Rare-earth doped polymer waveguides and light emitting diodes

Polymer-based optical waveguide amplifiers offer a low-cost alternative for inorganic waveguide amplifiers. Due to the fact that their refractive index is almost similar to that of standard optical fibers, they can be easily coupled with existing fibers at low coupling losses. Doping the polymer with rare-earth ions that can yield optical gain is not straightforward, as the rare-earth salts are poorly soluble in the polymer matrix. This thesis studies two different approaches to dope a polymer waveguide with rare-earth ions. The first one is based on organic cage-like complexes that encapsulate the rare-earth ion and are designed to provide enough coordination sites to bind the rare-earth ion and to shield it from the surrounding matrix. Chapter 2 describes the optical properties of Er-doped organic polydentate cage complexes. The complexes show clear photoluminescence at 1.54 mm with a bandwidth of 70 nm, the highest reported for an erbium-doped material so far. The luminescence lifetime is very short (~1 ms) due to coupling to vibrational overtones of O-H and C-H bonds. Due to this short luminescence lifetime, high pump powers (~1 W) are needed for optical gain in a waveguide amplifier based on these complexes. The pump power can be reduced if the Er is excited via the aromatic part of the complex, which has a higher absorption cross section. In Chapter 3 a lissamine-functionalised neodymium complex is studied in which the highly absorbing lissamine acts as a sensitiser. The lissamine is first excited into the singlet state from which intersystem crossing to the triplet state can take place. From there it can transfer its energy to the Nd ion by a Dexter transfer mechanism. Room-temperature photoluminescence at 890, 1060, and 1340 nm from Nd is observed, together with luminescence from the lissamine sensitiser at 600 nm. Photodegradation of the lissamine sensitiser is observed, which is studied in more detail in Chapter 4. The observed change in time of the spectral shape of the lissamine luminescence can be explained by assuming that two types of complexes exist. One type in which energy transfer to the Nd3+ ion can take place, and one that is not coupled to Nd. The highly absorbing sensitiser makes the standard butt-end coupling of the pump light into a waveguide amplifier impractical. The pump power can be used more efficiently by using a novel coupled waveguide system as described in Chapter 5. This employs gradual evanescent field coupling between parallel pump and signal waveguides. An alternative approach to make a rare-earth doped polymer waveguide is by combining the excellent properties of SiO2 as a host for the rare-earth with the easy processing of polymers. The optical properties of Er-doped silica films made by an acid-catalysed sol-gel synthesis are reported in Chapter 6. The Er exhibits long luminescence lifetimes of 10-12 ms, which indicates that OH from the wet chemical synthesis is successfully removed during the vacuum anneal treatment. Using a base-catalysed sol-gel synthesis, silica colloidal spheres with diameters of 175 and 340 nm were grown. Chapter 7 describes the luminescence properties of the 340 nm spheres, implanted with Er up to concentrations of 1.0 at. %. The Er shows a very long luminescence lifetime of 17 ms, and the radiative lifetime is estimated to be 20-22 ms, indicating a high quantum efficiency. This long luminescence lifetime is partly due to the low local optical density of states (DOS) in the free standing silica colloids. Optical gain calculations are made for the colloid/polymer waveguide that predicts a net gain of 8.7 dB at a pump power of 30 mW, for a 15 cm long waveguide. Such a length can be rolled up on an area of 16 mm2. In Chapter 8, calculations of the DOS are described for thin films as well as the spherical colloids. By comparing the calculation with experimentally probed decay rates, radiative and non-radiative components in the decay of Er are determined. Besides optical pumping of planar waveguide amplifiers it would be interesting if electrical pumping could be achieved. As a first step in this direction Chapter 9 reports 890 nm electroluminescence from lissamine-functionalised Nd complexes in a polymer light emitting diode. It is shown that the lissamine sensitiser plays a crucial role in mediating the energy transfer from the conjugated polymer to the Nd3+ ion, via singlet-singlet and triplet-triplet energy transfer. Finally, Chapter 10 gives an overview of important device considerations for the fabrication of optically and electrically pumped polymer-based planar optical amplifiers based on the novel materials concepts described in this thesis.