Liquid-crystalline azopolymers for the fabrication of nanostructured films

Author(s)

Thiago Francisco Costa Carpes Borges

• Document type: Master's Dissertation
• Press: São Carlos.
• Institution: Universidade de São Paulo (USP). Instituto de Física de São Carlos (IFSC/BT)
• Defense date: 2008-04-28

Examining board members

Osvaldo Novais de Oliveira Junior; Jonas Gruber; Cleber Renato Mendonça

• Advisor: Osvaldo Novais de Oliveira Junior

Abstract

Photoinduced birefringence and surface-relief gratings (SRGs) have been extensively investigated in azopolymer films obtained with various film-fabrication methods. Even though well-established models exist for amorphous azopolymers which explain the dynamics of photoinduced birefringence and mass transport leading to SRGs, the same is not true for liquid-crystalline azopolymers. In an attempt to try and resolve controversies in the literature, in this work we synthesized an azopolymer with two different molar masses, which were then employed in optical storage and photoinscription of SRGs. The synthesis was performed with 4,4-diphenylmethane-diisocyanate (MDI) and an azomonomer obtained in a 3-step procedure: synthesis of the azodye, incorporation of the flexible segment and functionalization of the monomer. The materials were characterized by ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H-NMR). The molar mass of the polymers was determined by high performance size exclusion chromatography (HPSEC). The liquid-crystalline properties of the azomonomer and azopolymers were confirmed via differential scanning calorimetry (DSC), polarized optical microscopy and X-ray diffraction, with a isotropic-liquid crystal phase transition occurring at ca 79oC and 84oC for the monomer and polymers, respectively. Stable Langmuir films made with the azopolymers could be formed at the air-water interface, which were transferred onto solid substrates in the form of Langmuir-Blodgett (LB) films. These LB films could be used in optical storage experiments, with the photoinduced birefringence being higher than in cast films of the same azopolymers, probably due to the better organization of the nanostructured LB films. SRGs could be photoinscribed on both types of film with a low-intensity laser beam, in contrast to the reports in the literature, according to which SRGs can only be inscribed on liquid-crystalline azopolymer samples if high laser intensities are used. Though the SRG amplitude was small and the photoinscription process still needs to be optimized, this finding may open the way for a host of new applications of liquid-crystalline azopolymers. (AU)