POLED SOL-GEL MATERIALS DOPED WITH PUSH-PULL CHROMOPHORES: NMP1-FP6 project 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). 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 Control Voltage V c Electro-optic waveguide Optical data pulses Constant light input

Push-Pull Chromophores: Molecular hyperpolarizability (induced dipole moment by an external electric field) p=E+EE+EEE+… Random orientation: cancellation of single contribution χ (2) = 0 Doping of hybrids sol-gel or polymer matrices Electro-Optical modulator: Oriented NL push pull organic dyes in hybrids sol-gel or polymer matrices Electric poling: the isolated molecule properties are transferred to the macroscopic materials Oriented dipoles: single contributions added as vectors χ (2) ≠ 0 Electro-optic waveguide Optical data pulses light input Control Voltage V c Lithographic process of active films: channel waveguides

Chromophores, Sol-gel precursors and Hybrid sol gel doped films Chromophore: UAS HD-02 Spacer: CbOH -The codoping with N-hydroxyethylcarbazole, CbOH, as physical spacer avoids dye aggregation -The covalent link of the chromophore by the epoxy- amino coupling reaction. Epoxy-amino coupling reaction Sol gel process

Films processes: Pretreatment and Poling SH signal Laser input Horizontal corona poling at high T (~300°C); In situ SHG measure  = 1368nm or 1600nm Example of NL coefficient measure and of the time stability of chromophore orientation in sol gel matrices; d 33 ~ 11pm/V

Films processes: Pretreatment and Poling Monitoring of the UAS HD-02 UV-vis absorption during thermal treatment in vacuum and poling in N 2 - 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 90°C + 120°C 4h +Poling Large time stability of cromophores orientation

Lithographic process for a Y-shaped 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 Electro-optic waveguide Optical data pulses light input Control Voltage V c SOL-GEL NL FILM

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 POLED SOL-GEL MATERIALS DOPED WITH PUSH-PULL CHROMOPHORES: NMP1-FP6 project