We report combined scanning near-field optical microscopy (SNOM) and near-field photocurrent (NPC) imaging of a binary conjugated polymer blend. We find phase separation on a scale of about 5 μm, with a good correspondence between topographic, fluorescence, and photocurrent images. We excited at 488 nm, a wavelength at which only one of the two polymers absorbs light. Under this illumination regions that are high in the topography image show high luminescence and photocurrent.

The photoluminescence (PL) efficiencies in the different regions of the sample were determined by calculating the absorbed energy using the Bethe-Bouwkamp model, and knowledge about the chemical composition of the different phases of the polymer blend. The calculation also allowed us to conclude that the photocurrent generation efficiency (current/absorbed photons) of the different polymer phases is comparable within the limit of confidence of this experiment (±10 %).

A 2,3-dibutoxy-1,4-phenylenevinylene comonomer was incorporated into a distyrylbenzene derivative 11. Novel 1,2-disubstituted-3,6-dibromobenzene comonomers 15 and 18 were prepared by directed metallation. Copolymerization of 11with a 9,9-dioctylfluorene-2,7-diboronate ester 1 yielded a green fluorescent polymer while copolymerization of 15 and 18 with the 9,9-dihexylfluorene-2,7-diboronate 22 afforded promising blue fluorescent polymers 23 and 24 respectively.

The synthesis of poly(2,3-dibutoxy-1,4-phenylene vinylene) (DB-PPV) has allowed the study of this material as the active layer in a multiple layer device using a composite combination of polymer and Alq3 with an oxadiazole as electron injection/transport layers. The luminous efficiency of the resulting device was significantly improved as a result of this combination of transport layers. An entirely new approach to the synthesis of monomers for PPV precursors is described in which the 2- and 5- substituents are introduced by directed metallation groups (DMGs) which ultimately become the bis(halomethyl) groups.

We studied the surface properties of indium-tin oxide (ITO) modified by wet (aquaregia, ultrasonication, RCA) and dry (oxygen- and argon-plasma) treatments. The surface modification was investigated by surface energy, surface morphology, sheet resistance, carrier concentration, carrier mobility, and workfunction measurements. We report that the studied oxygen-plasma treatment induces: the highest surface energy with the highest polarity, the smoothest surface, the highest carrier density but the lowest mobility, the lowest sheet resistance, and the highest workfunction (stable in air). Polymer light-emitting diodes fabricated with the oxygen plasma treated substrates give the best performance in terms of electroluminescence efficiency and device lifetime. This is attributed to a favorable surface modification of ITO anodes by oxygen-plasma.

We studied the influence of various surface treatments of indium-tin oxide anodes on the operational stability of high-efficiency green-emitting polymer light-emitting diodes, fabilicated with a doped poly(3,4-ethylene dioxythiophene) PEDOT hole transport layer, a polyfluorene-based emissive layer, and Ca-Al cathodes. The anodes were modified by physical (oxygen-plasma), chemical (aquaregia), or combined treatments. Oxygen-plasma improves the stability under constant current over all the other anodes, with half-brightness lifetimes (initial brightness, 200 cd/m2) two to five times longer than for untreated samples, and 1000 times longer than for aquaregia ones. We derive two major indications for optimisation of PLEDs. First, thermal management of the diode is of the uppermost importance. Second, the ITO anode and in general the electrical properties of the hole-injecting contact are crucial to device operation, even in the presence of a hole transport layer.

The synthesis of poly(1,4-phenylene vinylene)s (PPVs) containing a 2,3-dialkoxy substitution pattern has been developed. Poly[2,3-bis(2-ethylhexyloxy)-1,4-phenylene vinylene)] (BEH-PPV, 4) was prepared and its optical properties compared with the recently discussed poly(2,3-dibutoxy-1,4-phenylene vinylene) (DB-PPV, 1), which showed in contrast to classical 2,5-substituted PPV derivatives a notable blue-shift of the longest-wavelength absorption (λmax) and a considerable increase of the solid-state photoluminescence (PL) efficiency. The two statistical PPV copolymers 5 and 6 comprising 2,3-dibutoxy and dimethyloctylsilyl- or 2,5-bis(dimethyloctylsilyl) side-chains, respectively, were synthesized via the Gilch dehydrohalogenation route. Double-layer light-emitting devices (LEDs) were demonstrated to combine high electroluminescence efficiencies with low turn-on voltages.

The solid state luminescent properties of new statistical copolymers of 2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene and a porphyrin-substituted phenylene vinylene are reported. The photoluminescence, PL, emission shows an efficient energy transfer to the porphyrin, in spite of the small absorption coefficient of the porphyrin in the wavelength range of the poly [2-methoxy-5-(2'- ethylhexyloxy)-1,4-phenylene vinylene], MEH-PPV, emission. At a porphyrin content of 0.25%, by weight, the emission is already dominated by the porphyrin. The PL efficiency of these copolymers is significantly reduced from the value of 13% for MEH-PPV down to 3% for the copolymer with 10.84% of porphyrin. Efficient energy transfer is also observed in the emission spectra of light-emitting diodes.

A new poly(phenylenevinylene) [PPV] derivative 8 with dialkoxy substituents at the 2,3- positions of the phenylene ring of the polymer backbone has been prepared. This exhibited significantly different properties compared with the typical 2,5-dialkoxy substituted PPV derivatives. The polymer is not only significantly blue-shifted in its optical and luminescence properties but also has high photoluminescence (PL) and electroluminescence (EL) efficiencies. Investigation of the model oligomer 11 offers insight into this interesting behavior.

New oxadiazole-based polymeric materials have been synthesized either as side chain copolymers with polymethacrylate or as main chain copolymers carrying solubilizing elements such as hexafluoropropylidene or meta-linked aromatic spacer units. Many of these materials exhibit blue luminescence in the solid state. The materials have been evaluated by photoluminescence and cyclic voltammetry studies, and as the electron transporting layer in a two-layer electroluminescent device with poly(p-phenylenevinylene) (PPV) as the emissive layer. The major conclusion is that these materials function by providing large heterojunction offsets at the Highest Occupied Molecular Orbital (HOMO) which block the passage of holes through the device.

Conjugated polymers can be use to provide charge transport and emissive layers in a range of thin-film electroluminescent devices. Electroluminescence results from radiative decay of excitons which are formed by electron-hole capture. Device efficiency is particularly sensitive to the balancing of electron and hole currents injected from opposite electrodes, and this is best achieved at the heterojunction between two polymer layers with different electronegativities. We report here the properties of a conjugated polymer with high electron affinity, a cyano derivative of poly (p-phenylene vinylene), PPV. This polymer shows an electron affinity considerably higher than than that of PPV, and is therefore suitable for use as the electron transporting layer in heterostructure LEDs. It shows efficient photoluminescence due to radiative decay of singlet excitons, and photoinduced absorption in the IR, similar to that in PPV, which we attribute to excitations of photogenerated triplet excitons. EL devices formed with a heterojunction between PPV and this cyano derivative of PPV, with indium/tin oxide as positive electrode, PPV, cyano-PPV layers and an aluminium negative electrode, show internal quantum efficiencies as high as 4%.