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Microporous and Mesoporous Materials 197 (2014) 213220

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Microporous and Mesoporous Materials


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

Zeolite micromembrane fabrication on magnetoelastic material


using electron beam lithography
Vassiliki Tsukala a,b, Dimitris Kouzoudis b,
a
b

Foundation for Research and Technology Hellas, Institute of Chemical Engineering and High-Temperature Chemical Process, P.O. Box 1414, GR 265 04 Patras, Greece
Department of Chemical Engineering, University of Patras, GR-26504 Patras, Greece

a r t i c l e

i n f o

Article history:
Received 1 February 2014
Received in revised form 8 May 2014
Accepted 2 June 2014
Available online 26 June 2014
Keywords:
Micromembrane
LTA
Electron beam lithography
Secondary growth
Magnetoelastic

a b s t r a c t
In the present study, electron beam lithography (EBL) is employed in the manufacturing of patterns of
continuous Linde Type A (LTA) zeolite membranes. The patterns are down to the micrometer scale and
they are composed of LTA micromembranes having all three dimensions in the micrometer scale. The
control of the size and location of zeolite lms or membranes onto specic substrates, will lead to new
aspects for their use in microsensing, microelectronics and microreactor applications. Our focus is on
the microsensing eld, where a magnetoelastic ribbon (Metglas) is used as the sensing platform, since
the Metglas/zeolite lm composite has been successfully used for the detection of gases and VOCs in
the past. Here we report on the rst LTA zeolite micromembrane attached onto a previously EBL patterned PMMA coated Metglas substrate. The sensing ability of such a sensor could be signicantly
improved by using lower amount of zeolite lm since it could lead to shorter response and recovery
times. The conditions for the manufacturing of the LTA micromembranes onto the Metglas substrate
are investigated and discussed in terms of EBL, seeding and hydrothermal synthesis parameters.
2014 Published by Elsevier Inc.

1. Introduction
Because of their interesting and unique properties [1], zeolites
and their continuous lms have attracted great scientic interest
[2] over the past decades, which is demonstrated on their various
industrial applications such as catalysts in ne chemical and
petrochemical industry [3], adsorbents [4], and membranes for
separations or as reactors [5]. Their molecular sieving ability, controllable surface properties, well-dened porosity, large surface
area along with chemical, thermal and mechanical stability can
also be utilized in new advanced applications like microreactors
[6], chemical or gas sensors [7], microseparators [8], low dielectric
constant materials for microelectronic devices [9], electrodes [10],
biomedical science [11] and fuel cells [12]. Nevertheless, the
exploitation of zeolites in such advanced applications is often
prevented due to the powder form of synthetic zeolites, directing
efforts in the development of continuous zeolite lms of small size
so as to be implemented in the so-called microchemical systems
that also include other microdevices such as micromixers,
microheat exchangers, microactuators and microsensors [13].
Tailoring and controlling zeolite membranes size in the microscale range offers numerous advantages in many of the above
Corresponding author. Tel.: +30 2610996880; fax: +30 2610996846.
E-mail address: kouzoudi@upatras.gr (D. Kouzoudis).
http://dx.doi.org/10.1016/j.micromeso.2014.06.017
1387-1811/ 2014 Published by Elsevier Inc.

advanced applications [14]. Among the benets of micromembranes, the most obvious one is the elimination of defects (cracks
and holes), as the probability of a defect-free surface increases
for smaller membrane areas [15]. Other signicant aspects, especially for microreactor applications, are the elimination of temperature gradients thus minimizing hot spots, enhancing heat and
mass transfer properties and nally, improving yield, conversion
and selectivity through the reaction-permeation mechanism of
the desired product through the channels [16]. In the eld of zeolite membranes used for sensing applications, micromembranes
are of great demand, since lower mass could result in shorter
response time and subsequently shorter recovery [7]. Thus, the
sensitivity of the sensor could increase, especially when used as
microbalance (cantilever-based or Quartz Crystal Microbalance,
QCM) but also the selectivity of specic components can be
enhanced allowing for molecular recognition [17] (as electronic
nose sensors).
Important efforts have been made to fabricate patterned zeolite
lms or layers of crystals on solid substrates by combining both
zeolite-substrate adhesion techniques and pattern denition
methods adopted from microelectronics technology. The most
common substrates that have been used for patterned zeolite
membranes are silicon and glass, while siliceous zeolites are
preferred, mainly because of the chemical afnity. In order to
attach zeolites onto them, two adhesion techniques are commonly

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V. Tsukala, D. Kouzoudis / Microporous and Mesoporous Materials 197 (2014) 213220

used: casting and secondary growth. For the rst approach, the
most facile method is the direct attachment method, where the
zeolite crystals are assembled through covalent or ionic bonding.
The most widely used way of ionic bonding is simply by rubbing
[18] zeolite crystals on a patterned smooth substrate resulting in
uniformly, fully-packed layers of crystals. In a similar manner,
ultrasound agitation [19] and dip or spin coating methods of colloidal seed solutions have also been used but with less success in
terms of uniformity and coverage. The second approach is the secondary growth method, where zeolite crystals are intergrown to
form continuous lms attached onto the patterned substrates
under hydrothermal conditions. The zeolite type is controlled by
the seed type and synthesis conditions.
In order to pattern the substrates surface for zeolite crystals
attachment, three pattern denition methods have been mostly
employed that are also compatible with sensor technology:
microcontact printing, photoetching and lithography (photolithography or electron beam lithography), resulting in different
resolution and structure sizes [20]. Since the resolution of the
classic photolithography is limited by the wavelength of the light
used, electron beam lithography (EBL) has provided scientists with
a powerful tool for creating nano-scale structures. EBL utilizes a
highly focused electron beam to expose a resist-coated substrate
thus making it soluble (positive tone resist) or insoluble (negative
tone resist) to a photoresist developer. As the trend for everincreasing levels of miniaturization needs to be met also for zeolite
technology, in order to be integrated with sophisticated microdevices, the demand for high-throughput screening and decreased
sample mass [21] can be achieved using EBL technology. Other
advantages of EBL are the precise and easy pattern generation
using software tools and direct exposure onto the semiconductor
substrate [22] without the tedious and often expensive mask
preparation.
The majority of the studies on patterned layers of crystals or
lms have focused on siliceous MFI type zeolites (ZSM-5 and silicalite-1) and employed the previously mentioned methods and techniques. The most common substrates used are glass and silicon
wafers due to their smooth surface and chemical afnity with
the above siliceous zeolites. Using microcontact printing with poly
(dimethylsiloxane) (PDMS) stamp, Yoon and co-workers covalently
attached b-oriented ZSM-5 crystals on Si wafer. The crystals were
self-assembled (from their ethanol solution) after stamp-pressing
onto the wafer surface, forming monolayers with approximately
5 lm width [23]. Similarly, Yeung and co-workers [24] fabricated
ordered silicalite micromembranes and monolayers on Si wafers,
through secondary or direct growth and using photolithography
and etching techniques, in order to produce catalytic microreactors
and membrane microseparators, while later, they managed to
photopattern silicalite-1 membranes on Si wafer reaching 5 lm
small zeolite arrays [25]. Another technique was rst introduced
by Yoon and co-workers employing patterning through photochemical degradation of organic functional groups on glass, covalent bonding of ZSM-5 crystals and subsequent secondary growth
of continuous ZSM-5 membrane with approximately 200 lm feature [26]. A different approach, using TEM grid and chromium-gold
depositions, was employed by Yan and co-workers to fabricate
continuous, b-oriented silicalite membrane onto patterned Si
wafer, exploiting the weak interaction of gold surface and colloidal
zeolites [27]. Photoetching (both dry and wet) techniques were
investigated by Pellejero et al. for the fabrication of patterned silicalite lm on Si wafer, after the hydrothermal synthesis, achieving
10 lm structures [28]. More recently, Ozturk et al. [29,30] and Kirdeciler et al. [31] fabricated monolayers of ordered individual crystals of LTA and BEA type zeolites, through the manual assembly
method, onto Si wafers patterned using electron beam lithography,
with 500 nm features.

In the present study, a magnetoelastic material (Metglas) was


chosen as a substrate, which was successfully utilized by our group
as a sensing platform together with zeolite lms for the detection
of CO2 [32], VOCs [33] and stress[34]. Another reason for using
Metglas in the present study is the excellent adhesion of continuous LTA lms on it. A major drawback in these sensing applications
was the relatively slow response time, of the order of tens of
seconds, resulting from the slow adsorption and diffusion of the
detected species through the zeolite layer. A smaller size zeolite
feature, down to micro scale, could probably result in much shorter
diffusion time which is one of the objectives of micropatterning
LTA lms on a Metglas substrate.
Three novel ideas are introduced in the present work: (a)
electron beam lithography is employed for the rst time for the
in situ synthesis of micropatterned, continuous zeolite lms
through the secondary growth. (b) It is also the rst time that an
LTA lm is synthesized in the micrometer scale, revealing new
aspects of its future use in microsensing, microelectronics and
microreactor applications. Most of the zeolite micro-patterning in
the literature involves either MFI membranes or LTA microcrystals,
not LTA membranes. It should also be noted that LTA has a number
of industrial applications thus its micro-manipulation is of
paramount importance. And c) this is the rst time that a metallic
magnetoelastic material is used as a substrate for zeolite micromembrane patterning applications. Usually conventional substrates
such as Silicon wafers or glass are used.
2. Experimental
The e-beam lithography and secondary hydrothermal synthesis
procedure that was used to develop the micro-patterned LTA lm
is schematically represented in Fig. 1. The steps can be summarized
in the following list:
(a) Cleaning of the Metglas substrate
(b) PMMA spin-coating

Fig. 1. Schematic representation of the experimental procedure for the fabrication


of zeolite micromembranes on Metglas using EBL technology and secondary
growth.

V. Tsukala, D. Kouzoudis / Microporous and Mesoporous Materials 197 (2014) 213220

(c)
(d)
(e)
(f)
(g)

E-beam exposure
PMMA development
LTA seeding
LTA synthesis
Ultrasound Cleaning

Each individual step is described in detail in the following


paragraphs.
2.1. PMMA coating on Metglas
Several Metglas 2826 MBA (Fe40Ni38Mo4B18) ribbons from
Allied Signal with dimensions 6 mm  20 mm  28 lm were cut
and thoroughly washed with trichloroethylene (C2HCl3, Sigma
Aldrich) and methanol (CH3OH, SigmaAldrich) in ultrasonic bath
(SONOREX DIGITEC DT 100) for several 15-min cycles and were
nally dried at 80 C (Fig. 1a). For the e-beam lithography process,
a solution of 5% wt. of poly(methyl methacrylate) (PMMA, MW
350 K, SigmaAldrich), in propylene glycol methyl ether acetate
(PGMEA, SigmaAldrich) solution was prepared after 36 h of stirring at room temperature. Any un-dissolved PMMA particles were
removed by ltration (Chromal Xtra PTFE-45/25) and approximately 0.5 lL was spin-coated (Spin150, SPS) on the Metglas surface at 4000 rpm for 60 s (Fig. 1b). The PMMA-coated Metglas
was then hot-baked at 130 C for 30 min in order to remove the
PGMEA solvent. The PMMA lm thickness was measured using
White Light Reectance Spectroscopy (FR-Basic, ThetaMetrisis) to
be approximately 450 nm.
2.2. Electron beam lithography
The system for the electron beam lithography (EBL), Xedraw2
(XENOS Semiconductor Technologies GmbH), consists of the 3-axis
movable stage (XeMove), the beam blanking system (XeSwitch),
equipped with a Faraday cup, and the pattern generator software
(Exposure Control Program, ECP). The XeSwitch is mounted on a
JSM-6610LV (JEOL) scanning electron microscope for the beam
control and the beam current is measured through the Faraday
cup connected to a Keithley 6430 multimeter.
The PMMA-coated Metglas was attached on the XeMove stage
and the exposure was performed after appropriate adjustment of
the SEMs accelerating voltage, spot size, beam focus and astigmatism correction and suitable pattern denition, where the dwell
time is calculated for given: eld size, beam current and exposing
dose (Fig. 1c). After the exposure, the patterned surfaces were
developed by isopropanol/water (IPA/H2O, 7/3) solution for 60 s
and dried with nitrogen (Fig. 1d).
All tests were performed using accelerating voltage of 10 kV,
the beam load current was kept constant at 40 mA, the tension
of the beam blanker was adjusted at 35 V and the spot size was
set to 50 which resulted in a Keithley reading of approximately
200 pA. For the determination of the most suitable dose for the
PMMA resist exposure, several doses in the range of 10200 lC/cm2
were tested.
2.3. LTA seed synthesis
Typically the LTA lm synthesis begins with seeding, i.e. the use
of previously prepared crystals which later develop, during the
synthesis, and form a continuous lm. Following the lithography
and development processes, seeding was applied by LTA seeds of
two different sizes: micro-sized and nano-sized one. The crystals
were prepared via the hydrothermal method using the conditions
described by: (1) Thompson et al. [35] and (2) by Jafari et al. [36]
resulting in micro-sized and nano-sized crystals respectively.
For micro-sized ones, sodium hydroxide (NaOH pellets, 98%,

215

SigmaAldrich) was dissolved in distilled water (Millipore, MilliQ8) and divided in two equal parts in polypropylene bottles. The
silicon source (TEOS 98%, SigmaAldrich) was added to one part,
while aluminum source (sodium aluminate, Al2O3  55%,
Na2O  45%, SigmaAldrich) was added to the other one. Both
solutions were stirred in room temperature until clear for approximately 4 h. Then, the aluminum solution was added to the silicate
one under stirring to form the synthesis gel with molar ratio: 3.165
Na2O/Al2O3/1.926 SiO2/128 H2O. The gel was aged for 1 h under
stirring at room temperature and then heated at 80 C for 24 h in
sealed polypropylene bottle. Following the synthesis, the crystals
were collected using vacuum ltration (Whatman No. 2) and
washed with distilled water until pH reached 9. Afterwards, the
crystals were dried at 100 C for several hours, characterized
(XRD and SEM), pulverized and re-dispersed in water (1% wt.) to
form the seeding solution.
Slightly different conditions were used for the synthesis of
nano-sized crystals. Briey, sodium hydroxide (NaOH pellets,
98%, SigmaAldrich) was dissolved in distilled water (Millipore,
Milli-Q8) and the organic template (tetra-methyl-ammonium
hydroxide, TMAOH, 25%, SigmaAldrich) was added. This solution
was divided in two equal parts in polypropylene bottles and the
silicon source (LUDOX SM-30, SigmaAldrich) was added to one
part, while aluminum source (aluminum isopropoxide, Al(OiPr)3,
98%, SigmaAldrich) was added to the other one. Both solutions
were stirred in room temperature until clear for approximately
2 h. Then, the silicate solution was added to the aluminum one
under stirring to form the synthesis gel with molar ratio: 0.32
Na2O/Al2O3/6 SiO2/7.27 (TMA)2O/350 H2O. The gel was aged for
4 days under stirring at room temperature and then heated at
80 C for 24 h. Following the synthesis, the crystals were collected
after several cycles of: (i) centrifugation (8000 rpm for 15 min,
Eppendorf Centrifuge 5804), (ii) re-dispersion in water and (iii)
ultrasonication (Elmasonic S30H), until pH reached 9. Afterwards,
the crystals were dried at 100 C for several hours, pulverized
and characterized. After their characterization, the nanocrystals
were re-dispersed in water (1% wt.) to form the seeding solution.
Then, the entire patterned PMMA-coated Metglas was drop-casted
(2 times) with one of the above solutions and dried for approximately 10 min at 85 C (Fig. 1e) in order to promote crystallization
of homogeneous zeolite lm and to accelerate the growth rate.
2.4. LTA membrane synthesis
Following the seeding, the zeolite membrane was hydrothermally synthesized on the patterned substrate by the secondary
growth. The seeded and patterned PMMA-coated Metglas was
transferred on a polypropylene bottle with the seeded side facing
downwards in order to avoid agglomeration from the bulk. The
sample was kept elevated in the horizontal position with the aim
of two exterior placed magnets (Metglas is iron rich so it is
attracted by magnets). Two basic (NaOH) aqueous solutions
were prepared separately under stirring at 50 C: one containing
the silica source (Sodium Silicate Solution, SigmaAldrich) and
one with the aluminum source (Sodium Aluminate, Sigma
Aldrich). The aluminum solution was ltered (Whatman No. 2)
and slowly added to the silica solution under stirring resulting in
the nal synthesis gel with molar ratio: 2.68 Na2O/Al2O3/2.53
SiO2/150 H2O. Subsequently, the synthesis gel was transferred in
the polypropylene bottle containing the Metglas sample and the
hydrothermal synthesis was carried out at 100 C for various
crystallization times (Fig. 1f). At the end of the synthesis, the
sample and the bulk crystals (for further examination) were
separated from the mother liquor under vacuum ltration
(Fig. 1g), washed with distilled water several times using ultrasound bath and nally dried at 100 C overnight so as to reveal

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V. Tsukala, D. Kouzoudis / Microporous and Mesoporous Materials 197 (2014) 213220

LTA micromembranes on the exposed Metglas surface and dry


crystals correspondingly.

3. Results and discussion


In order to achieve precise and accurate exposure of the desired
patterns using e-beam lithography, several factors need to be considered: type of resist, substrate, developer, e-beam energy, dose,
development time and temperature [37]. Since the most commonly used positive resist is PMMA, the appropriate development
conditions (developer type, time and temperature) are well documented [38]. High e-beam energy (accelerating voltage) creates
numerous backscattered electrons thus giving rise to signicant
proximity effect (developed pattern is wider than the scanned pattern). On the other hand, low e-beam energy results in divergence
of the beam from mutual electrostatic repulsion by the electrons.
Therefore, an intermediate value of 10 kV accelerating voltage
has been chosen in order to minimize those effects. What still
needs to be determined is the dose (energy deposited per unit area
that is actually measured in terms of current deposited per unit
area, lC/cm2) that results in maximum pattern accuracy and
minimum remaining PMMA lm thickness. For this purpose,
several doses in the range of 10200 lC/cm2 were tested on the
same sample consecutively for features of 10 lm and accelerating
voltage of 10 kV. In Fig. 2, light grey areas show the Metglas
exposed area while the darker ones show the intact PMMA lm.
XeDraw2 has the ability of exposing consecutive features with
increasing or decreasing dosage when a dose scale factor is implemented in the source code. The most satisfactory results were
obtained in the range of 2090 lC/cm2, as patterns deviate considerably outside this range. This is because at higher doses the proximity effect raises signicantly resulting in wider features and at
lower doses the PMMA is underexposed thus the features are
narrower. The actual width of the structures was determined using

SEMs measurement tool. The mean width of all the stripes at each
dose was calculated and the percent error from the 10 lm programmed value is plotted against exposure dose, as shown in
Fig. 3. The relation is almost linear in the range of 2050 lC/cm2
while the percent error minimizes at about 40 lC/cm2 and thus
this optimum dose was chosen for the rest of the current work.
Since seeding is critical for the membrane formation, the crystals collected (using the above mentioned methodologies for micro
and nano-sized seeds) were examined and characterized with SEM
and XRD. Their average size was estimated using SEMs software
tool to be about 3.5 lm for the micro-sized crystals and about
90 nm for the nano-sized crystals, as can be seen in Fig. 4a and b,
respectively. Their crystallinity and anticipated chemical formula
were conrmed using XRD measurements (Fig. 5a and b) through
the database PDF-2 (01-073-2340).
The effect of seeding was examined on three samples treated
under the same hydrothermal conditions for 3 h at 100 C: (a)
without any seeds, (b) with micro-sized seeds and (c) with nanosized seeds. As can be seen in Fig. 6, the effect of seeding is a determining factor for the membrane synthesis, since no membrane is
grown onto the unseeded sample (Fig. 6a) after the hydrothermal
synthesis. Nevertheless, in the sample seeded with the micro-sized
crystals (Fig. 6b), the membrane is quite inhomogeneous and
consists of several uneven features where zeolite lm is grown,
probably covering the larger seed crystals or agglomerates. In the
sample seeded with the nano-sized crystals (Fig. 6c), the membrane synthesized is considerably more uniform. All subsequent
studies were therefore performed using nano-sized seeds, taking
also into account that smaller features can be achieved with those
seeds.
The duration of the hydrothermal synthesis is another signicant factor for the membrane formation, since it affects the
thickness, uniformity and purity of the membrane. In order to
investigate this effect, several samples were prepared via EBL
patterning of the PMMA coating and seeded with nano-sized LTA

Fig. 2. SEM images of the patterns generated with exposure dose ranging from 20 to 90 lC/cm2.

V. Tsukala, D. Kouzoudis / Microporous and Mesoporous Materials 197 (2014) 213220

Fig. 3. The relationship between the percent error and the exposure dose.

217

crystals. Indicative SEM images after the seeding are shown in


Fig. 7a for a square pattern with dimensions of 44.75 lm. The
coverage of the exposed Metglas surface with seeds is signicantly
higher than in the PMMA surface, as can clearly be seen from the
magnication of the marked area (Fig. 7b). This observation is in
accordance with the studies of Yilmaz et al. [39] showing negative
charge of developed PMMA lms, thus repulsing the LTA seeds
from its surface. Following the seeding, all samples were hydrothermally treated for 15 h and indicative SEM images are shown
in Fig. 8 (af) for six different times. After 1 h of synthesis
(Fig. 8a) the crystallization has already begin and the membrane
is covering most of the exposed Metglas surface. In the second hour
of synthesis (Fig. 8b), the membrane is almost uniform and
well-dened, while large crystals from the bulk try to incorporate.
Fully grown and uniform membrane is observed after 3 h (Fig. 8c)
having embodied large zeolites from the bulk. Those phenomena
become more important for longer synthesis duration (Fig. 8df):

Fig. 4. SEM images of the micro-sized (a) and the nano-sized (b) LTA seed crystals.

Fig. 5. XRD spectra of the micro-sized (a) and the nano-sized (b) LTA seed crystals.

Fig. 6. SEM images after 3 h of hydrothermal synthesis at 100 C for the un-seeded sample (a), micro-seeded sample (b) and nano-seeded sample (c).

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Fig. 7. SEM images of the patterned surface seeded with nano-sized crystals (a) and higher magnication of the exposed Metglas/PMMA interface (b).

Fig. 8. SEM images of the LTA micromembranes synthesized after: (a) 1 h, (b) 2 h, (c) 3 h, (d) 3.5 h, (e) 4 h and (f) 5 h.

as the membrane grows, more crystals are incorporated and since


those crystals protrude, the lm growth over them produces a nonuniform membrane with uneven height. Subsequently, optimum
hydrothermal synthesis duration should be around 3 h, at the conditions examined. Preliminary observation of the continuity of the
lms, in terms of micro-cracks and holes, was performed using the
back-scattered electrons detector attached on the JSM-6610LV
microscope. The image analysis using this detector is very helpful
when examining different materials since the contrast depends on
the average atomic number of each material. Thus for different
materials (zeolite/Metglas), cracks give a very sharp contrast.
Down to our SEM resolution limit (about 90 nm for these samples)
no cracks were observed. Nevertheless, defects in the nano-scale
may be present, as the accuracy of this technique is limited to only
a surface observation and the SEMs specications.
It is noteworthy that in all cases, the LTA lm was synthesized
only onto the exposed parts of the substrate, where the PMMA lm
was minute or absent. This remarkable effect, the selective synthesis of LTA on the exposed Metglas areas and not on the PMMA
unexposed areas, can perhaps be explained in terms of repulsive
forces. LTA is known to be a highly polar material with extra negative ions in its structure, due to its high aluminum content [40]
thus its precursors are also negatively charged in alkali media
[41]. On the other hand, as already mentioned, developed PMMA

has a slight negative charge, thus repelling the LTA seeds and
precursors during seeding and synthesis respectively. Therefore,
the traditional chemical lift-off process, typically needed to all
lithographic procedures in order to totally remove the PMMA lm,
can thus be eliminated. Only an ultrasound-aided cleaning with
water is needed so as to remove the extra debris of LTA precipitates left from the synthesis solution. This process leaves the
PMMA layer intact, available for a second lithographic step without
any further coating or pattern alignment for a second exposure. For
example, the left over PMMA can be utilized to develop micro
channels in order to connect the LTA micromembranes in our samples, a study that will be examined in the future. Characteristic
example of the unnecessary PMMA removal step in order to reveal
the micro-structures, is shown in Fig. 9. The images show a
micromembrane on the same sample (hydrothermally treated for
3, 5 h at 100 C) before (Fig. 9a) and after (Fig. 9b) the lift-off in
acetone ultrasound bath. However, PMMA lm must be removed
if no further exposure is needed, since it would affect the sensors
performance and in addition, undesired sediments are washed
away.
In order to exploit those LTA micromembranes in sensing
applications, the entire surface of the Metglas must be uniformly
covered with them. As an example, since the typical dimensions
of a Metglas strip are 20 mm  6 mm, a 5% coverage with LTA

V. Tsukala, D. Kouzoudis / Microporous and Mesoporous Materials 197 (2014) 213220

219

Fig. 9. SEM images of the LTA micromembranes before (a) and after (b) the lift-off process.

gure, the reproducibility of the patterned features is satisfactory.


Nevertheless, statistically minor defects, like the absence of a
micromembrane in one of the features, cannot always be
eliminated.

4. Conclusions

Fig. 10. SEM image of a Metglas sample showing a small area with 48 LTA
micromembranes.

micromembranes would translate into approximately 3000 square


micromembranes with 44.75 lm side. In Fig. 10, a characteristic
small fraction of such a sensor, showing 48 of the 3000 micromembranes, is given, prior the lift-off process. The corresponding XRD
spectrum of the sensor is given in Fig. 11, where the amorphous
background is characteristic of the Metglas, conrming the
crystallization of LTA type membrane. As it is evident from this

In the present study, electron beam lithography was employed


in the manufacturing of micropatterned, continuous LTA zeolite
membranes on a Metglas magnetoelastic substrate. This substrate
was chosen because it has been successfully used in the past
coated with a continuous LTA membrane as the chemically active
layer for sensing applications. Even though the technique needs
further improvement, the patterns are composed of continuous
LTA membranes and are down to micrometer scale, which is a rst
step towards developing faster contactless sensors. In addition, this
methodology could be applied in the manufacturing of micromembranes of different zeolite types.
The optimization of the LTA micromembranes manufacturing
process, in order to control their thickness and uniformity should
be further examined, by using different seeding methods and
especially by improving the secondary growth parameters like
duration, temperature or even synthesis gel composition. The nal
step will be the use of the patterned structures as sensors for
the detection of different gasses and VOCs and determination of
the response times. Finally, as it was mentioned above, another

Fig. 11. XRD spectrum of the Metglas sample with the LTA micromembranes.

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V. Tsukala, D. Kouzoudis / Microporous and Mesoporous Materials 197 (2014) 213220

direction will be the development of microchannels between the


micromembranes using a second lithography process on the
unexposed PMMA lm.
Acknowledgments
The present study is nancially supported by the Research
Committee of the University of Patras under the K. Karatheodori
grant (Project Code D-153).
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