Sensors and Actuators B 21 (1994) 39-50

Zeolites as sensitive materials for dielectric gas sensors

K. Alberti, F. Fetting
Imtitit p

Chmiwhe Technologie der Technischen Hochschule Lkmutadt, Petmwwhnsse 20, Domtadt,

Germany

Received 20 October 19% in revised form 12 November 1993; accepted 26 November 1993

Abstract
Modern sensors are becoming increasingly important as key components in the progressive automation of industrial processes.
Particular interest is attached to sensors that can be miniaturized, such as the capacitive gas sensors for hydrocarbons described
in this paper. Coating planar interdigital capacitors with highly selective zeolites can improve the performance,
particularly
the selectivity, of gas sensors. The response of the sensor is measured by the change in the capacitance of the interdigital

capacitors at a frequency of 1 kHz. The influence of the capacitor structure and of differently modified molecular sieves on
the sensor characteristics has been studied by means of impedance spectroscopy. The design of the sensor and the way in
which it functions are discussed.
Keywords: Dielectric gas sensors; Zeolites

1. Introduction

Modern sensors are of growing interest both in the

industrial field and in the domestic market. A high
degree of automation of industrial processes can only
be achieved by the increasing use of sensors. Whereas
previously it was necessary to resort to time-consuming
and expensive analytical methods, these tasks have now
been taken over by advanced sensor systems. Specific
sensors for the measurement of chemical parameters
will be of particular interest in the future, since they
can be used in a wide range of areas [ 11, and miniature
sensors will make an above-average contribution in this
respect [2]. The future development of sensors will
focus mainly on attempts to integrate the sensor system
and its electronics onto a single chip [3]. New types
of sensor systems such as semiconductor sensors [4,5]
and metal oxide sensors [6-S] point in this direction
[9]. In these systems the changing conductivity of the
sensor layers is used as the measurable parameter.
Another route that is being followed is the production
of dielectric gas sensors. The basic structural element
in these sensors consists of a planar capacitor having
electrodes with a comb-like design, which has been
used in a special form for this work. Most of the
applications of this sensor principle have so far been
devoted to the measurement of atmospheric humidity.
The response of the sensor is measured by the ca-

0925-4005/94/X17.00 0 1994 Else&r Science S.A. All rights reserved

SSDI 0925-4005(93)01211-L

pacitance of the capacitors, which changes as a function

of the humidity [l&14].
The work presented here has involved fundamental
experiments aimed at demonstrating the suitability of
zeolites in the construction of a selective sensor system
for measuring hydrocarbons. The use of zeolites as the
sensitive material opens up an interesting possibility
of improving the selectivity of chemical gas sensors [15].

2. Zfxdites
Zeolites are highly porous crystalline aluminosilicates.
They exhibit a number of unusual chemical and physical
properties determined by their special crystal structure,
which contains uniform pores and channels having
dimensions of the order of smaller molecules. So far
about 40 naturally occurring zeolites and more than
200 synthetic zeolites are known, and their chemical
composition may be descriied by the following molecular
formula [16]:

The common structural elements of the zeolites are

the AlO,- or SiO, tetrahedra. The three-dimensional
linking of the tetrahedra via their vertices leads to the
build-up of a crystal lattice with the cavities and channel
structures typical of zeolites [17,18].The negative charge

40

K Alberti, F. Fetting I Sensors and Actuators B 21 (1994) 39-50

of the AlO,- tetrahedra is balanced by interchangeable

metal cations, which are present inside the channels
and cavities. Selective ion exchange can be used to
modify the material properties of the zeolites to provide
a wide range of possible applications [19].
In their dehydrated state the zeolite crystals have a
very large internal surface area ranging from 400 to
more than 1000 m/g, which results from their system
of channels and cavities. The strong electrostatic fields
within the crystals and the close contact of the sorbate
molecules with the zeolite framework, combined with
the large internal surface area, give rise to a high
adsorption capacity. Zeolites are able to adsorb particular molecules selectively or to convert them catalytically in a structurally selective manner.
The main areas of application of zeolites are their
use as catalysts in a number of important reactions
[2&30], as adsorbents [31,32] and as ion exchangers
(33,341.As a result of their special properties, zeolites
have recently received increasing attention in materials
science [35]. For example, recent studies have been
concerned with the use of zeolites as solid electrolytes
for ion-selective membranes, or as electrode materials
for battery systems [36-391. In the field of sensor
technology too, zeolites have been used as filter layers
to increase the selectivity of non-selective sensors. For
example, the response of MOS gas sensors has been
changed by coating the catalytically active palladium
gate electrode with zeolites [40]. Membranes containing
embedded ZSM-5 crystals have been used to coat a
surface acoustic wave (SAW) component [41].

Hexagonal Prism
Fig. 1. Structure of zeolite X built of units with four-membered and
six-membered rings. Pore openings are built of L&membered rings.
Positions of cations are described in Table 2.

Table 2
Cation positions of zeolite X (see Fig. 1)
Position

Description

in centre of hexagonal prism

&him sodalite cage near hexagonal prism

II

in centre of 6-membered rings behveen aand ,%c.age

II

near 6-membered rings between cr- and /3cage (within supercage)

III

near 4-membered rings of supercage

111

near 4-membered rings shifted to the

2.1. The selection and descriptionof zeolites ased in

this work

inthOr

The Type X zeolites and mordenite were chosen as

typicalwide-pored zeolites, and were used in the lithium,

sodium and potassium forms. The zeolites employed
are listed in Table 1, together with their pore sizes.
Figs, 1 and 2 show the structures of the Type X
zeolites and mordenite used (see also Tables 2 and 3),
and indicate the possible positions for the metal cations
to maintain charge neutrality. Zeolite X is built up of
units consisting of four- and six-membered rings.
The characteristic structural units of mordenite are
five-membered rings that form long chains. The latter
are linked to each other via four-membered rings, giving
Table 1
Pore diameters of zeolites used
Zeolite

Pore diameter
(a)

-IMaX
Mordenite

0.74
0.67 X 0.7

Sodalite Cage

Supercage

IV

in centre of u-cage

in centre of ll-membered
hvo rr-cages

VI

in centre of @cage

rings between

rise to a system of channels having twelve- and eightmembered ring apertures [42].
2.2. Characterizationof the zeolites
The zeolites employed were modified by ion exchange
and by calcination. The structure, composition and
adsorption properties of the zeolites used were characterized by X-ray dilfraction, IR spectroscopy, electron
microscopy, chemical analysis (AAS) and adsorption
measurements. The concentrations of the exchanged
alkali-metal cations are given in Table 4.

IL AMti,

41

F. F&t@ / Sensorsand Actitorx B 21 (1994) 3%50

Fig. 2. Structure of zeolite mordenite. Mordenite possesses fewer cation positions than xeolite X. Positions of cations are described in Table
3.

Table 3
Cation positions of mordenite (see Fig. 2)
Position

Description

within centre of distorted E-membered

rings in side pockets

II

near E-membered rings averted from

main channels

III

within side pockets

Iv

at entrance of side pockets

within centre of main channels

VI

in main channel near wall

capacitors having comb-like interlocking finger electrodes. The capacitors take up very little space but
possess a large electrode area, which can easily be
coated with sensitive materials as a result of the planar
structure. Thin layers of zeolite can then act as a gassensitive dielectric. Fig. 3 shows diagrammatically the
structure of an interdigital capacitor having an electrode
finger width w, a separation between the electrodes s
and a thickness t. The carrier substrate has a relative
dielectric constant Q, that of the gas-sensitive layer
being Q. The dashed lines show the axes of symmetry
of the unit cell.

Table 4
Analyses of metal-ion exchange for xeolite X and mordenite
cation
exchanged

Exchange
(at.%)

Method of
analysis

zeolite x
Lithium
Sodium
Potassium

11.8
15.7
16.2

AAS
AAS
EDXb

SensorChip

CapacitorElectrodes

MordeIlite
Lithium

1.8

AAS

Sodium
Potassium

3.9
5.9

EDX
EDX

Atomic absorption spectroscopy

bElectron diffraction X-ray.

3. Interdigital capacitors
The basic sensor elements used in this work are
interdigital capacitors produced by modem semiconductor technology. Interdigital capacitors are planar

I
Fig. 3. Sketch of interdigital capacitor.

42

K Alberti, F. Fetting I Sensors and Actuators B 21 (1994) 39-50

4. Experimental
4.1. Production of the interdigital capacitors
The interdigital capacitors were produced on silicon
and quartz carrier substrates by using thin-f& technology. The dimensions of the carrier in the completed
capacitors were 7.5 mmx 8.5 mm. The capacitors were
constructed with different electrode widths, w = 10 and
20 pm. The ratio of the width of the electrodes to
their distance apart is one (see Fig. 3). The length of
the electrodes is 4.2 mm and their total width 5.8 mm.
Table 5 summarizes the capacitances of the uncoated
interdigital capacitors and includes the different dimensions and substrate materials employed. Before
carrying out the coating process, the capacitors were
attached to TO-8 bases using a high-melting solder
(melting point 400 C). The capacitor electrodes were
connected to the pins on the base with gold wire.

Fig. 4. REM picture of interdigital capacitor coated with zeolite.

4.2. Sensor preparation

A specially developed process was used to produce
thin layers from the powdered samples of zeolite. The
latter, in the form of aqueous suspensions, were sprayed
through a template onto the heated capacitor surface
by means of compressed air. The experimental set-up
under optimized conditions was a suspension of 0.5
wt.%, a gas pressure of 1.5 bar and a surface temperature
of the capacitor of 130 C. This produced homogeneous
layers having a thickness of 70-90 I.crn (Fig. 4). For
future work, however, a silk-screen process seems to
be more appropriate.
4.3. Description of the sensor measuring system
The sensor measuring system comprised a gas metering section, the heatable measurement chamber for
the gas sensors and the electronic instrumentation for
performing the impedance measurements. The hydrocarbon n-butane was used as the model gas over the
concentration range O-l.0 vol.%, and synthetic air was
used as the carrier gas. The flow rate of the carrier
gas during all the measurements was 1 Urnin. The gas
sensors were connected to an impedance meter (Hewlett-Packard, type HP 4284A) by means of screened
Table 5
Capacitance of uncoated interdigital capacitors (frequency used: 1
Hz)
Capacitor structure
(width/distance)

Capacitance (pF)

20 &2O jun on silicon

10 pm/l0 fim on silicon
10 pm/l0 gm on quartz glass

120
132
23

(fl

PF)

Kc

R ws

Fig. 5. Equivalent circuit of interdigital capacitor coated with zeolite

with impedance elements to be considered.

coaxial cables via a selector switch box which was also

screened. A program developed for data acquisition
enabled the impedance measurements to be performed
automatically.
4.4. Impedance spectroscopy measurements
The impedance spectroscopy measurements were carried out by measuring the complex impedance over the
frequency range 20 Hz-l MHz. The capacitance C,
and resistance R, derived from the complex impedance
can also be measured directly at a fixed, predetermined
frequency. The measurements made as a function of
time to determine the response behaviour of the gas
sensors were performed in this way at a frequency of
1 kHz.
The computer-aided evaluation of the impedance
spectra was performed with the IM5d impedance measurement system using an integrated data-acquisition
and analysis system. An appropriate equivalent-circuit
diagram was developed for calculating the resistance
and capacitance of the zeolite-coated interdigital capacitors (Fig. 5). This computer model was developed
with regard to all occurring electrochemical processes.
The geometric cell capacitance C,= CIDC,derived from

K Albeni, F. FettingI Senrom and Actuators B 21 (1994) 39-50

the structure of the capacitor, the electrolytic resistance

of the zeolite layer R(zeolite layer) and the difision
processes and crystal-boundary effects were included
to provide complete modelling of an equivalent-circuit
diagram. The capacitance due to electrode polarization
is allowed for as a capacitance C,,, and the polarization
resistance is taken into account in the resistance RWB.
In the case of non-homogeneous electrolytes such as
compressed powders, sintered samples and zeolite layers
composed of small zeolite crystals, the equivalent-circuit
diagram is extended to include the crystal-boundary
capacitance C, and the crystal boundary resistance
RKI. Similar equivalent-circuit diagrams were also developed for interdigital capacitors coated with inorganic
or organic materials. These capacitors are used as
humidity sensors [43-45].

5. Experimental results
5.1. Results of the impedance spectroscopy studies

The behaviour of gas sensors will first be demonstrated

by taking the interdigital capacitor coated with zeolite
Na-X as an example. Fig. 6 shows the impedance
spectrum of a sensor coated with zeolite Na-X when
exposed to increasing concentrations of n-butane gas
with the measurements being made at 200 C. The plot
of the experimental data as an impedance spectrum
shows an almost semicircular shape with minor deviations from the ideal shape. The centre of the semicircle
,,O-Z

[kOhm]

43

is positioned slightly below the real axis. The effect of

increasing the concentration of the gas over the range
O-l.0 vol.% on the first semicircle, which defines the
effects within the volume of the zeolite layer, can be
clearly recognized. The impedance circle for the subsequent impedance elements appears to some extent
in the low-frequency region of the spectrum. The experimental data for the subsequent impedance elements
only vaguely indicate the influence of butane owing to
limitations in the experimentally applied frequency
range. The experimental data were interpreted by applying a generally acknowledged model that describes
electrochemical effects through an assembly of equivalent circuits, as was detailed in Section 4.4 (Fig. 5).
The resistance R(zeolite) and the capacitance Cm,
the elements of main interest, were assigned to the
resistance of the zeolite layer and the geometrical
capacitance of the interdigital capacitor, respectively.
Possible influences at the grain boundaries are also
accounted for in the equivalent circuit as C, and R,.
From the impedance spectra it can be seen directly
that as the concentration of the n-butane test gas is
increased, the resistance of the zeolite layer decreases.
The corresponding capacitance values can be calculated
from the diagram. The values of the capacitances and
resistances of the equivalent circuit were fitted to the
experimentally derived values by iteration. It should
be noted that, in the model used, all single parts must
be included in order to get the best fit between experimental data and the theoretical model.
The values of the resistance R(zeolite) and the capacitance C,, calculated from these impedance spectra
on the basis of the equivalent-circuit diagram for the
zeolite-coated interdigital capacitor (Fig. 5) are summarized in Table 6 for the measurements made at 200
C. The above-mentioned non-ideal behaviour should
be taken into account as an explanation for minor
discrepancies between these results and values derived
directly from the plot in Fig. 6. No conclusion can be
drawn for the elements C,,, and RwB because the
frequency range in the experimental set-up was too
small. A direct assignment of the model parameters
to all the electrochemical processes involved needs
Table 6
Values of capacitances C,, and resistance R(zeolite) of Na-X sensor
(calculation was performed according to equivalent-circuit diagram
in Fig. 5)

50

100

150
2

200

250

Concentration
of n-butane
(WI.%)

GDC

R(zeolite)

(PF)

(W

0
0.2
0.5
1.0

208*2
214*2
218f2
222*2

210f2
193*2
177*2
170f2

300

[kOhm]

Fig. 6. Impedance spectra of Na-X sensor with various n-butane

concentration between 0 and 1.0 vol.%: 0, 0%; 0, 0.2%; 0, 0.5%;
A, 1.0%.

44

K Alberti, F. Fettiq

I Senrom and Actuators B 21 (1994) 39-50

additional investigations and cannot be given at the

present time.
The capacitance CIoc calculated from the impedance
spectra increased from 208 to 222 pF. The adsorption
of hydrocarbon led to an increase in the polarizability
of the zeolite frameworkxation system. The increase
in the polarizability of the zeolite layer was therefore
the cause of the observed increase in the capacitance
of the capacitors.
Moreover, the interactions of the adsorbed molecules
with the zeolites led to an increase in the ionic conductivity of the zeolite layer. The resistance of the
zeolite layer, R(zeolite), can therefore also be used as
a parameter in addition to the capacitance. In contrast
to the capacitance CID,-, the electrolytic resistance
R(zeolite) decreased from 210 to 170 kfl as the hydrocarbon concentration was increased.
The activation energies of the ionic conductivity were
determined from temperature-dependent
impedance
measurements. The activation energy was calculated
from the slope of the straight line in an Arrhenius
plot of the conductivity against the reciprocal temperature (Fig. 7). The values obtained for the activation
energies as a function of the concentration of butane
are given in Table 7.
-11.00

-13.00

D-f]

0.0% Butane

M
M

0.2% ButMe
0.5% Butane

o------d

1.0% ~tEme

The increased ionic conductivity is therefore a consequence of a reduction in the activation energy of the
ionic conductivity, and is closely connected with the
adsorption of the hydrocarbon.
The other parameters of the equivalent-circuit diagram were also determined by computer. However,
because of the small number of experimental points
in the appropriate frequency range, the resulting relatively large error had to be taken into account when
assessing the data. The values of the impedance element
C, measured at 200 C are given in Table 8. The
observed changes in the capacitances were within the
limits of experimental accuracy. The conclusion can be
drawn that within the limits of experimental error, these
parameters were not changed significantly by the adsorption of the hydrocarbon. This has therefore confirmed that the principal effect of the adsorption is on
the polarizability of the zeolite layers, and that it
therefore causes the increase in the capacitances. Crystal-boundary effects and electrode effects appeared not
to have any significant influence on the dielectric behaviour of the sensors.
However, for practical sensor applications it is sufficient to measure directly the capacitance C, or the
resistance R, at a fixed frequency, instead of using the
very time-consuming method of measurement described
above. Fig. 8 shows the typical variation of the relative
change in capacitance of the Na-X-coated sensor, in
which the capacitor structure was 20 q/20 Frn on a
silicon substrate, over the temperature range SO-200
Table 8

Capacitance

-15.00

x
.a

E
8

values

of impedance. element C,

of Na-X sensor for

200 C

-17.00

-19.00

8
u
c

-21.00

Capacitance

0
0.2
0.5
1.0

70*1
67fl
69*1
68fl

(oF)

1.80

Concentration of n-butane
(vol. %)

2.20

2.60

3.00

3.40

IO 3/~(~)

t5 AC/co

[Xl

Fig. 7. Arrhenius plot for Na-X sensor with various n-butane concentrations.

12 --

9 --

Table 7
Activation energies of Na-X sensor forvarious n-butane concentrations

-0

Concentration of n-butane
(vol.%)

Activation energy
(kJ/mol)

0
0.2
0.5
1.0

57.9
55.4
50.2
49.9

0.8
0.4
0.0
Contentionofn-Butane1%by Volume]

0.2

1.2

Fig. 8. Relative change. in capacitance of Na-X sensor between 50

and 200 C as a function of n-butane concentration (frequency 1
kHz): 0, 50 c; 0, 100 c; 0, 150 c; A, 200 C.

K Alberti, F. Felling / Semom and Achtators B 21 (1994) 39-50

C, the measurements being made at a frequency of

1 kHz. The plot of the change in capacitance as a
function of the butane gas concentration shows that
after a relatively steep increase in capacitance at low
concentrations, there is a transition to a flatter curve,
which tends towards a saturation level at higher concentrations.
The changes in capacitance exhibited an interesting
variation with temperature. Results obtained from adsorption measurements under comparable experimental
conditions showed that the number of adsorbed molecules decreased sharply as the temperature increased.
The relative changes in capacitance showed a behaviour
which differed from this, since as the operating temperature was increased the output signal first decreased,
but then increased again. The Na-X sensors showed
the lowest measurable effect at 100 C, and the highest
effect at 200 C. The smaller number of adsorbed
molecules is obviously more than compensated at the
high temperature of 200 C by the stronger interactions
of the molecules wi@ the zeolite matrix, and by the
resulting increase of the polarizability of the zeolite
layer. When the positive effect of the higher temperature
on the sensitivity under the given experimental conditions is taken into account, it is seen that the optimum
operating temperature for the sensors is 200 C. A
higher temperature also has a favourable effect on the
sensor response. The response of the Na-X sensor at
different concentrations of n-butane at 200 C is shown
in Fig. 9.
The sensor responded immediately to the gas by
showing an increase in capacitance, and the change in
capacitance reached a stable fmal value within a short
period. After stopping the gas feed, the capacitance
decreased almost at the same rate. The characteristic
t, period, in which the sensor signal reaches 90% of
its final value, was 6-S min in the adsorption stage,
depending on the concentration, and 7-9 miu in the
desorption stage. The desorption of the n-butane was
almost complete, and after a few minutes the sensor

45

signal returned to its initial value. Irreversibly adsorbed

molecules caused almost no increase in the base capacitance, and any undesirable effects due to drift could
be largely suppressed.
5.2. The injfuence of the structure of rhe capacitor
Differences in the geometry of the capacitor had
hardly any effect on the sensor characteristics. Interdigital capacitors with electrode dimensions of 10 pm/
10 m on a silicon substrate showed almost the same
behaviour over a wide range of frequencies as sensors
having electrode dimensions of 20 pm/20 pm. Fig. 10
illustrates the behaviour of the capacitors with electrode
dimensions of 10 cLm/lOpm during the adsorption of
the hydrocarbon. The diagram shows the relative
changes in capacitance at different concentrations, the
curve for the Na-X sensor with the capacitor structure
20 pm/20 pm being shown as a dashed line.
5.3. The infbence of the substrate material
Whereas the different electrode geometries of the
capacitors had almost no effect on the behaviour of
the sensors, a change in the substrate material had a
more obvious effect. The basic behaviour of the sensors
during the adsorption is not affected by the substrate
material. The advantage is rather in a better ratio of
the active capacitance to the inactive capacitance of
the sensors as a result of employing a substrate material
with a lower dielectric constant. In fact the sensitivity
of the sensors with a quartz substrate was increased
significantly compared with those having a silicon substrate. Fig. 11 shows the obvious improvement in the
sensitivity of the sensors having a quartz substrate
compared to those with a silicon substrate.
5.4. The influence of different alkali-metal cations
The dielectric behaviour of the zcolite layers is determined essentially by the mobile cations within the

AC lpF1

Frquency
0

IO

20

30

40
t

50

b0

10

50

Imtnl

Fig. 9. Response behaviour of Na-X sensor under various butane

mncentrations at 200 C. The gas was dosed for 15 min.

[kHz]

Fig. 10. Comparison of Na-X sensors with electrode dimensions of

20 pm/24l m (dashed curve) and IOpmlq (continuous curve) on
silicon substrate at 200 c: 0, 0.2%; 0, 0.5%; A, 1.0% X, 1.0%
(20 fimD&m).

46

R Alberti F. Fetting / Seams

and Achrators B 21 (1994) 39-M

and the highest sensitivity at 200 C. The relative changes

in capacitance were found to be smaller than in the
case of the Na-X sensors. The sensitivity level of the
Na-X sensors, particularly at the operating temperature
of 200 C, was not achieved. For measurements made
at a frequency of 1 kHz the level was about 50% lower
than the values measured for the Na-X sensors. The
variation with temperature was less than for the NaX sensors.

OL

0.4

0.2

C!cmenuation

0.6

0.8

1.2

ofn-Butane[% by Volume]

Fig. 11. Influence of substrate material. Na-X interdigital capacitor

(10 fim/lO pm) at 200 C (frequency 1 kH2): 0, quartz (loom/
10pm); +, Si (10 e/l0
pm).

8 AC/Co [X]
1

5.4.2. Sensors incorporatingzeolite K-X

Sensors incorporating layers of potassium-X zeolite
exhibited completely different behaviour. In contrast
to the Qpe X zeolites containing lithium or sodium,
contact with the hydrocarbon produced almost no effects
on the dielectric behaviour that could be detected
electrically. The maximum changes in capacitance for
the K-X sensor only amounted to 0.24%.
This surprising result is at variance with the adsorption
behaviour of the zeolite samples. The results of gravimetric adsorption experiments with the alkali metaldoped type X zeolites did not indicate that any major
difference in behaviour was to be expected. This can
be taken as a further indication that the dielectric
properties of the zeolites are influenced irimarily by
the nature of the replacement cations. This surprising
behaviour was also found, without exception, in the
other zeolite samples of difference crystal structure
that were examined, and this will be considered in
Section 6.
5.5. The influence of differences in the zeolite structure
55.1. Sensors, incorporabng Na mordenite

0.2

0.4

0.6

0.8

1.2

Concentrationof n-Butane [% by Volume]

Fig. 12. Relative change in capacitance of L.&Xsensor between 50
and 200 C as a function of n-butane concentration (frequency 1

kHz): 0, 50 c; 0, 100 c; 0, 150 c; A, ux) C.

zeolites. Replacement of the sodium ions with alkalimetal cations of lithium and potassium has an obvious
effect on the dielectric behaviour of the sensors, since
a close correlation exists between the ionic mobility
and the polarizability of the zeolite layers, and therefore
a change occurs in the charge distribution in the zeolite.
5.4.1. Sensors incorporatingzeolire Li-X
The behaviour of the Li-X sensors differed only
slightly from that of the Na-X-coated sensors, as shown
in Fig. 12. In this case the sensor again exhibited the
lowest sensitivity for measurements made at 100 C,

Fig. 13 shows the impedance spectra of the Na

mordenite sensor at 200 C under the influence of
increasing concentrations of butane gas. The observed
effect is caused by the increase in the polarizability of
the zeolite layers in both the mordenite sensors and
the zeolite X sensors. The interactions with the gas
again lead to a decrease in the electrolytic resistance,
as described above.
The typical variation in the relative change in capacitance for different concentrations of gas is shown
in Fig. 14 for measurements made at a frequency of
1 kHz. Sensors incorporating Na mordenite layers exhibited a high sensitivity on exposure to n-butane. As
with the sensors previously examined, the Na mordenite
sensors showed the smallest observed effect at 100 C
and the largest at 200 C. In the case of the Na
mordenite sensors the optimum operating temperature
is therefore again 200 C.
The higher sensitivity of the Na mordenite sensors
compared with the Na-X sensors for measurements
made at 1 kHz should be emphasized. The relative
change in capacitance at 200 C and a concentration

K Alberti,

F. Felting

I Sensors

and Actuators

B 21

(1994)

47

39-50

-Z [kOhm]
150

0.2

0.4

Concenwticm

0.0

0.2

1.2

of n-Butane[% by Volume]

Fig. 15. Relativechange in capacitanceof Li-mordenite sensorbetween

50 and 200 C as a function of n-butane concentration (frequency
1 kHz): 0, 50 c; 0, 100 c; 0, 150 C, A, 2QOC

,,Ac

[PFI

100
2

[kOhm]

Fig. 13. Impedance spectra of Na-mordeoitc. sensor at 200 C for

varioos n-butane concentrations: *, 0.0%; q,0.2% 0, 0.5%. A, 1.0%.

.t7

10

20

Fig. 16. Response b&&our

1.0 vol.% n-butane.
cl

0.2

0.4

Conccnmticm

0.8

0.8

30
t [min]

40

50

80

of Li-mordenite sensor at 200 C with

1.2

of n-Butaae[% by Volume]

Fig. 14. Relative change in capacitance of Na-mordenite sensor

between 50 and 200 C as a function of n-butane concentration
(frequency 1 kHz): 0, 50 c; 0, 100 C; 0, 150 T; A, 200 C.

of 1 vol.% n-butane was about 24%, compared with

about 19% for the Na-X sensor. The Na mordenite
sensors are therefore also very satisfactory sensors.
5.5.2. Sensors incorporating Li mordenite
Sensors having Li mordenite layers show a high
sensitivity on exposure to n-butane, but the temperature
dependence differs from the previous results. The variation of the relative change in capacitance with the
concentration of gas is shown in Fig. 15. The interdigital
capacitors coated with Li mordenite showed less variation with temperature and frequency than the Na
mordenite sensors, as had also been found on changing
from type X zeolites containing sodium to those containing lithium.
Whereas the sensitivity of the Li-X sensor was sig
nificantly lower than that of the Na-X sensor, the
difference was very much smaller in the case of the

mordenite sensors. It was also surprising that the lowest

sensitivity of the Li mordenite sensor occurred at 50
C. The typical response of the Li mordenite sensor
is shown in Fig. 16,90% of the final value being reached
after 7 min. The signal measured from this sensor is
very stable and shows no drift of the final value. The
Li mordenite sensors were therefore just as good as
those containing Na mordenite. In contrast to the NaX and Li-X sensors, the Na and Li mordenite sensors
both exhibited the same high sensitivity.
5.5.3. Sensors incorporating K mordenite
In the experimental results discussed so far for the
behaviour of the Na mordenite and Li mordenite sensors,
wide agreement was found with results for the corresponding zeolite X sensors. It was therefore not at
all surprising that the K mordenite samples were found
to be unsuitable for use as the sensor layer under the
given experimental conditions. Contact with the hydrocarbon produced almost no measurable change in
the dielectric properties of the interdigital capacitors
coated with K mordenite.

48

K Alberti, F. Fetting t Scnm-s and Actuators B 21 (1994) 39-50

6. Discussion
Dielectric sensors react to the adsorption of gas
molecules by exhibiting characteristic changes in the
electrical properties of their dielectric. The predominant
effects occur in the polarizability and in the conductivity
of thedielectric. The change in the relative dielectric
constant is proportional to the change in the capacitance
of a capacitor, a parameter that is easily measured.
Zeolites differ from other adsorbents in both their
exceptionally large internal surface area and in their
precisely defined pore diameter, which is of the order
of molecular dimensions. The mutual interactions with
adsorbed molecules are therefore particularly strong
as a result of the close contact of the molecules with
the zeolite matrix. According to Barrer and SaxonNapier [46], negative sites in the zeolite framework
combine with the positively charged cations coordinated
with it to form a dipole, with its associated electrical
dipole moment [47]. Adsorbed molecules influence the
position of the cations to an extent depending on the
strength of the interactions. Adsorbed hydrocarbons
lead to a decrease in the field strength in the zeolite,
and this increases the mobility of the cations within
the channels and cavities. The displacement of the
cation positions is accompanied by a change in the
dipole moment, and as a result of the interactions with
the zeolite framework, dipoles are also induced in the
adsorbed molecules, or any existing dipole moments
are increased. The two effects taken together give rise
to the obvious, measurable increase in the capacitances
of the zeolite-coated interdigital capacitors as soon as
they come into contact with the hydrocarbon.
In addition to the polarization effects, the transport
of charge carriers takes place in an electric field. The
original studies of the mobility of cations in zeolites
were carried out by Barrer and Rees [48], who found
a linear relationship between the activation energy of
the self-diGsion and the polarizability of the replaceable
cations. Freeman and Stamires confirmed the results
of Barrer and Rees by means of electrical conductivity
measurements [49]. They studied zeolites A, X and Y
in which various cations had been exchanged. They
established that the conductivity was purely ionic, and
found that the activation energy depended greatly on
the nature of the cations and on the type of zeolite.
They interpreted this in terms of the existence of
different cation positions for the different alkali-metal
cations in the zeolite framework.
The adsorption of molecules has a strong influence
on the mobility of the cations. The adsorbate molecules
provide additional opportunities for coordination of the
cations, as a result of which the strength of the bond
to the zeolite framework is weakened. Adsorbed hydrocarbons reduce the field strengths as a result of
charge delocalization, and therefore the energy barriers

for the migration of the cations are lowered [SO].The

conductivity of the zeolites therefore increases as a
consequence of the adsorption process. When the loading is low the conductivity initially increases with the
number of adsorbed molecules, and this continues until
a saturation effect occurs at a high loading [51].
Analysis of the impedance spectra showed that the
observed effect is primarily due to the increase in the
polarizability of the zeolite layers. Zeolite layers containing lithium and sodium are characterized by a high
sensitivity to the hydrocarbons employed. The adsorption of the hydrocarbon causes a decrease in the
activation energy of the ionic conductivity. The enhanced
mobility of the cations also leads to an increase in the
polarizability of the zeolite layers, which causes the
capacitance of the coated interdigital capacitors to
increase.
Sensors having layers of zeolites that contain potassium exhibit a markedly different behaviour from
that described above, since in this case contact with
the hydrocarbon produces almost no change in the
dielectric properties. This surprising result cannot be
explained in terms of different adsorption behaviour,
indeed no differences in behaviour were found in the
gravimetric adsorption experiments performed on the
zeolite samples. Instead, the reason for this behaviour
must lie in the different effects that adsorption has on
the polarizability of the zeolite layers.
If the polarizing effect of the cations is considered,
it is seen that the smaller the radius of the cations
and the higher the loading, the greater this effect. The
polarizing effect of the alkali-metal cations therefore
decreases from lithium to potassium. However, this
does not explain the abruptly changing behaviour of
the zeolite layers. Special conditions within the zeolite
crystal must be invoked to explain the abrupt change
in the dielectric properties.
Within the zeolite crystals different cation positions
exist, and the occupation of these positions by the
alkali-metal cations is the crucial factor in determining
the dielectric behaviour of the zeolite layers. The spatial
requirements of the cations play an important role, and
differences in the occupation of the positions occur,
depending on the size of the cations. In zeolite X
lithium and sodium achieve optimal coordination in
the hexagonal prisms (cation position I) and in the
centre of the six-membered rings in the zeolite framework (cation position II). In mordenite the small cations
are located in the centre of the lateral axes (cation
position I).
On the other hand, the larger cations prefer an eightmembered ring environment for coordination. They are
too large to achieve optimum coordination in the sixmembered ring environment. For example, for this
reason, the larger potassium cation is found only in
cation position II or IV in mordenite. The coordination

K. Alberti,F. Fetting/ Sensorsand ActuatorsB 21 (1994) 39-50

49

nancial assistance was also provided by the Verband

der Chemischen Industrie (Fonds der Chemie).
Preparation of the capacitors was carried out by
Dornier GmbH, Friedrichshafen. We want to thank Dr
C. Plog and Dr J. Haas for helpful support.

Fig. 17. Coordination of alkali-metal cations in zeolite X in cation

position S II.

of the different-sized alkali-metal cations in zeolite X

is shown in Fig. 17, taking the cation position S II as
an example [52]. The potassium, rubidium and caesium
cations are too large for sufficient space to be found
for them at the centre of the six-membered ring.
Differences in the occupation of the cation positions
do not affect the adsorption behaviour to the same
extent as they atfect the dielectric properties. The
occupation of cation positions I and II by small cations
appears to be the most important factor in the dielectric
behaviour of the zeolites when they are in contact with
the hydrocarbon gas. The interactions with the hydrocarbon obviously have a signilicantly greater effect on
the small alkali cations in their positions than on the
larger cations. The differences in the structure of the
zeolites are of somewhat minor importance in this
respect.

7. Conclusions
The suitability of zeolites as sensitive materials for
dielectric gas sensors used to detect hydrocarbons has
been demonstrated by the present work. Interdigital
capacitors produced by modem semiconductor technology have been used as the basic sensor elements,
and these have been coated with zeolites doped in
dierent ways. The production of the interdigital capacitors by semiconductor technology also permits the
integration of the measurement electronics and a microchip heater on a single component, and this facilities
the coupling of several sensors into a sensor array.
The adsorption of particular gases leads to a change
in the dielectric constants of the zeolite layer in these
sensors. The sensor response is the change in the
capacitance of the interdigital capacitors under the
influence of the gas. The presence of mobile cations
in the zeolite is the crucial factor in their mode of
operation. The adsorption of the hydrocarbons results
in an increase in the polar&ability and a decrease in
the activation energy of the ionic conductivity.
Acknowkdgements
This work received financial support from the Federal
Ministry for Research and Technology. Valuable fi-

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Biographies
Klaus Alberti received his Dipl. Ing. degree in 1989
and his Ph.D. in chemical engineering in 1991 at the
Technical University of Darmstadt. His thesis was concerned with the development and study of the gas
sensor presented in this paper. In 1992 he moved to
the University of Cambridge, UK, working on
MAS-NMR studies of porous catalyst systems. He is
now with the Hoeehst Company.
Frirr Fetting received hi Ph.D. in physical chemistry
in 1955 at the University of Giittingen. Habilitation
took place in 1%2 at the Technical University of
Hannover. Since 1966he has been professor for chemical
technology at the Technical University of Darmstadt.