Abstract—We report on the absorption properties of hybrid
sol-gel materials based on the 3-glycidoxypropyltrymethoxysilane
(GPTMS) precursor in the spectral region 0.5–7 THz. THz
transmission properties of such materials are quite good and,
even if not comparable with the most transparent polymers, still
their chemico-physical, structural, and electro-optical properties
make them attractive alternative systems for applications in the
THz field. An attempt to explain the relationship between
compositional and structural characteristics of the investigated
materials with their transmission behaviour is presented.
I. INTRODUCTION
n the last years the THz region has attracted growing
interest, both for the theoretical relevance (in molecular
spectroscopy, for instance) and for the several practical
applications in high-speed communication and security
imaging. However, suitable techniques to control and generate
THz waves are still lagging behind, pushing the research to
develop THz technologies for electronics and photonics. In
particular, the realization of guided systems for THz
transmission is of fundamental importance to solve problems
of efficient radiation manipulation, and integration on a single
chip device of sources and detectors, in the so called “THz
gap” (0.3-10 THz). Many materials have already been studied
in this spectral region. In this work, an investigation on hybrid
sol-gel systems has been carried out in order to explore their
potentialities as transparent media in the THz region. Hybrid
organic inorganic sol-gel materials present the outstanding
advantage of joining together the properties of glassy and
polymer systems, giving the possibility to widely tailor
material electro-optical and structural features to experimental
requirements.
We report on the transmission properties and absorption
coefficients of hybrid organic-inorganic sol-gel materials
prepared starting from an organically modified alkoxide
containing an epoxy ring, the 3-
glycidoxypropyltrimethoxysilane (GPTMS) precursor. An
attempt to explain the relationship between compositional and
structural characteristics of the investigated materials with
their transmission behaviour has been given. The lowest
absorption coefficients of such hybrid sol-gel materials in the
THz region are found when unpolymerized epoxy rings are
present, and in the case of systems that are poor of un-reacted
hydroxyl groups (-OH) interacting through hydrogen bonds.
II. EXPERIMENTAL
GPTMS was hydrolyzed both in acidic and basic
conditions. Acidic conditions were realized by adding HCl
(1N) in molar ratio GPTMS:H
2
O:HCl = 1:3:0.3, while basic
conditions was obtained by adding NaOH (1N) in molar ratio
GPTMS:H
2
O:NaOH = 1:3:0.003. Both solutions were left to
react for 1h under reflux at 80 °C. Sols were filtered with a 0.2
μm Millipore filter. Epoxy polymerization of GPTMS-based
hybrid systems was achieved by using a Lewis acid catalyst,
1% weight on total solution. Samples were prepared by
casting the solution into Teflon molds, and applying a thermal
treatment at 70 °C for 24h. Flat slabs of typical thickness
ranging from hundreds μm to a few mm are obtained.
Infrared absorption spectra in the range 4000-400 cm
-1
were
recorded by Fourier Transform Infrared spectroscopy (FTIR)
(Perkin-Elmer 2000) on similar films deposited by spin
coating on silicon wafers (100), and thermally treated at 70 °C
for 24h, with a resolution of 4 cm
-1
. Ultraviolet and visible
absorption spectra the range 200-2000 nm have been recorded
with a UV/VIS/NIR spectrophotometer (Jasco V-570) on
sample slabs, with a resolution of 1 nm. THz transmission
measurements have been performed with a Bruker IFS66v
Fourier Transform Interferometer at the SISSI infrared
beamline of the ELETTRA storage-ring, by using both
synchrotron and conventional (Globar) sources. A He-cooled
bolometer detector with a filter in the range 0-250 cm-
1
was
used, together with a 50 μm mylar beamsplitter.
Measurements have been taken at a 4 cm
-1
spectral resolution.
III. RESULTS
Four kinds of sol-gel systems have been examined in the
present study, that were synthesized starting from a GPTMS
precursor: GPTMS in acidic synthesis (GH), GPTMS in basic
synthesis (GB), and the respective polymerized systems
(polymerized GH and polymerized GB). Epoxy
polymerization of GPTMS-based hybrid systems consists in
the ring opening of the cyclic ether group that, through a
cationic polymerization mechanism, leads to the formation of
polyethylene oxide (PEO) oligomeric chains in the hybrid
network.
FT-IR spectra of the investigated systems are reported in
Figure 1. The decrease of the epoxy C-H stretching peaks at
3060 and 2995 cm
-1
, and of the asymmetric ring stretching
peak at 915 cm
-1
indicates the ring opening reaction.
P. Prosposito
a
, L. Brigo
b
, G. Della Giustina
b
, A. Perucchi
c
, S. Lupi
d
, and G. Brusatin
b
a
Dipartimento di Fisica, Università di Roma Tor Vergata, INSTM and MINAS-Lab, Via della Ricerca
Scientifica 1, 00133 Rome, Italy
b
Dipartimento di Ingegneria Meccanica – Settore Materiali, Università degli Studi di Padova, Via
Marzolo 9, 35131 Padova, Italy
c
Sincrotrone Trieste S.C.p.A., Area Science Park, I-34012 Basovizza, Trieste, Italy
d
CNR-IOM Laboratorio TASC and Dipartimento di Fisica, Università di Roma La Sapienza, Piazzale
Aldo Moro 2, I-00185 Rome, Italy
Transmittance of hybrid sol-gel materials in the THz region
I
978-1-4244-6656-6/10/$26.00 ©2010 IEEE