selectivity are of utmost importance. CWA can be broadly classied into four categories: nerve
agents, choking agents, blister agents and blood agents [1]. Sarin
(o-isopropyl methylphosphonouoridate) is one of the most deadly
nerve agent classied as a weapon of mass destruction as per UN
Resolution 687 [1]. The short and long term symptoms experienced
by its exposure to human body includes miosis (pinpoint pupils),
blurred and dim vision, nausea, vomiting, diarrhea, copius secretions, muscle twitching/asciculations, dyspnea, seizures, memory
loss and even death [2]. Since Sarin is highly toxic and restricted,
research is often carried out on its simulant. An ideal chemical agent
simulant would mimic all relevant chemical and physical properties of the CWA without its associated toxicological properties.

Corresponding author. Tel.: +91 9811563101.


E-mail address: drguptavinay@gmail.com (V. Gupta).
http://dx.doi.org/10.1016/j.snb.2014.10.015
0925-4005/ 2014 Elsevier B.V. All rights reserved.

Di-methyl methyl phosphonate (DMMP) is a well known simulant


of Sarin [1].
Various techniques are utilized for the detection of nerve agents
like conductometry, Surface Acoustic Wave (SAW), reectance
spectrometry, capillary electrophoresis, surface enhanced Raman
spectroscopy (SERS), ion mobility spectrometry (IMS), gas chromatography in combination with mass spectrometry etc. [26].
Reectance spectroscopy technique offers a limited level of detection and is complex, expensive and bulky [6]. Ion mobility
spectrometers can detect CWA in real-time and are portable.
But, this technique requires a radioactive source, and has poor
selectivity along with high cost [6]. The major limitations of
gas chromatography-mass spectroscopy include elaborate sample preparation, complicated instrumentation and requirement of
technically trained personnel for operation and analysis [5]. Conductometric and SAW sensors are effective for the online detection
of CWA. Amongst them, SAW technology is considered to be advantageous because of high sensitivity, fast response and wireless
detection in inaccessible areas. SAW sensors are based on the propagation of acoustic wave through a piezoelectric substrate. As the
acoustic wave propagates, any changes to the characteristics of the
propagation path affect the velocity or amplitude of the wave. The
changes in SAW velocity/frequency can be measured and calibrated
with the concentration of target vapors.

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V.B. Raj et al. / Sensors and Actuators B 207 (2015) 375382

Table 1
Processing parameters for the deposition of ZnO thin lms as sensitive layer.
Target
Sputtering pressure
Gas composition
Sputtering power
Substrate temperature
Target to substrate distance

6 dia. Zn metal (99.9% pure)


1040 mT
Ar + O2 (30100%)
300 W
Room temperature (no heating)
8.5 cm

Few articles were reported in literature related to the detection


of DMMP using SAW sensors [710]. Recently diamond nanoparticles dispersed on SAW devices were used for the detection of
DMMP vapors [7]. However, sensor exhibits poor selectivity and
was sensitive to other vapors (NH3 , ethanol etc.). Various polymers (uoropolyol, polyisobutylene, bisphenol) were also utilized
as chemical interface layer on the surface of SAW devices for the
detection of DMMP vapors [810]. The low sensitivity, cross selectivity and poor stability were major concern. Some selectivity was
obtained for DMMP vapors by depositing hexauoroisopropanol
groups functionalized hydrogen-bond acidic siloxane polymer on
the surface of QCM [11]. Electrochemical incorporation of CuPc in
conducting polypyrrole was also carried out for sensing DMMP
vapors [12]. Although sensor was insensitive to few interferants
yet methanol was giving signicant response. It is to be noted that
metal oxides were not exploited much as chemical interface layer
on SAW devices despite the fact that they are stable and exhibits
good sensitivity toward DMMP vapors using conductometric technique [13]. The composites of SnO2 with various other oxides (NiO,
Y2 O3 , Nb2 O5 , CuO, Yb2 O3 , BaO and La2 O3 ) were also used as sensing element [13]. However the operating temperature was quite
high and sensitivity was poor for DMMP. Single walled CNTs were
also utilized for the detection of DMMP using conductometric technique [14]. However, the sensor was sensitive to other CW agents
and was not selective to DMMP. Selectivity toward DMMP vapors
can be improved by using MIP (molecularly imprinted polymers)
layers [15]. However, for on-eld applications they are not preferred because of slow response and recovery time [15]. Hence
efforts are still continuing toward the enhancement of sensitivity
and selectivity toward DMMP detection at room temperature.
It is to be noted that lot of efforts have been made toward the
development of SAW sensors for the detection of toxic gases and
vapors. Surprisingly systematic efforts for understanding the origin
of factors affecting the sensing mechanism of SAW vapor sensors
are very rare. Since SAW sensors are highly sensitive to surface perturbations, the properties of sensitive overlayer play a crucial role.
Further it is to be noted that the adsorption of target vapors is sensitive to various properties of the sensing layer including porosity,
surface roughness, stress, electrical conductivity, surface defects
etc. Hence to improve the SAW sensor response characteristics, it
is important to understand the SAW gas/vapor sensing mechanism
and their dependence on the various properties of the sensitive thin
lm.
In the present report, ZnO thin lms are deposited on the surface
of SAW device under various deposition conditions and selective
detection of DMMP is demonstrated with enhanced response. The
origin of sensing mechanism for DMMP is identied and correlation
with lm properties is established.

Fig. 1. XRD spectra of ZnO thin lms of different thickness (2080 nm) deposited at
20 mT on ST-X Quartz.

and surface morphology of the ZnO thin lms have been investigated using X-ray diffractometer (Bruker D8 Discover) and atomic
force microscope (AFM) (VEECO CP-II) respectively. The optical
band gap of the ZnO thin lm is evaluated from the transmission
data obtained using a double beam UV-Visible spectrophotometer
(Perkin Elmer, Lambda 35). Infra-red (IR) spectroscopic measurements were carried out using Perkin Elmer instrument (Model:
Frontier).
ZnO thin lm coated SAW resonators are placed as frequency determining element in Colpitt oscillator conguration as
described earlier [16]. For sensing vapors, a laboratory-assembled
vapor generation and delivery system is developed [17,18]. A small
quantity of liquid is placed at the bottom of a corrugated glass tube,
and the carrier (N2 ) is passed continuously through it. The carrier
gas (N2 ) from the source is bifurcated into two paths, controlled
by individual ow controllers, one carrying the test gas and the
other only carrier to the sensor surface. The schematic of the vapor
generation and delivery system has been published earlier [17,18].
Fast switching solenoid valves have been used to ensure continuous
ow of vapors with negligible ow disturbance during switching of the solenoids. The ow rates are maintained at 120 ml/min.
SAW oscillators are used in differential frequency conguration to
minimize the effect of various environment uctuations. The SAW
sensor system having ve oscillators is utilized where four oscillators having ZnO coated SAW device are used as sensors and the
fth one with bare SAW device is used as reference. A specially
designed pentagonal sensor cell made up of stainless steel has been
designed and fabricated for this purpose. Due to the pentagon shape
of the sensor cell, the sensor oscillators will be exposed equally and
simultaneously to target vapors. The schematic of the sensor cell
has been shown in earlier publication [17]. The difference frequencies (f) of reference and ZnO coated SAW oscillators are measured
through a frequency counter interfaced with PC for real time data
acquisition. For stabilized response, the sensor oscillators are kept
in a continuous ow of carrier gas for about 30 min prior to sensing
experiments.

2. Experimental

3. Results and observations

One-port SAW resonators obtained from RF Monolithic are used


in the present work. The uncoated SAW resonator has a center
frequency of f0 = 433.9 MHz. The device package is cut open for
the deposition of ZnO thin lm and the processing conditions are
presented in Table 1. The thickness of the ZnO lm is monitored
by surface proler (Dektak-150A). The crystallographic structure

3.1. Structural property


XRD pattern of ZnO thin lms of different thickness (2080 nm)
deposited at 20 mT pressure under reactive gas ambient of 50%
Ar and 50% O2 is shown in Fig. 1a. The XRD pattern of ZnO thin
lms shows reection corresponding to (0 0 2) plane of the wurtzite

V.B. Raj et al. / Sensors and Actuators B 207 (2015) 375382

377

Table 2
Various material properties (stress, crystallite size, surface roughness and binding energy) of ZnO thin lms of different thickness deposited at different sputtering pressure
and processing oxygen percentage.
Material properties of ZnO thin lms

Stress 10 (dynes/cm )
Crystallite size (nm)
Average surface roughness (nm)
Bond strength (kJ/mol)
10

ZnO lms of different thickness


(nm)

ZnO lms (40 nm) at different pressure (mT)

ZnO lms (40 nm) at different gas


composition Ar:O2 (O2 %)

20

40

60

80

10

20

30

40

30

50

70

100

5.5
10
10

2.9
17
4

2.1
19
3

1.5
20
2

4.6
9
4
4.93

2.9
17
3
4.93

3.7
15
13
4.93

5.9
13
6
4.93

4.2
17
3
4.98

2.9
17
3
4.93

2.4
17
3
4.90

1.6
17
4
4.88

structure. It indicates the growth of oriented ZnO thin lms having


its c-axis normal to the surface of substrate. The growth of preferred
c-axis orientation is attributed to the minimum surface free energy
of (0 0 2) plane in wurtzite ZnO structure [19,20]. The (0 0 2) XRD
peak for all ZnO thin lms was observed at Braggs angle (2) lower
than the reported value (34.42 ) for bulk ZnO [19,20]. The deviation of 2 (from bulk ZnO) is associated with the presence of stress
which might be attributed to the presence of native defects [18].
The deviation from 2 bulk value and hence the presence of stress is
minimum (1.5 1010 dynes/cm2 ) in 80 nm thin ZnO lm indicating
that the presence of native defects reduces with increase in thickness of ZnO lm. The value of stress for ZnO thin lms of different
thickness is evaluated and is shown in Table 2. The crystallite size
of ZnO thin lms is calculated using the well known Scherrer formula [18]. The crystallite size of the ZnO thin lms increases from
10 to 20 nm with increase in thickness from 20 to 80 nm (Table 2).
The XRD experiments for the ZnO thin lms (40 nm) grown at different sputtering pressure (1040 mT) and different O2 percentage
(30100%) in reactive gas mixer of Ar and O2 have been performed.
The position (2) of (0 0 2) peak shifts toward the higher angle from
34.09 to 34.32 with increase in the oxygen percentage from 30%
to 100% in reactive gas composition. The deviation of 2 from the
bulk value and hence the value of stress is minimum for the lms
grown at 20 mT sputtering pressure (Table 2). Thus stress in the
ZnO thin lm increases when deposited at other pressure (10 mT).
At low pressure (<20 mT), the ionic species bombard the substrate
surface while lm processing with high energy thereby resulting in

possible defect formation in various forms (Zn interstitials and


oxygen vacancies) in the deposited ZnO thin lm. While at high
pressure (30 mT), the energy of the ionic species on substrate
surface is small due to extensive collision in the plasma. Hence
possibility of atoms to be absent from the lattice point increases
since mobility of the ad-atoms is less on the substrate surface and
they do not have sufcient energy to be in the equilibrium position
[21]. The crystallite size of ZnO thin lms increases from 9 to 17 nm
with increase in sputtering pressure from 10 to 20 mT and then
decreases to 13 nm with further increase in sputtering pressure to
40 mT (Table 2). However no signicant variation in the value of
crystallite is found for ZnO thin lms deposited at different gas
compositions.
Fig. 2 shows AFM images of the surface of ZnO thin lms (40 nm)
deposited at different sputtering pressures. It can be seen from Fig. 2
that ZnO thin lms deposited at 20 mT are smooth, having minimum average surface roughness. However the surface roughness
of ZnO thin lms grown at different composition of reactive gases
Ar + O2 (30100% O2 ) are almost same (Table 2).
3.2. Optical transmission
The optical transmission of ZnO lms of different thickness
(2080 nm) deposited at 20 mT pressure was studied in the wavelength range of 2001100 nm (Fig. 3) and found to exhibit good
transmission (80%) in visible region. The transmission data shown
in Fig. 3 has been taken several times however no signicant

Fig. 2. AFM image of the surface of ZnO thin lms deposited at different sputtering pressures (1040 mT).

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V.B. Raj et al. / Sensors and Actuators B 207 (2015) 375382

Fig. 3. UVvis transmission spectra of ZnO tin lms of different thickness


(2080 nm).

variation was observed. Transmission was found to decrease continuously with increase in thickness of the ZnO thin lms from 20 to
80 nm. The optical bandgap, Eg of the ZnO thin lms were estimated
from the plot of (h)2 versus h, where is the absorption coefcient and h is the photon energy. The estimated value of optical
bandgap of the ZnO thin lms increases slightly from 3.2 to 3.23 eV
with increase in thickness from 20 to 80 nm. The obtained values
of Eg are in good agreement to the corresponding values reported
by other workers for ZnO thin lm grown by various techniques
[22,23]. However no signicant change in band gap was observed
for the ZnO thin lms deposited at different sputtering pressures
and reaction gas compositions.
3.3. FTIR measurements
Fourier transform infra-red (FTIR) spectra of ZnO thin lms
deposited at different sputtering pressure (1040 mT) is shown
in Fig. 4a. The FTIR spectra (Fig. 4a) show an absorption band in
the region 400440 cm1 corresponding to E1 (TO) mode, which
are in agreement with earlier reports for ZnO lms and bulk conrming the formation of Zn O bond [24,25]. No signicant shift
in this absorption band is observed (Fig. 4a) for the ZnO thin lms
deposited at different sputtering pressures (1040 mT). However, a
continuous shift in the absorption band toward higher wavenumber was observed with increase in oxygen percentage (30100%)
in the reactive gas mixture (Fig. 4b). The frequency of absorption
mode depends on the relative masses of constituent atoms, force
constants of the bonds, and relative arrangement of the atoms [26].
Bond energy of Zn O bond calculated using E1 (TO) mode is found
to increase from 4.88 to 4.98 kJ/mol with decrease in oxygen percentage from 100 to 30% (Table 2).
3.4. Sensing response
The transient response characteristics of SAW sensor
(ZnO/SAW) having ZnO thin lm of different thickness (2080 nm)
with exposure to headspace vapors of DMMP (1600 ppm) is shown
in Fig. 5a. It can be seen from Fig. 5a that a decrease in the differential frequency (f) has been observed for all prepared sensor
with exposure to DMMP vapors. The magnitude of differential
frequency shift increases from 20 to 52 kHz with increase in
thickness of ZnO thin lm from 20 to 80 nm (Fig. 5a). The sensors
were found to regain the baseline during the recovery cycle when
DMMP vapors were removed (Fig. 5a). It is important to point
out that when the thickness of ZnO overlayer was 80 nm, the

noise or random uctuation in frequency was less than 20 Hz.


However when the thickness of ZnO thin lm increased to 100 nm
and above, the noise or uctuation in frequency increased to few
kilohertz. The sensor response of the ZnO/SAW sensor is also in
kHz. Hence ZnO lms of higher thickness (100 nm) are not taken
into consideration in the present work.
The variation in sensing response toward headspace vapors of
DMMP for ZnO/SAW sensor having ZnO thin lms deposited at
different growth pressures is shown in Fig. 5b. With increase in
sputtering pressure from 10 to 20 mT for deposition of ZnO thin
lms, the magnitude of differential frequency shift increases from
22 to 30 kHz (Fig. 5b). However, with further increase in growth
pressure from 20 to 40 mT, the sensing response toward DMMP
decreases from 30 to 25 kHz (Fig. 5b). Fig. 5c shows the response
of ZnO/SAW sensors having ZnO sensing layer grown under different oxygen percentage (30100%) in reactive gas composition
(Ar + O2 ) on exposure to DMMP vapors. The magnitude of differential frequency shift for ZnO/SAW sensor increases from 20 to 45 kHz
(Fig. 5c) with decrease in O2 percentage from 100 to 30% in reactive
gas ambient.
The variation of response time and recovery time of ZnO/SAW
sensor toward DMMP vapors is shown in Fig. 6a as a function of
the thickness of sensing ZnO lm. The value of both response time
and recovery time increase gradually from 8 to 37 s and 3 to 12 min
respectively with increase in thickness of sensing ZnO lm from
20 to 80 nm (Fig. 6a). The observed variation indicates that DMMP
vapor molecules take more time to adsorb as well as desorb on the
surface of SAW sensor having thicker ZnO sensing layer. It is important to note from Fig. 5a and 6a that sensor response, response time
and recovery time of ZnO/SAW sensor for DMMP vapors increases
with increase in thickness of ZnO thin lm. Hence, there is a tradeoff between response/recovery speed and sensing response of the
ZnO/SAW sensor. It may be seen that for 40 nm thin ZnO (deposited
at 20 mT pressure with) sensing layer, the negative shift in differential frequency is about 30 kHz having small value of response time
(20 s). The response time was found to increase to the signicant
value (>30 s) for thicker ZnO thin lm (60 nm) whereas, sensitivity
to the DMMP vapors was moderate. Hence, thickness of ZnO layer
for SAW sensor was chosen as 40 nm.
The variation in response time and recovery time of ZnO/SAW
sensor as a function of growth pressure and O2 percentage of
ZnO sensing layer is shown in Fig. 6b and c. The response time
for DMMP vapors (Fig. 6b) of SAW sensor with ZnO sensing layer
grown at lower sputtering pressure (20 mT) was found to be relatively smaller (20 s). The response time is relatively high (26 s) for
the ZnO thin lm deposited at higher sputtering pressure (30 mT).
Similarly, recovery time (Fig. 6b) for ZnO lm grown at low pressures (20 mT) was relatively small (<5 min) in comparison to that
obtained at higher pressure (20 mT). The response time was found
to increase linearly from 18 s to 25 s with increase in oxygen percentage from 30% to 100%, whereas recovery time shows a slow
decrease from 5.2 min to 4.8 min (Fig. 6c). Therefore, ZnO thin lm
deposited with 30% O2 in the sputtering gas mixture (Ar and O2 )
was exhibiting a high sensing response (45 kHz) with relatively fast
response speed (18 s) and hence optimum for the efcient detection
of DMMP vapors.
In order to study the selectivity, effect of the presence of common interferants (methanol, ethanol, acetone, benzene, xylene,
N2 O, and H2 ) on the sensing response of ZnO/SAW sensor were
studied after passing the respective vapors onto the sensor surface. The sensitivity (ratio of sensors response to the concentration
of respective target vapors) of the ZnO/SAW sensors having 40 nm
thin ZnO sensing layer grown under optimized condition toward
these interferants is shown in Fig. 7. The relative sensitivity of
ZnO/SAW sensor obtained for DMMP vapors is also included in
Fig. 7 for comparison. It can be noted from Fig. 7 that ZnO/SAW

V.B. Raj et al. / Sensors and Actuators B 207 (2015) 375382

379

Fig. 4. FTIR spectra of ZnO thin lms (40 nm) at (a) different sputtering pressure (1040 mT), and (b) gas composition Ar + O2 (30100% O2 ).

sensor exhibit a much higher sensitivity toward DMMP vapors as


compared to other interferant vapors, indicating good selectivity of
the prepared ZnO/SAW sensor toward DMMP vapors. The selection
of interferants has been done from practical point of view. DMMP
mimic the actual chemical warfare agent Sarin. Detection of Sarin
needs to be performed at the battleeld, defense laboratories etc.
where the possibility of commonly available gases/vapors like H2 O,
H2 NOx SO2 , NH3 etc. and volatile organic compounds (methanol,
ethanol, acetone, benzene, xylene) will be more.
The sensing response of the ZnO/SAW sensor was also studied
toward different concentration (51600 ppm) of DMMP vapors and
the observed variation is shown in Fig. 8. The magnitude of differential frequency shift of ZnO/SAW sensor was found to increase
continuously (3.945.0 kHz) with increase in the concentration of
DMMP vapors from 5 to 1600 ppm (Fig. 8). At high concentration the
value of frequency shifts increases exponentially. The exponential
rise might be because of the recombination of DMMP vapors with
each other and thus forming multilayers on the surface of ZnO giving large values of frequency shifts. There is also possibility of small
condensation of DMMP vapors on the surface of ZnO thin lm.
4. Sensing mechanism and discussions
The bare SAW sensor oscillator (without any ZnO coating) was
giving frequency shift of only 100 Hz with exposure to 200 ppm

DMMP vapors and hence the ZnO/SAW sensor is giving signicant


improvement in the sensor response. The resonant frequency of
ZnO coated SAW oscillators are less than that of uncoated SAW
oscillator (f0 ) by few MHz. The difference frequency (f = f0 fs )
is initially reset to zero value (in the absence of target gas). Thus
increase in the center frequency of ZnO/SAW sensor oscillator (fs )
due to interaction with target gas results in a negative difference
frequency (f), while decrease in fs will give positive difference frequency (+f) [17]. Various factors including mass loading,
acoustoelectric interaction, elastic changes, temperature, pressure,
etc. may contribute toward the response of SAW sensor [27]. In the
present case, pressure was kept constant on the surface of SAW
sensor by maintaining a constant ow of target vapors. The effect
of small temperature changes on the response of SAW sensor is
minimized by measuring differential frequency under dual SAW
oscillator conguration. Hence mass loading, acoustoelectric interaction, and elastic changes are the main perturbation effects which
are expected to contribute to the observed sensing response characteristics of ZnO/SAW sensor. It is known that the mass loading
effect causes a decrease in the frequency of SAW sensor oscillator
and therefore differential frequency is expected to increase (i.e.,
+f) [28]. On the other side, an increase in the elasticity of the sensing layer increases the frequency and hence differential frequency
decreases (f). The acousto-electric interaction may result in
either increase or decrease in frequency of SAW sensor depending

Fig. 5. Variation of sensing response of the ZnO/SAW sensor having ZnO thin lm (a) of different thicknesses (2080 nm), (b) at different sputtering pressure (1040 mT) and
(c) different oxygen composition (30100% O2 ).

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V.B. Raj et al. / Sensors and Actuators B 207 (2015) 375382

Fig. 6. Variation of response time and recovery time of the ZnO/SAW sensor having ZnO thin lm (a) of different thicknesses (2080 nm) (b) at different sputtering pressure
and (c) different oxygen composition (30100% O2 ).

Fig. 7. Relative sensitivity of ZnO/SAW sensor to DMMP vapors and other interferant
vapors.

upon the change in electrical conductance [29]. A decrease in resistance of the sensitive coating leads to a decrease in SAW velocity
thereby resulting in a decrease in frequency.
The effect of acousto-electric interaction on the velocity and
hence frequency of the SAW device is given by [28]:
K2

V
= cm f0  (s )

V
2

1
1 + (V0 Cs /s )

where, K2 is the electromechanical coupling coefcient,  s is the


sheet conductivity of the sensitive coating, Cs is the capacitance
per unit length of the device, V0 is the unperturbed SAW velocity,
V is the change in SAW velocity with exposure to target vapors. In
order to identify the contribution of electrical loading on the sensing response, an independent experiment was carried out. Since the
ZnO thin lm is coated over the IDTs (inter digital transducers), the
resistance of the ZnO lm across the IDT ngers is measured under
the exposure of DMMP vapors. No signicant change in the resistance of ZnO thin lm with exposure to DMMP vapors is observed in
the present work indicating the negligible contribution of acoustoelectric interaction toward the sensing response.

Fig. 8. Response of ZnO/SAW sensor having optimized ZnO thin lms with exposure
to DMMP vapors at different concentrations.

The change in SAW velocity and hence difference frequency (f)


because of mass loading and elastic changes is given as [28]:
V
= Cm f0  (s ) + Ce fo h
V0



5
Vo2

 

+

 + 2

where  and  are the Lames constants, Cm and Ce are the sensitivity coefcients of mass and elasticity respectively, h is the
thickness of the ZnO sensing thin lm and s is the surface density (mass per unit area) of the sensing thin lm. In the present
case, differential frequency of ZnO/SAW sensors with exposure to
DMMP vapors decreases i.e., f is negative. So contribution of mass
loading toward the observed sensing response is also insignicant
and change in elasticity is expected to contribute toward the sensing mechanism. The surface morphology of the sensing layer can
signicantly inuence the response characteristics. If the vapor
molecules get adsorbed on rough and porous surface of the sensing

V.B. Raj et al. / Sensors and Actuators B 207 (2015) 375382

lm, the elastic stiffness of the lm increases [28]. This will result
in increase in the frequency due to elastic changes and hence differential frequency of SAW sensor should decrease as observed in
the present case.
It can be seen from Fig. 5a that sensitivity of the ZnO/SAW
sensor toward DMMP vapors increases with increase in thickness
(2080 nm) of ZnO thin lms. The presence of pores plays a major
role in the vapor sensing phenomena. The exact analysis of the evaluation of pores can be performed by the adsorption isotherms using
BET technique [30]. However the evaluation of porosity of thin lms
by BET method can be quiet cumbersome since it requires sophisticated instrumentation and complex mathematical model [30]. The
indirect way of getting information about the porosity is by the
evaluation of refractive index. The refractive index of ZnO thin lms
was performed using SPR (surface plasmon resonance) technique.
The experimental details of the SPR technique have been published
earlier [31]. The refractive index of ZnO thin lms was found to
decrease from 2.51 to 2.33 with increase in the lm thickness from
40 to 80 nm. With decrease in refractive index the average porosity increases [31]. Hence in the present case with increase in the
thickness of ZnO thin lms, average porosity increases. Increase in
elasticity is not only conned to the surface but is also related to the
bulk property of the sensing lm. With increase in porosity, more
vapors molecules get trapped on the lm surface and hence the
magnitude of differential frequency shift increases. The response
time and recovery time of the ZnO/SAW sensor also increases with
increase in the thickness of ZnO thin lm from 20 to 80 nm, since
more trapped vapor molecules at pores or grain boundaries need
more time to adsorb and desorb from the surface.
The response of ZnO/SAW sensor toward DMMP vapors
increases with increase in sputtering pressure from 10 to 20 mT,
thereafter response decreases with further increase in sputtering
pressure (30 mT) (Fig. 5b). The observed variation can be correlated with the crystallite size of sensitive thin lm. The crystallite
size of ZnO thin lm was found to increase from 9 nm to 17 nm with
increase in sputtering pressure from 10 to 20 mT and decreases
from 17 to 13 nm with further increase in sputtering pressure to
40 mT (Table 2). The voids present between the larger crystallites results in trapping of more target vapor molecules, and thus
increase in the elasticity of ZnO lm (deposited at 20 mT) exhibits
enhanced response. Further, the response time and recovery time
for the ZnO/SAW sensors having ZnO thin lms deposited at higher
sputtering pressures increases (Fig. 8) due to increase in the surface roughness of the sensing layer at higher sputtering pressure
(30 mT).
The sensitivity of ZnO/SAW sensor toward DMMP vapors
increases for ZnO thin lm deposited with decrease in the oxygen gas percentage from 100% to 30% O2 in reactive gas ambient
(Fig. 5c). It may be noted that the amount of trap centers are nearly
same due to same crystallite size and surface roughness of ZnO
thin lms grown in varying O2 percentage. The contribution of elastic loading might be more for the ZnO sensing layer having strong
bond strength for Zn O bond. Since bond energy of ZnO thin lms
increases with decrease in oxygen content (Table 2) in processing reactive gas, the SAW velocity and hence frequency increases.
Hence higher the value of bond strength of ZnO lm (at 30% O2 ),
more is the differential frequency shift toward DMMP vapors.
Different metal oxides (ZnO, SnO2 , TiO2 and TeO2 ) have also
been exposed independently to DMMP vapors and it was found
that ZnO/SAW sensor was giving differential frequency shift f
of 0.6 kHz whereas SnO2 /SAW, TiO2 /SAW and TeO2 /SAW sensors
were giving comparatively low values of differential frequency
shifts (f 0.1 kHz) with exposure to 0.5 ppm DMMP vapors.
Hence ZnO thin lm coated SAW sensor was more sensitive toward
DMMP vapors as compared to other metal oxides. Since sensing
was performed at room temperature and DMMP vapors were able

381

to desorb from the surface of ZnO easily, there is little possibility


of any complex bonding. In literature, it has been shown in several
reports that metal oxide thin lms (especially ZnO) have the tendency to adsorb DMMP vapors [32]. However very few reports are
available related to the adsorption of DMMP vapors at room temperature since at low temperature there is possibility of any strong
bond which can be characterized [32]. The free surface of ZnO contains free Zn2+ and O2 ions [32]. Generally, DMMP interact with
the metal oxide surface through the phosphonate group present in
it [32]. Also the surface of ZnO contains various defects. Thus, the
phosphonate group present in DMMP molecule might be forming
weak bond with the free ions and defects present on the surface of
ZnO. The obtained results show that the prepared ZnO/SAW sensor
using optimized ZnO thin lm as sensitive coating has the capability to detect DMMP vapors efciently over wide concentration
range.
5. Conclusions
The processing parameters of ZnO sensing layer greatly inuence the sensing response characteristics of ZnO/SAW sensor
toward DMMP vapors. With increase in thickness of ZnO lm,
sensitivity toward DMMP vapors increases. The ZnO lm grown
under optimized conditions including 20 mT processing pressure
and reactive ambient of 30% O2 and 70% Ar exhibits the enhanced
sensitivity. A change in elasticity of the ZnO thin lms with exposure to DMMP vapors is the dominant sensing mechanism. Large
value of crystallite size and bond energy (Zn O) for ZnO thin lm
seems to favor the elastic loading effect. The ZnO/SAW sensor having optimized ZnO thin lm is able to detect very low levels of
DMMP vapors with good selectivity and fast response time (18 s).
Acknowledgements
Authors acknowledge nancial support from University Grants
Commission (UGC), and DRDO (Defense Research and Development
organization). The authors are also thankful to Anshu Goyal (Solid
State Physics laboratory, DRDO) for characterization (XRD) of ZnO
thin lms.
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Biographies
V. Bhasker Raj received his BSc (2005) and MSc (2007)
and PhD (2014) in Physics from University of Delhi, Delhi,
India. His research interests are in SAW sensor systems
that include development of SAW oscillator, sensor characterization, development of metal oxide lms for sensor
coatings and temperature stability of SAW devices. He
has also worked in the eld of Gas Chromatography for
explosives and chemical warfare agents.

Harpreet Singh received his BSc (H) (2007) in electronics


from University of Delhi, Delhi and MSc (2009) in electronics from Kurukshetra University, Kurukshetra, Haryana.
He is working as a research fellow at Solid State Physics
Laboratory (DRDO), Delhi since 2010. He is involved in
passivation of SAW device, development of RF and Digital
subsystem (FPGA and PLD) and development of E-Nose.

A.T. Nimal received his BSc (1991) and MSc (1993) in


Physics from Government Arts College, Bharathiar University, Coimbatore and PhD (2004) in Physics from National
Physical Laboratory, Delhi, and University of Delhi, Delhi.
He is working as a scientist at Solid State Physics Laboratory, Delhi since 1997. Presently he is involved in the
design and development of SAW devices such as delay
lines, dispersive delay lines, resonators and lters for the
above sensors and signal processing. He is also involved in
the development of low noise SAW oscillators, RF subsystem, digital subsystem (MCU, PLD and FPGA) and sensor
characterization. He has also worked in the eld of high TC
superconducting thin lms and transition edge bolometer
IR sensors during his PhD.
Monika Tomar received her BSc, MSc and PhD degrees
in Physics in 1996, 1998 and 2005 respectively, from the
University of Delhi. Presently, she is Assistant Professor
at Miranda House College, University of Delhi, India. Her
research interests include piezoelectric thin lms for Surface acoustic wave devices and sensors, oxide thin lms
and nanostructures for gas sensing and biosensing applications, photonic devices etc.

M.U. Sharma received his BSc (1983) and MSc (1985)


in physics from Kurukshetra University, Kurukshetra,
Haryana. He is working as a scientist at Solid State Physics
Laboratory, DRDO, Delhi since 1986. His research interests
are E-beam Lithography, Photo mask fabrication and SAW
Technology including fabrication of SAW devices and its
application as sensors.

Vinay Gupta received the BSc, MSc, and PhD degrees in


physics in 1987, 1989, and 1995, respectively, from the
University of Delhi, New Delhi, India. He also worked as
a Reader in physics at DDU College, University of Delhi.
Presently, he is a professor in the Department of Physics
and Astrophysics, University of Delhi. He is a recipient of
BOYSCAST fellow and MRSI medal. His current research
interests are in piezoelectric thin lms and layered structures, semiconductor and surface acoustic wave (SAW)
sensors, ferroelectric lms for electro optic applications,
and nano-structured oxide materials for multifunctional
application.