Sensors and Actuators B 94 (2003) 337–342

Zeolite-modified microcantilever gas sensor for indoor air quality control

Jia Zhou a,b , Po Li a , Song Zhang c , Yingcai Long c , Feng Zhou c , Yiping Huang a,∗ ,
Pengyuan Yang c , Minhang Bao a
a ASIC and System National Key Lab, Department of Microelectronics, Fudan University, 220 Handan Road, Shanghai 200433, China
b Department of Mechanical Engineering, Jinshan Campus, East-China University of Science and Technology,

1166 Songjin Road, Shanghai 201512, China

c Chemistry Department, Fudan University, 220 Handan Road, Shanghai 200433, China

Received 29 January 2002; received in revised form 25 October 2002; accepted 16 April 2003

Abstract

To control indoor air quality, a novel freon gas sensor of piezoelectric microcantilever coated with zeolite has been developed in this
paper. Excited by an ac voltage, the microcantilever is employed to detect the concentration of sample freon-12 gas ranged from 0 to
100 ppm by the effect of the specific MFI zeolite modification. High selectivity and sensitivity combined with excellent repeatable and
reversible performances are shown. The relationship between the frequency shift in percent and the concentration of freon gas is linear.
The minimum mass changing of 3.5 × 10−9 g and the sensitivity of −0.0024%/ppm are determined from the experimental results.
© 2003 Elsevier Science B.V. All rights reserved.

Keywords: Microcantilever; Zeolite; Gas sensor; Freon

1. Introduction A microcantilever in resonating mode has attracted inten-

sive interest these years on account of its much higher sen-
A micro-total analysis system (␮-TAS) or a “Lab-On-Chip” sitivity than the classical methods [1–3]. Cantilevers used as
for integrated chemical and biochemical analysis has grown nanoscale sensors for atomic force microscope (AFM) have
dramatically in the past decade. The concept extends the recently been extended beyond those of a surface-imaging
scope since its introduction by Manz at Transducers’89 tool. The masses of such sensors are typically in nanogram
and now encompasses analysis and synthesis for applica- range, thus enabling short response time (milliseconds) and
tions ranging from chemistry through to biology. By using high sensitivity well beyond what is achievable with stan-
a high degree of parallelism in the designs it has become dard techniques. Such micromechanical sensors have been
clear that automation of high sample throughput is possible. configured to be used as calorimeters and surface stress sen-
Meanwhile, an enormous amount of researches have been sors. A piezoelectric microcantilever in resonating mode,
devoted to the development to miniaturize chemical and which shifts its resonance frequency due to mass loading,
biochemical sensors, which has great effect on expanding has shown very high sensitivity for sensing chemicals and
the application fields, such as quality and process control, has broad and potential application areas related to environ-
disposable diagnostic biosensor for medical analysis, fra- mental control [4], artificial nose [5], drug discovery [6],
grance design, oenology, and as sensing devices for gaseous etc. Air quality is one aspect of environmental control. With
analytes. However, the miniaturization of chemical sensor the extensive use of air conditioner, problems with freon gas
is of great complexity, functionality and compactness, and emission have increased in recent years. Rapidly and accu-
the sensitivity of the device and consequently the analytical rately determining the concentration of freon gas plays an
power should be enhanced. Therefore, it is important to find important role on air quality control and assay, especially
a sensor with a high sensitivity and easy to be miniaturized on indoor air quality control.
and mass-produced. Although cantilever presents high sensitivity, in order
to recognise different specific chemicals, improving the
sensor’s selectivity becomes one of the critical factors. A
∗ Corresponding author. Tel.: +86-21-6564-2069; great many researches of sensing materials have been done
fax: +86-21-6564-8267. to increase selectivity, including polymer [7,8], metal [3],
E-mail address: [email protected] (Y. Huang). oxide [4] and so on. Zeolites are the subject of intense

0925-4005/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0925-4005(03)00369-1
338 J. Zhou et al. / Sensors and Actuators B 94 (2003) 337–342

interest as chemical sensors and as advanced materials. The Table 1

nano-sized channel system of the zeolites provides a size Theoretical and experimental resonance frequencies
and shape-selective matrix for absorbed molecules while Frequency (Hz) Mode index i
maintaining a high surface-to-mass ratio. Microcompos- 1 2 3 4
ite coatings with molecular sieving properties have been Theoretical 1697 10634 29815 58426
deposited on surface acoustic wave devices [9], quartz Experimental 1646 9276 28500 –
microbalances [10], and zeolite composites [11].
In this paper, as a special application of indoor air quality
As can be seen from the cross-sectional view of the micro-
control, study on novel microcantilever sensor with a piezo-
cantilever in Fig. 1, the microcantilever is composed of five
electric layer working in the resonating mode modified with
different materials. Here we assume the properties of such a
a thin-layer MFI type zeolite to determine freon-12 gas is
multilayer structure follow a rule of mixtures approach [14].
firstly to be reported. Such microcantilever shows high se-
Therefore, the natural frequency of the composite beam can
lectivity and sensitivity for the determination of freon-12.
be expressed as follows:



λ2i Ei li λ2i Ei li
2. Theoretical Background fi = =
2πL2 Aρc 2πL2 mc /L

A straight elastic beam model is applied here. Its reso- ρc tc = ρi ti mc = ρc AL (4)
nance frequency is calculated by using Newton’s second
equation of motion. The details are given in [12] and later. where mc , ρc and tc are the mass, density and thickness of the

composite beam, Ei , li , ρi and ti are the Young’s modulus,
∂ 4w ∂ 2w EI the moment of inertia, the density and the thickness of each
c2 4 (x, t) + 2 (x, t) = 0 c= (1)
∂x ∂x ρA layer, respectively.
Table 1 gives the resonance frequencies of our microcan-
where w(x, t) is the motion of the beam, ρ the density of the tilevers. The resonance frequencies from experiments show
beam, A the cross-sectional area, E and I are the Young’s some shift-down comparing to their theoretical ones, which
modulus and the moment of inertia of the beam. By solving relates to the deposition of the zeolite layer.
Eq. (1), we obtain the following solutions: Working as a mass-sensitive transducer, the microcan-
tilever translates the mass changing by the adsorption of the
w(x, t) = W(x)T(t) T(t) = A cos(ωt) + B sin(ωt)
zeolite layer to specific gas molecules to mechanical fre-
W(x) = C1 cos(βx) + C2 sin(βx) + C3 cosh(βx) quency shift and finally to electrical signal output. The rela-
+ C4 sinh(βx) tionship between the frequency shift fi and mass loading

mc can be calculated from the equation followed accord-
EI
ωi = (βi L)2 ωi = 2πfi (2) ingly:
ρAL4

fi 1
where fi is the resonant frequency of the beam, L the length = −1 (5)
fi mc /mc + 1
of the beam. With the boundary condition of the one end
fixed cantilever beam, i.e. cos(βi L) cosh(βi L) = −1 its nat- The above equation can be developed as a series
ural frequency fi in hertz can be expressed as follows [11]:    

fi 1 mc 3 mc 2 15 mc 3
λ2i EI = + + + ··· (6)
fi = (3) fi 2 mc 8 mc 48 mc
2πL 2 ρA
when mc /mc is small enough, the first item on the
where λi is a dimensionless parameter tabulated in [13]. right can approximate the relationship between fi /fi and

Fig. 1. Structure of the piezoelectric microcantilever. The dimensions are length 970 ␮m, width 300 ␮m and thickness 3 ␮m.
 J. Zhou et al. / Sensors and Actuators B 94 (2003) 337–342 339

mc /mc , i.e.

fi 1 mc
= (7)
fi 2 mc
Moreover, by introducing a thermal equilibrium constant—
the partition coefficient K to quantify the adsorption behavior
of a zeolite layer with regard to different analytes, we find
[15]
KMa VZ Cs
mc = C K= (8)
Vm × 106 Cg
where Cs and Cg are the analyte concentration in the zeolite
and in gas phase in mol/l, respectively, Ma is the molar
weight of the analyte, VZ the volume of the zeolite layer,
Vm the molar volume (ppm). Under the assumption of an
ideal gas (Vm p = RT), inserting Eq. (8) into Eq. (7), then Fig. 2. Measuring system. The microcantilever is excited by the PZT thin
yields the linear relationship between fi /fi , which explicitly layer, which works as an actuator here by the action of a 50 mV ac voltage
expresses the sensitivity of the microcantilever sensor S, i.e. with a frequency sweeping from the Network Analyzer HP-4395A. The
doppler laser interferometer OFV3001/512 detects the resonance of the
fi /fi KMa VZ p
S= = × 10−6 (%/ppm) (9) microcantilever and its output signals are displayed on HP-4395A.
C 2RTmc
where p is the ambient pressure, R the molar gas constant,
T the temperature. chloro–fluoro-hydrocarbons on MFI zeolite is in the range
of 33–61 kJ·mol−1 , indicating a stronger interaction be-
tween these organics and the frameworks. The fact gives
3. Experimental the possibility for using these zeolites as an adsorbent
to remove or absorb the chloro–fluoro-hydrocarbons in
A PZT layer has been deposited onto the substrate layer air and as a sensitive material in an instrument of anal-
of Si3 N4 /SiO2 with two Pt electrodes that actuate the micro- ysis. A specific recipe for the applicable zeolite solution
cantilever to vibrate under an ac voltage. The dimensions of is made by Chemistry Department at Fudan University
the structure are 970 ␮m long, 300 ␮m wide and 3 ␮m thick. [16].
The cantilever surface is rinsed carefully with acetone
3.1. Sample chamber setup (analytical grade) solution and air-dried. Before applied, the
MFI type zeolite solution is diluted by double-distilled wa-
When working, the sensor is housed in a sample chamber ter to suspending solution about 0.002% (w/v). Thin layer
made of stainless steel (volume: 310 ml). The measurement of zeolite is formed onto the cantilever after it accepted a
system (Fig. 2) involves a Doppler Laser Interferometer droplet (0.2 ␮l) of the diluted solution and is baked at 100 ◦ C
OFV512/3001 (Polytec GmbH, Germany) and a Network for 10 min in the oven.
Analyzer HP4395-A (Hewlett-Packard, USA). Thin film
PZT layer excites the sensing element to vibrate at 50 mV ac 3.3. Cantilever sensor measuring
voltage within a sweeping frequency range. The detection
is carried out by focusing on the first two resonance peaks. In this experiment, freon-12 is chosen as the main sample
Since the focusing frequencies are very low (<10 kHz), in gas. Its concentration ranges from 0 to 100 ppm. In the se-
order to get precise measurement the sweep points is set to quence of concentration from low to high, freon-12 is drawn
201 and thus the measuring time is set to 188.4 s per sweep into the testing chamber that has been evacuated by a pump
automatically. and the focused resonance frequency is recorded. The sens-
ing experiments during desorption of molecules from zeo-
3.2. Cantilever sensor coated with a thin layer of zeolite lite are also done under control, i.e. the detection goes on
while the concentration of freon in the testing chamber is
An exclusively freon-sensitive MFI type zeolite solu- decreased at a controlled rate. Such tests are designed for
tion is applied in our work. Such siliceous zeolite with checking the gas on and off characteristics and the repeti-
perfect Si–O frameworks exhibits highly hydrophobic and tion property of the microcantilever as well. To verify the
organophilic characters [16,17]. The saturated loading of high selectivity of the microcantilever, two tests have been
water vapor on it usually is lower than 10 mg/g at ambient conducted: (a) microcantilever with MFI at the atmospheres
temperature. On the other hand, the loading of freon-12 of freon-12 and ethanol; (b) bare microcantilever (without
on MFI zeolite is 211 mg/g [18]. The adsorption heat of any modification) at the same atmospheres.
340 J. Zhou et al. / Sensors and Actuators B 94 (2003) 337–342

Table 2
Responses of microcantilever sensor to freon-12 gasa
Compound Equation Correlation Linear range Detection
(ppm) limits (ng)
Freon-12 y =−0.0024x 0.9931 0–100 3.5
− 0.01 b
a Under the same experimental conditions as stated in Fig. 3.
b The units of y and x are %/ppm and ppm, respectively.

sponses of the microsensor. The y-axis gives the amplitudes

of vibration in dB. Those grey curves are the responses at
vacuum tested before freon of different concentrations is
pumped in, while the dark curves are the responses to freon
of different concentrations whereafter. It can be seen that
there are clear frequency shifts of the zeolite microsensor
by changing chamber condition with and without freon gas.
Along with the increasing concentration, the trend of fre-
quency shift-down is distinguishable. Compared with the re-
sults in the vacuum, the lower frequency with a lower peak
at the concentration of 100 ppm freon is clearly observed,
which can be assured to mass loading for adsorption of freon
molecules to the MFI type zeolite on the surface of the mi-
crocantilever sensor.
Fig. 3b shows the linear relationship between the fre-
quency shift and the concentration of freon from 0 to
100 ppm. Based on the frequency shift, the mass loading
m can be calculated from Eq. (5). Here the minimum
Fig. 3. Experimental results. (a) Direct response curves of the micro- detectable mass loading of 3.5 × 10−9 g corresponding to
cantilever in vacuum and in the ambience of different concentrations of the concentration of 10 ppm is reached. Moreover, the sen-
freon-12. The frequency shifts down with a lower peak corresponding to sitivity of the microcantilever also can be obtained from the
100 ppm freon-12 compared with that in vacuum. (b) Linear responses of slope of the linear relationship between the frequency shift
frequency shift in percent vs. concentration of freon-12 ranged from 0 to
100 ppm.
and the concentration. The sensitivity has been found to
be −0.0024%/ppm. Table 2 presents the result of the data
analysis.
4. Results and discussion Fig. 4 shows the reversed frequency shift accompanying
with the desorption of freon molecules from the zeolite
To demonstrate the sensitivity of the microcantilever sen- sensor. According to the measuring cycle time 188.4 s, the
sor modified with a thin-layer MFI type zeolite to analyte, desorption process from 100 ppm to 0 is conducted by con-
a series of freon-12 gas with the concentration from 0 to trolling the total period as 942 s. The frequencies shift up
100 ppm are tested. Fig. 3a shows the direct measuring re- linearly and almost back to its original value—the small

Fig. 4. Responses accompanying the desorption of the freon-12 molecules from MFI type zeolite surface. Frequency shifts up with the increase of the
concentration. The measuring cycle time is 188.4 s.
 J. Zhou et al. / Sensors and Actuators B 94 (2003) 337–342 341

Fig. 5. Gas-on and repetitive properties of the gas sensor presented by its responses to 100 ppm freon-12. The right plug-in plot shows the identical
frequency of 1642 Hz with different amplitudes in six sweeps.

Fig. 6. Selectivity tests. (a) Responses of microcantilever with MFI to (䉬) freon-12, (䉱) ethanol. (b) Responses of bare microcantilever to (䊏) freon-12,
(䊉) ethanol.

difference is convinced due to the some higher vacuum zeolite shows great response to freon-12 gas with different
pressure at the end than that at the beginning, which results concentration, but no response to ethanol in the concentra-
from the control of time but not directly accurate pressure tion in 100–500 ppm, respectively (see Fig. 6). The results
during measurement. show that the thin layer MFI type zeolite at the surface of
To test the gas-on and repetitive properties of the mi- microcantilever is not only sensible but also very selectable
crocantilever sensor, six sweeps in the ambient of 100 ppm to response of the freon-12 gas. Under the control test, the
freon-12 are made focusing on the first frequency. To acquire bare microcantilever shows no evident frequency shift at
the quick gas-on response with the same accuracy (sweep- different concentration of freon-12 and ethanol. Therefore,
ing point number = 201), we set the starting frequency to the microcantilever modified with MFI type zeolite presents
1625 Hz to assure to reach the focused peak within 20 s. high selectivity characteristics to freon-12 against the inter-
Fig. 5 presents the six responses when the sensor is exposed ference gas, such as ethanol.
to the 100 ppm freon-12 within 20 s. The six sweeps are
conducted in two separate days with a interval of 1 week.
All of them demonstrate the identical frequency of 1642 Hz, 5. Conclusions
but with different amplitudes, which can be separated into
two groups: one with the amplitude around −3 dB, the other For the first time, a novel piezoelectric microcantilever
around −5 dB. Gas-off experiments are also carried out in sensor with a layer of microporous material zeolite has been
the same way but after 20 s evacuation. Frequencies come fabricated and used to determine the freon-12 gas in this
back to their original values with a relative error lower than paper. Because of the effect of zeolite, high selectivity has
0.5% within 20 s after the evacuation starts. During the test- been obtained simultaneously in addition to intrinsic high
ing period about 3 months, the responses of microcantilever sensitivity of the piezoelectric microcantilever in resonance.
to freon-12 gas show very good repeatability and sensitivity. A linear relationship between the frequency shift of the mi-
The freon-12 gas recognition capability of the microc- crosensor and the concentration of freon-12 gas is also ob-
natilever sensor modified with MFI type zeolite has been tained. The sensitivity of microsensor to the response of
performed with the control of the bare microcantilever. It freon gas is −0.0024%/ppm and a minimum detectable mass
is found that the microcantilever with a layer of MFI type loading of 3.5×10−9 g is exhibited when the specific zeolite
342 J. Zhou et al. / Sensors and Actuators B 94 (2003) 337–342

MFI sensitive to freon-12 gas is applied. Very good repeata- [5] M.K. Baller, H.P. Lang, A cantilever array-based artificial nose,
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[11] K. Hoffmann, F. Marlow, J. Caro, Zeolites 16 (1996) 281.
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[12] S.S. Rao, Mechanical Vibrations, Addison-Wesley, Reading, MA,
also very thankful to Dr. YaolinWang, Xiaozhen Huang and 1986.
Bin Xiong at Shanghai Institute of Metallurgy for their pro- [13] R.D. Blevins, Formulas for Natural Frequency and Mode Shape,
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