Poly charge transfer processes

In order to learn about the true quantum efficiency of photogeneration one therefore has to study the photoinduced charge generation mechanism at faster time scales. Pump probe spectroscopy utilising a few optical-cycle laser pulses (5-6 fs) in the visible spectral range with broadband frequency conversion techniques [89] now makes it possible to study extremely fast optically-initiated events with unprecedented time resolution. Such a setup was used to time-resolve the kinetics of the charge transfer process from a polymer chain to a fullerene moiety in thin films of poly[2-methoxy, 5-(3, 7 -dimethyl-octyloxy)]-p-phenylene vinylene (MDMO-PPV) and [6,6]-phenyl C6i butyric acid methyl ester (PCBM). Solutions prepared from 1 wt% solutions of toluene on thin quartz substrates were studied. 

The polymerization of allyl acetate has been studied reasonably extensively in the effort to elucidate the mechanisms of the polymerization process. The utility of poly(allyl acetate) as a resin is believed to be negligible. Nevertheless, this compound has been polymerized in bulk, in solution, and in emulsion. There is mention of a cationic polymerization process and of radiation-induced charge-transfer processes. 

The ruthenium oligothienylacetylide complexes 93 (Chart 5.30) [106] and the oligothienylferrocene complexes 94a and b were electrochemically polymerized [107]. The voltammetry of poly-94a and poly-94b films contains redox waves due to both the ferrocene and backbone redox couples. Low-energy absorption bands appear upon oxidation of both the Fe centers and the conjugated backbone in the UV-Vis-near-IR spectrum of the films, and these have been attributed to charge-transfer processes. The poor solubility of 94b prevents electropolymerization at room temperature however, polymer films can be prepared at elevated temperatures. Electropolymerization of 95, in which hexyl chains have been added to increase the monomer solubility, has also been reported [108]. 

The reaction of PANI in its oxidized form (both in doped and undoped form) with water, resulting in the formation of superoxide, was studied with ESR spectroscopy by Otsuka et al. [506]. Electrode kinetics of various charge transfer processes at poly(o-phenylenediamine), poly(Af-methylaniline), and poly(iV-ethylaniline) were investigated by Chiba et al. [507]. 

The poly-TV-vinylcarbarzole trinitrofluorenone (PVK TNF) charge-transfer complex [21-23] was the first commercial organic photoreceptor used in electrophotography by IBM. The photoconductivity of this material is comparable to that of amorphous selenium, but its utilization in practical devices was limited, owing to its toxicity and long transit-time value, comparable, as for most single-layer photoreceptors, to the development process time. 

Poly(phenylmethylsilane) (PMPS) was investigated by Kepler et al. (1983, 1984, 1987). Figure 32 shows the wavelength dependence of the absorption and the normalized photocurrent. The spectral dependence of the photocurrent indicates that carrier generation occurs by an extrinsic process which results primarily from an interaction of charge-transfer excitons with the surface. The argument is similar to that proposed earlier by Kepler (1976) to describe hole... 

Hole transport in polymers occurs by charge transfer between adjacent donor functionalities. The functionalities can be associated with a dopant molecule, pendant groups of a polymer, or the polymer main chain. Most literature references are of doped polymers. The more common donor molecules include various arylalkane, arylamine, enamine, hydrazone, oxadiazole, oxazole, and pyrazoline derivatives. Commonly used polymers are polycarbonates, polyesters, and poly(styrene)s. Transport processes in these materials are unipolar. The mobilities are very low, strongly field and temperature dependent, as well as dependent on the dopant molecule, dopant concentration, and the polymer host This chapter reviews hole transport in polymers and doped polymers of potential relevance to xerography. The organization is by chemical classification. The discussion mainly includes molecularly doped, pendant, and... 

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