POLED SOL-GEL MATERIALS DOPED WITH PUSH-PULL
CHROMOPHORES: NMP1-FP6
project
Giovanna Brusatin, Gioia Della Giustina, Massimo Guglielmi
Department of Mechanical Engineering– Materials Sector, University of Padova
Mauro Casalboni, Fabio De Matteis
Dipartimento di Fisica, Università di Roma "Tor Vergata“
Massimiliano Dispenza, Anna Maria Fiorello, Mauro Varasi
SELEX S.I., Roma - Finmeccanica – Roma
Sigurd Schrader, Bernd Grimm
University of Applied Sciences Wildau Engineering Physics Wildau
The aim of the ODEON project is
the development of innovative
multifunctional nano-materials for
optoelectronic devices.
The research has been carried out
by design, synthesis and fabrication
of a demonstrator of an
interferometric electro-optical
modulator (Mach-Zender).
Constant
light input
Optical data
pulses
Electro-optic
waveguide
Control
Voltage Vc
Electro-Optical modulator: Oriented NL push pull organic
dyes in hybrids sol-gel or polymer matrices
Doping of hybrids
sol-gel or polymer
matrices
Push-Pull Chromophores: Molecular
hyperpolarizability (induced dipole
moment by an external electric field)
p=aE+bEE+gEEE+…
Optical data
pulses
Control
Voltage Vc
light input
Electro-optic
waveguide
Random orientation:
cancellation of single
contribution χ(2) = 0
Lithographic
process of active
films: channel
waveguides
Oriented dipoles: single
contributions added as
vectors χ(2) ≠ 0
Electric poling: the
isolated molecule
properties are
transferred to the
macroscopic
materials
Chromophores, Sol-gel precursors and
Hybrid sol gel doped films
OH
O
O
O2N
N
N
N
N
CH3
Spacer: CbOH
Chromophore: UAS HD-02
-The codoping with N-hydroxyethylcarbazole, CbOH, as
physical spacer avoids dye aggregation
-The covalent link of the chromophore by the epoxyamino coupling reaction.
O
O
O2N
O
O
Si
O
O
Si O
O
O
+
O
N H N
N
H+
H
H
O
N
N
O
HO
N
NSi
O
O Si
O
H
O
O
CH3
OH
O
O
O
O2N
N
N
O
Si
O
O
O
OH
O
Si
O
O
N
N
O
CH3
H
N
N
H
H
Si
N
H
Epoxy-amino coupling reaction
O
O
O
Si
O
O
Sol gel process
Films processes: Pretreatment and Poling
normalized d33
1.0
Laser input
0.8
0.6
0.4
0.2
0.0
SH signal
0
20 40 60 80 100 120 140 160
time (days)
Example of NL coefficient measure and of the time
stability of chromophore orientation in sol gel
Horizontal corona poling at
matrices;
d33 ~ 11pm/V
high T (~300°C);
In situ SHG measure
l = 1368nm or 1600nm
Films processes: Pretreatment and Poling
90°C + 120°C 4h
+
Poling
Large time stability of
cromophores
orientation
Monitoring of the UAS HD-02 UV-vis
absorption during thermal treatment
in vacuum and poling in N2
before baking
before poling-after baking
2h 90°C under vacuum
after poling
2h 90°C + 2h 120°C
6kV in N2
2.0
absorbance
- absorption remains intense at 120°C and after
poling
- CbOH is partially removed during the prebaking in
vacuum and is totally removed after poling
- under the electric field the inorganic crosslinking is
completed
- the thermal treatment produce a further organic
condensation between epoxy and amine
- the presence of amine determine basic catalysis of
the sol and protection against photobleaching
1.5
1.0
0.5
0.0
300
400
500
600
wavelength (nm)
700
800
Lithographic process for a Y-shaped waveguide
Optical data
pulses
SOL-GEL NL FILM
Control
Voltage Vc
light input
Electro-optic
waveguide
SEM microscopy images of a Y-branched
waveguide patterned by traditional lithographic
process (using RIE) on doped sol gel films
Light injection and light confinement by an Y-shaped
optical fiber produced by direct patterning
POLED SOL-GEL MATERIALS DOPED WITH PUSH-PULL
CHROMOPHORES: NMP1-FP6
project
ODEON PARTNERS
INS: INSTM – Firenze
University of Padova, Department of Engineering and Chemistry, Giovanna Brusatin,
Massimo Guglielmi, Danilo Pedron, Renato Bozio
University of Milano Bicocca: Giorgio A. Pagani, Alessandro Abbotto, Luca Beverina
University of Napoli, Department of Chemistry, Antonio Roviello, Roberto Centore
C.N.R. of Firenze, IFAC – Applied Physics Institute: Emilia Giorgetti, Stefano Sottini
University of Sassari, Department of Architecture and Planning, Plinio Innocenzi
UTV: NeMO - Dip. di Fisica Università di Roma – Tor Vergata, Mauro Casalboni
ENS: ENS Lyon, Chantal Andrau
ENG: CNRS and University of Strasbourg, Alain Fort
UHA: Hamburg University Department of Chemistry Martin-Luther, Jürgen Heck
UKA: Physikalische Chemie Universitaet Kaiserslautern, Hans-Georg Kuball, Graziano
Archetti
UAS: University of Applied Sciences Wildau Engineering Physics , Sigurd Schrader
AMS: SELEX, Alenia Marconi Systems, Annamaria Fiorello, Massimiliano Dispenza, Mauro
Varasi
WEI: Weizmann Institute of Science, Dep. of Organic Chemistry, Israel M. E. van der Boom
CEA: CEA-SACLAY DRT-LITEN DTS/CS, Lionel Sicot, Dr. Pierre-Alain Chollet
ULP: IPCMS-GONLO Alain Fort
KTH: Theoretical Chemistry Royal Institute of Technology, Stockholm , Hans Agren