Conjugated polymers properties

Polymers. The Tt-conjugated polymers used in semiconducting appHcations are usually insulating, with semiconducting or metallic properties induced by doping (see Flectrically conductive polymers). Most of the polymers of this type can be prepared by standard methods. The increasing use of polymers in devices in the last decade has led to a great deal of study to improve the processabiUty of thin films of commonly used polymers. 

Table 2 shows the present state-of-the-art for the electrical conductivity of doped conjugated polymers. The magnitude of the electrical conductivity in polymers is a complex property determined by many stmctural aspects of the system. These include main-chain stmcture and TT-ovedap, molecular... 

The science and technology of conducting polymers are inherently interdisciplinary they fall at the intersection of three established disciplines chemistry, physics and engineering hence the name for this volume. These macromolccular materials are synthesized by the methods of organic chemistry. Their electronic structure and electronic properties fall within the domain of condensed matter physics. Efficient processing of conjugated polymer materials into useful forms and the fabrication of electronic and opto-electronic devices require input from engineering i. e. materials science (more specifically, polymer science) and device physics. 

The opportunity to synthesize new conjugated polymers with improved properties began to attract the attention of a larger number of synthetic chemists in the 1980s. Equally important was the subsequent development of stable, processible metallic polymers. As a result of these efforts, we now have a class of materials which exhibit a unique combination of properties the electronic and optical properties of metals and semiconductors in combination with the processing advantages and mechanical properties of polymers. 

In this contribution, we discussed effects of disorder on the electronic properties of quasi-one-dimensional Peierls systems, like the conjugated polymer fraus-poly-acetylene. Since polymer materials generally are rather disordered and the effect of disorder on any quasi-one-dimensional system is strong, a proper description of these materials requires consideration of such effects. 

Figure 9-1. Materials overview a few sclcclcd conjugated polymers and Ihcir properties have been compiled and ihe following abbreviations arc used DO-PPP...Poly(2-decyloxy-l,4-phcnylcnc), EHO-PPP...Poly(2-(2 -elhylliexyloxy)-l,4-phcnylenc), CN-PPP... Poly(2-(6 -cyano-6 -incthyl-licplyloxy)-l,4-phcnylene), m-LPPP... methyl-substituted ladder-type Poly( 1,4-phenylcne), and PLQY=phololuinincs-ecncc quanluni yield.

While there is much to discuss about order in films of different conjugated molecules, a comprehensive survey of the structural properties of various conjugated polymers can be found in Ref. [9]. This section focuses on the relation between microscopic order and macroscopic properties, and on structure-property relations. 

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-... 

Additional chemical stability can be given to PPVs by substitution at the vinyl-ene carbons. Thus, CN-PPV and PPV-DP are more stable than their parent polymers [173]. Carter et al. [172] showed that a random copolymer of PPV containing non-conjugated segments is considerably more stable to photooxidation than the fully conjugated polymer. Of course, the electrical and optical properties are also altered by these substitutions. 

Several attempts to use otganic polymeric semiconductors as the active component in photovoltaic devices have been reported during the last two decades. Interest in the photovoltaic properties of conjugated polymers like polyacelylcne, various derivatives of polythiophenes and poly(para-phenylene vinylene)s arose from... 

At this point it might be appropriate to comment on the conflicting requirements of the synthesis. The large interest which other conjugated polymers such as polypyrrole, polyanilinc or poly(parattracted originates, firstly, from their attractive physical properties, but also from the sim-... 

D. Baeriswyl in Electronic Properties of Conjugated Polymers III (Eds. H. Kuzmany, M. Mcli-ring. S. Roth). Springer. Beilin. 1989. p. 54. 

The proposed scenario is mainly based on the molecular approach, which considers conjugated polymer films as an ensemble of short (molecular) segments. The main point in the model is that the nature of the electronic state is molecular, i.e. described by localized wavefunctions and discrete energy levels. In spite of the success of this model, in which disorder plays a fundamental role, the description of the basic intrachain properties remains unsatisfactory. The nature of the lowest excited state in m-LPPP is still elusive. Extrinsic dissociation mechanisms (such as charge transfer at accepting impurities) are not clearly distinguished from intrinsic ones, and the question of intrachain versus interchain charge separation is not yet answered. 

In general. Figure 9-2 b to c show strategies to make conjugated polymers more proeessible but it must be noted that the different synthetic approaches do not only result in different degrees of (a) chemical purity but also alter (b) the physical properties due lo intrinsic differences. Compared to a pure conjugated... 

The flexibility of the substrate, the ease, and the low costs of fabrication of this DFB-polynter laser offer a very promising way to novel surface-emitting laser devices which take full advantage of the properties of conjugated polymers. 

The rest of this chapter will focus primarily on results using the soluble PPV-based polymer MEH-PPV. The results obtained for MEH-PPV are typical of the conjugated polymers used in LEDs. The models and results presented are generally applicable. They describe the operation of a wide range of polymer LEDs if the appropriate polymer film properties arc used. 

Conjugated polymers, including optically active polymers and dendronized polymers that are very useful in electrical and optical fields and asymmetric catalysis, will continue to attract interest from chemists and materials scientists. It is well anticipated that more and more polymers with interesting structures and properties will be synthesized from the transition metal coupling strategy. 

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