Chemical conjugated polymers

Polyheterocycles. Heterocychc monomers such as pyrrole and thiophene form hiUy conjugated polymers (4) with the potential for doped conductivity when polymerization occurs in the 2, 5 positions as shown in equation 6. The heterocycle monomers can be polymerized by an oxidative coupling mechanism, which can be initiated by either chemical or electrochemical means. Similar methods have been used to synthesize poly(p-phenylenes). 

These conjugated polymers can be chemically and electrochemically reduced and reoxidized in a reversible manner. In all cases the charges on the polymer backbone must be compensated by ions from the reaction medium which are then incorporated into the polymer lattice. The rate of the doping process is dependent on the mobiHty of these charge compensating ions into and out of the polymer matrix. 

The rigid chemical structure of a conjugated polymer helps in the movement of electrons. That stiff structure, however, has limited its use. They are like uncooked spaghetti and do not easily entangle themselves. Polymer chain entanglements are necessary to achieve high viscosities, which are required to create fibers out of these polymers. 

Table 13-1. Chemical structures of representative luminescent conjugated polymers.

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. 

Figure 15-29. Chemical structures of the conjugated polymers used in the device and the device structure of the laminated solar cell. For the top half of the device, A1 or Ca was evaporated on glass substrates, and the acceptor material MEH-CN-PPV (and a small amount of POPT, usually 5%) was spin coaled. The half with the POPT (and a small amount of MEH-CN-PPV, usually 5%) was spin coaled on 1TO substrates and heated to 200"C under vacuum belore the device was laminated together by applying a light pressure.

The PES measurements arc performed with reference to the Fermi level of the photoclectron spectrometer, in solid specimens, as dealt with here, by the way the spectroscopy works. Thus, in cases when the Fermi level shifts due to some chemical modifications of the sample, i.e., in the intercalation of graphite or other layered compound [16] or in the doping of conjugated polymers 1171, il is necessary to account for the change in the Fermi energy level before interpreting spec-... 

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... 

In recent years further concepts have been developed for the construction of polymer-based diodes, requiring either two conjugated polymers (PA and poly(A-methyl-pyrrole) 2 > or poly(A-methylpyrrole in a p-type silicon wafer solid-state field-effect transistor By modifying the transistor switching, these electronic devices can also be employed as pH-sensitive chemical sensors or as hydrogen or oxygen sensors 221) in aqueous solutions. Recently a PPy alcohol sensor has also been reported 222). 

Preliminary measurements of electrical conductivity of the conjugated derivatives of PBTAB, PBTB and PTTB obtained by the above treatment with bromine vapor are poor semiconductors with a conductivity of the order 10 °S/cm which apparently is not due to doping. Subsequent electrochemical or chemical doping of these polymers lead to 4-6 orders of magnitude increase in conductivity. Ongoing studies of the electrical properties of these conjugated polymers with alternating aromatic/quinonoid units will be reported elsewhere. 

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