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

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

Hybrid TiO2: polymer photovoltaic cells made from a titanium oxide precursor

Hybrid TiO2:polymer photovoltaic cells were made from mixtures of titanium(IV) isopropoxide and poly[2-methoxy-5-(3',7'-dimethyloctyl)-p-phenylene vinylene] (MDMO-PPV) or poly(3-octyl thiophene) (P3OT) via hydrolysis in air. Cells were made with varying titanium(IV) isopropoxide:polymer ratios. Current–voltage measurements (at 0.7–0.8 sun equivalent) of a TiO2:P3OT (10 vol.% TiO2) photovoltaic cell show a short-circuit current of 0.7 mA/cm2, an open-circuit voltage of 450 mV and a fill factor of 0.41, resulting in a calculated AM1.5 (100 mW/cm2) power conversion efficiency of 0.17%. Devices based on MDMO-PPV and TiO2 (20 vol.% TiO2) show an open-circuit voltage of 600 mV and a short-circuit current of 0.6 mA/cm2 (at 0.7 sun equivalent), resulting in a calculated AM1.5 power conversion efficiency of 0.22%

Reduction of escape cone losses in luminescent solar concentrators with cholesteric mirrors

The Luminescent Solar Concentrator (LSC) consists of a transparent polymer plate containing luminescent particles. Solar cells are connected to one or more sides of the polymer plate. Part of the light emitted by the luminescent particles is guided towards the solar cells by total internal reflection. About 25% of the dye emission is typically emitted within the optical escape cone of the matrix material and is lost due to emission from the top. We study the application of selectively-reflective cholesteric layers to reduce these losses. We have implemented these mirrors in the ray-tracing model for the LSC. The simulations show that an optimum in performance can be obtained by selecting an appropriate centre wavelength of the cholesteric mirror. External Quantum Efficiency measurements were performed on LSC devices with a mc-Si, GaAs or InGaP cell and a dichroic mirror. This mirror shows a similar behavior as the cholesteric mirror. The results show that for a 5x5 cm2 LSC the mirror does improve the EQE in the absorption range of the dye

Femtosecond spectroscopic studies of photoinduced electron transfer in MDMO-PPV:ZnO hybrid bulk heterojunctions

The photophysics of charge carriers (polaron) in MDMO-PPV:ZnO hybrid bulk heterojunction is studied at 80 K by femtosecond transient absorption spectroscopy. A short-lived positive polaron is observed in the blend phase in MDMO-PPV:ZnO blend films with a weight ratio of 1:1 and 1:2. Further increase of ZnO weight ratio results in a significant quenching of the polaron absorption. The results are discussed in the concept that both pristine polymer and MDMO-PPV:ZnO blend phases coexist in the blend films. It is concluded that a polaron is photogenerated within the excitation laser pulse (<100 fs) and electron transfer efficiency is highest in blend films 1:1 and 1:2. Lack of the interfacial area and faster back electron transfer process are discussed to be responsible for the quenching of the electron transfer efficiency in blend film 1:3

Hybrid solar cells using a zinc oxide precursor and a conjugated polymer

We describe a new method towards bulk-heterojunction hybrid polymer solar cells based on composite films of zinc oxide (ZnO) and a conjugated polymer poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV). Spin-coating diethylzinc as a ZnO precursor and MDMO-PPV from a common solvent at 40 % humidity and annealing at 110 °C provides films in which crystalline ZnO is found to be intimately mixed with MDMO-PPV. Photoluminescence and photoinduced spectroscopy demonstrate that photoexcitation of these hybrid composite films results in a fast and long-lived charge transfer from the polymer as a donor to ZnO as ato be obtained n acceptor. Using the ZnO-precursor method, hybrid polymer solar cells have been made with an estimated air-mass of 1.5 (AM 1.5) energy conversion efficiency of 1.1 %. This new method represents a fivefold improved performance compared to similar hybrid polymer solar cells based on amorphous TiO2

Hybrid solar cells using a zinc oxide precursor and a conjugated polymer

We describe a new method towards bulk-heterojunction hybrid polymer solar cells based on composite films of zinc oxide (ZnO) and a conjugated polymer poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV). Spin-coating diethylzinc as a ZnO precursor and MDMO-PPV from a common solvent at 40 % humidity and annealing at 110 °C provides films in which crystalline ZnO is found to be intimately mixed with MDMO-PPV. Photoluminescence and photoinduced spectroscopy demonstrate that photoexcitation of these hybrid composite films results in a fast and long-lived charge transfer from the polymer as a donor to ZnO as ato be obtained n acceptor. Using the ZnO-precursor method, hybrid polymer solar cells have been made with an estimated air-mass of 1.5 (AM 1.5) energy conversion efficiency of 1.1 %. This new method represents a fivefold improved performance compared to similar hybrid polymer solar cells based on amorphous TiO2

The solar noise barrier project: 1. Effect of incident light orientation on the performance of a large-scale luminescent solar concentrator noise barrier

In this work we describe the relative performance of the largest luminescent solar concentrator (LSC) constructed to date. Comparisons are made for performance of North/South and East/West facing panels during a sunny day. It is shown that the East/West panels display much more varied performance during the day, as the structural elements of the barrier interfere with solar illumination and cause shading, but perform similarly for both front and back illumination conditions. The results of a more extended, 200 day measurement period mirror the results of the single sunny day results. This work demonstrates the importance of frame design to minimize self-shading of the LSC panels