Ultralarge and Thermally Stable Electro‐optic Activities from Diels–Alder Crosslinkable Polymers Containing Binary Chromophore Systems

Poled electro-optic (EO) polymers have enabled many advances in the exploration of high-speed and broadband information technologies. Polymer based EO devices have been demonstrated to have large bandwidths (over 110 GHz), low driving voltages, and sustain their performance in a flexible form or under extreme environmental conditions. For optical circuits, EO polymers can be easily integrated with striplineor ring-structured waveguides made of sol–gels, low-loss fluorinated polymers, silicon slots, conducting oxides, and photonic crystals. Recently, EO polymers have also been utilized for the generation/detection of a gap-free pulsed THz system with a bandwidth up to ca. 12 THz. Large numbers of discrete photonic components need to be inserted into integrated systems of telecommunication and silicon microphotonics, especially where an extreme amount of data is required to travel in a very small space. Therein lies the great challenge for polymer-based EO technologies: to have thermally stable EO coefficients (r33) of around 500 pm V at wavelengths of 1.31 or 1.55 lm. Currently, the most commonly used materials for polymeric EO devices are based on poled polymers with r33 values around 50–80 pm V at wavelengths of 1.31 or 1.55 lm. In these materials, dipolar nonlinear optical (NLO) chromophores have been doped or incorporated at a level of ca. 20– 25 wt % to reach their maximum r33 values. [5–10] Beyond such a moderate loading of chromophores, strong intermolecular electrostatic interactions severely limit the poling-induced polar order and cause phase-separation problems between chromophores and polymers. To further improve EO activity, research efforts have focused on developing shape-engineered chromophores with high molecular optical nonlinearities (lb), where lb is a product of first hyperpolarizability and the dipole moment of the NLO chromophore, and increasing order within the matrices by controlling the nanoscale architecture of macromolecules. In our recent study we have demonstrated, using Diels–Alder (DA) “click chemistry” to post-functionalize NLO chromophores onto polymers, that high chromophore loading levels (up to 35 wt %) and large r33 values (up to 110 pm V) could be achieved in in situ generated side-chain dendronized NLO polymers with non-reacted chromophores as guest dopants. This opens a new avenue to explore optimal host–guest combinations and to develop an efficient way to control lattice hardening in these hybrid polymers. The ultimate goal is to simultaneously achieve very large EO activity, good thermal stability, high optical transparency, and excellent mechanical properties within the same material via molecular design and facile processing. In this paper, we report a novel method to disperse a highly efficient secondary chromophore into in situ crosslinked NLO polymer networks, leading to both enhanced EO activity (> 260 pm V at 1.31 lm) and alignment stability at 85 °C. In photorefractive (PR) polymers and liquid-crystal (LC) systems, binary chromophore mixtures have been shown to elevate the loading density of small dipolar dyes without causing phase separation. We have extended this further by incorporating highly polarizable NLO chromophores into these binary systems. In addition, DA click chemistry has also been employed to improve the physical properties of these materials. This combined effort demonstrates that binary mixtures of large-bl chromophores can be loaded into side-chain NLO matrices and efficiently poled to give EO activities higher than the summed value of two added chromophores. These systems can also be mildly cured to ensure a thermally stable EO response. The EO polymers studied in this work exist as a three-component host–guest system (Fig. 1). The host polymer is a copolymer, poly[(methyl methacrylate)-co-(9-anthracenyl methyl methacrylate)] (PMMA-AMA), with around 10 mol % of the anthracenyl moiety. To this host, AJC146 was added together with compound 1a, 1b, or 1c as binary guest chromoC O M M U N IC A TI O N S