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Zeolite LTA micromembrane fabrication

on Metglas using E-Beam Lithography


E-Beam
Lithograph
y
Laboratory

Vassiliki Tsukala, Dimitris Kouzoudis


Department of Engineering Sciences, University of Patras, GR-26504, Patras, Greece

Zeolites are aluminosilicate nanoporous crystalline materials


which, in their membrane form, demonstrate controllable surface
properties, well-defined porosity, large surface area along with
chemical, thermal and mechanical stability. As a result, they can be
utilized in new advanced applications like sensors, microreactors,
microseparators, as low-k materials for microelectronic devices,
microelectrochemical cells and biomedical.
The ability of tailoring and controlling zeolite membrane size in
small-scale offers numerous advantages, therefore many researches
have focused on patterning zeolite membrane1. They have employed
three
methods:
microcontact
printing,
photoetching
and
photolithography, resulting in micro-scale structures and they have
fabricated only siliceous zeolite membranes (MFI, ZSM-5, Sil1) on
glass or silicon substrates2.
The use of a more versatile technique, like Electron Beam
Lithography (EBL), other functional substrates and various zeolite
types could enhance micromembrane technology and applications.

Objectives

Results

In order to investigate the conditions of zeolite


micromembrane fabrication,
1) Tests were performed to evaluate
optimum EBL dosage of the PMMA
coated on Metglas and 40C/cm2
chosen for minimum proximity effect
high accuracy.

the
film
was
and

BT3_30_2 LTA crystals

30000

Lin (Counts)

Introduction

Hydrothermal synthesis was carried out for various crystallization


duration in order to examine membrane formation

20000

10000

0
5

10

20

30

40

2-Theta - Scale
BT3_30_2 LTA crystals - File: BT3_30_2.raw - Type: 2Th/Th locked - Start: 5.000 - End: 40.004 - Step: 0.020 - Step time: 87.5 s - Temp.: 25 C (Room) - Time Started: 5 s - 2-Theta: 5.000 - Theta:
Operations: Import
01-073-2340 (C) - Sodium Aluminum Silicate Hydrate - Na12Al12Si12O48(H2O)27 - Y: 109.59 % - d x by: 1. - WL: 1.5406 - Cubic - a 24.61000 - b 24.61000 - c 24.61000 - alpha 90.000 - beta 90.000 - ga

2) Nano-sized LTA crystals were synthesized


with average diameter of approximately
95nm.
3) Hydrothermal synthesis was carried out for various durations, in
order to examine membrane formation, and it was concluded that
the crystallization was complete in less than 24 hrs. Both
nanozeolites and membranes were attached only on the exposed
Metglas surface, due to repulsive forces of the negatively charged
PMMA surface and LTA precursors3.

This study focused on three major goals:


1) To employ EBL for the patterning of the substrate surface in the
micro-scale
2) To use a magnetoelastic material (Metglas, Fe40Ni38Mo4B18) as a
substrate for future sensing applications
3) To fabricate LTA zeolite type (|Na+12(H2O)27|8 [Al12Si12O48]8)
micromembranes onto magnetoelastic substrate as candidate
sensitizing layer

Fabrication methods

The experimental procedure consists of the following steps

3 hrs

5 hrs

24 hrs

35 hrs

Finally, LTA micromembranes were synthesized using EBL dose of


40C/cm2 and seed crystals with 95nm average size under
hydrothermal conditions at 85oC for 20 hrs. The LTA type zeolite was
confirmed by XRD while structures as small as 50x20m
(parallelogram) and 40m (circle) were achieved.
BT3_30_1 LTA (b side)
13000

12000

11000

10000

9000

Seeding
The Metglas substrate was drop-seeded with LTA nanocrystals (1%
in H2O) synthesized hydrothermally from a mixture with molar
ratio: Al2O3/6SiO2/0,32Na2O/7,27(TMA)2O/350H2O at 80oC for 24
1. Substrate
hrs.
Synthesis
The LTA micromembranes grew
hydrothermally onto the patterned and
2. Coating
seeded surface of Metglas at 85oC
from a solution with molar ratio:
4,17Na2O/Al2O3/1,87SiO2/460H2O.
3. EBL
The Metglas was dried and treated with
acetone in ultrasonic bath for the lift-off
4. Seeding
of PMMA.
SiO2
Source
Base
Water

Al2O3
Source
Base
Water

5. Synthesis

Heating

Heating

Lin (Counts)

E-beam lithography
The Metglas substrate was cleaned and spin-coated with PMMA
(polymeric photoresist, 5% in PGMEA). Patterns were generated
with the XeDraw 2 (XENOS GmbH) system attached to the SEM
(JEOL, JSM-6610LV) for various dosages and developed with
IPA/H2O (7:3).

8000

7000

6000

5000

4000

3000

2000

1000

0
5

10

20

30

40

2-Theta - Scale
BT3_30_1 LTA (b side) - File: BT3_30_1_side_B.raw - Type: 2Th/Th locked - Start: 5.000 - End: 40.004 - Step: 0.020 - Step time: 87.5 s - Temp.: 25 C (Room) - Time Started: 2 s - 2-Theta: 5.000
Operations: Import
01-073-2340 (C) - Sodium Aluminum Silicate Hydrate - Na12Al12Si12O48(H2O)27 - Y: 73.73 % - d x by: 1. - WL: 1.5406 - Cubic - a 24.61000 - b 24.61000 - c 24.61000 - alpha 90.000 - beta 90.000 - ga

Conclusions
Both LTA seed crystals and membrane were successfully attached
on the exposed Metglas surface.
Appropriate conditions for LTA micromembrane fabrication on
Metglas were investigated.
It is the first time that continuous LTA film was fabricated in the
micro-scale and also the first time that EBL was employed for this
purpose.

References
1. J. Coronas, J. Santamaria, Chem. Eng. Sci., 59 (2004) 4879-4885
2. Z. Ming, Z. BaoQuan, L. XiuFeng, Chin. Sci. Bull., 53 (2008) 6, 801-816
3. E. Yilmaz, H. Sezen, S. Suzer, Angew. Chem. Int. Ed., (2012) 51, 5488-5492

Acknowledgments
This study is funded by the Research Committee of the University of Patras,
under the K. Karatheodori Grand (Project No. D-153).

Contact Information
SiO2
Al2O3
H2O
M+OH-

SiO2
Al2O3
H2O
M+OH-

6. Lift-off

D. Kouzoudis
koudoudis@des.upatras.gr

V. Tsukala
vtsukala@iceht.forth.gr

http://www.des.upatras.gr/Nanolab/welcome.html

ICSAAM 2013
5th International Conference on Structural Analysis of Advanced Materials
23 - 26 September 2013, Island of Kos, Greece