Molecule-Doped Polymers

The effective carrier mobilities and their dependence on concentration for benztriazole derivatives embedded in polycarbonate were explained by the percolative aspects in photoconductivity [296]. The observed field dependence of the mobility for polycarbonate films doped with diethynylaminobenzaldehy-de-diphenyl hydrazone cannot be accounted for by any known hopping model [297]. The influence of the nature of the polymer matrix on photogeneration and transport properties of the molecule doped polymers was investigated in some papers [57, 58, 298, 299],... 

At very high dopant concentrations, transport occurs direcdy between the dopant molecules. The polymer acts only as a binder in most cases. Taking TPD-doped PVK as an example, at low TPD concentrations the hole mobihty first decreases from 3 x 10 cm /Vs to 10 cm /Vs with increasing TPD concentration, because TPD molecules act as hole traps (48,49). At higher TPD concentrations, new direct transport channels between the TPD molecules open up and the hole mobihty increases to lO " cm /Vs for ca 60% TPD doping (Table 1, entries 9—11) (48,49). In this case, there is no evidence for unusual interaction between TPD and PVK that affects the hole transport process. 

In molecular doped polymers the variance of the disorder potential that follows from a plot of In p versus T 2 is typically 0.1 eV, comprising contributions from the interaction of a charge carrier with induced as well as with permanent dipoles [64-66]. In molecules that suffer a major structural relaxation after removal or addition of an electron, the polaron contribution to the activation energy has to be taken into account in addition to the (temperature-dependent) disorder effect. In the weak-field limit it gives rise to an extra Boltzmann factor in the expression for p(T). More generally, Marcus-type rates may have to be invoked for the elementary jump process [67]. 

There have been numerous studies of the electrical and emission properties of conjugated polymer-, small molecule-, and molecularly doped polymer-based OLEDs. The current-voltage and radiance-voltage characteristics have been nica sured as a function of thickness of the organic layer, temperature, different metal electrodes, etc. in an attempt to understand the device physics. A major factor in hibiting progress is the purity of the organic impurities that are incorporated dur-... 

Synthetic polymers are best known for their insulating dielectric properties which have been exploited for numerous applications in both the electrical and electronic industries. It was found recently that some polymers can also be rendered conductive by an appropriate treatment, thus opening the way to a new field of applications of these materials (2, 3). Usually, electrical conductivity is obtained by doping a neutral polymer, rich in unsaturation, with donor or acceptor molecules. These polymers are rather difficult to synthesize, which makes them very expensive besides they are often sensitive to environmental agents, like oxygen or humidity, thus restricting their practical use to oxygen-free systems. 

Technically important electrochemical reactions of pyrrole and thiophene involve oxidation in non-nucleophilic solvents when the radical-cation intermediates react with the neutral molecule causing polymer growth [169, 191], Under controlled conditions polymer films can be grown on the anode surface from acetonitrile. Tliese films exhibit redox properties and in the oxidised, or cation doped state, are electrically conducting. They can form the positive pole of a rechargeable battery system. Pyrroles with N-substituents are also polymerizable to form coherent films [192], Films have been constructed to support electroactive transition metal centres adjacent to the electrode surface fomiing a modified electrode,... 

A number of other characteristics are required in order to ensure a viable polymeric conductor. Chain orientation is needed to enhance the conducting properties of a polymeric material, especially the intermolecular conduction (i.e., conduction of current from one polymer molecule to another). This is a problem with many of the polymers that are amorphous and show poor orientation. For moderately crystalline or oriented polymers, there is the possibility of achieving the required orientation by mechanical stretching. Liquid crystal polymers would be especially advantageous for electrical conduction because of the high degree of chain orientation that can be achieved. A problem encountered with some doped polymers is a lack of stability. These materials are either oxidants or reductants relative to other compounds, especially water and oxygen. 

Later on a lot of research into the photosensitivity of the polymer matrix with various inserted molecules was carried out. A great deal of attention was focused on molecule doped polycarbonates. The photoconduction mechanism in such systems has many common features with the same mechanism for doped PVC. 

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