Conjugated doping

Polyquinolines are good electrical insulators as indicated by conductivity values in the order of 10 15 —10 12 S/cm (101). However, by virtue of their extended conjugation, doped, wholly aromatic polyquinolines offer potential for high conductivity. Rigid polyquinolines display highest values of conductivity, generally on the order of 8—11 S/cm. 

Optical applications that have been considered do not require the presence of free electrons, only that of extended conjugation doping is unnecessary. Several CPs, particularly the PDAs, have very large third-order susceptibilities x(3) their nonlinear optical properties are currently under active study, and operation of simple devices has been demonstrated, but we are far from being able to consider actual technical developments. 

It was recently shown that doping poly(pPIN) with iodine produces a semi-conductive material, with conductivities of about 8 X 10 S cm typical of non-conjugated doped polymers [99]. This material also showed a large quadratic electro-optic effect which would make it useful for non-linear optics applications [100]. 

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. 

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. 

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... 

Recently, polyimines include the synthesis of long alkoxy (Cg-Cig) side chain derivatives [188,189], which are presumably soluble to some extent in organic solvents and derivatives containing fluorene cardo unit [190]. Trifluoromethyl groups [191] in the polymer backbone provide solubility in organic solvents. Studies of the electrical conductivity of doped conjugated aromatic polyimines and alkoxy derivatives have been reported [188], and the values are in the range of 10 to 10 S/ cm. 

Polyacetylene is considered to be the prototypical low band-gap polymer, but its potential uses in device applications have been hampered by its sensitivity to both oxygen and moisture in its pristine and doped states. Poly(thienylene vinylene) 2 has been extensively studied because it shares many of the useful attributes of polyacetylene but shows considerably improved environmental stability. The low band gap of PTV and its derivatives lends itself to potential applications in both its pristine and highly conductive doped state. Furthermore, the vinylene spacers between thiophene units allow substitution on the thiophene ring without disrupting the conjugation along the polymer backbone. 

There have been very few examples of PTV derivatives substituted at the vinylene position. One example poly(2,5-thienylene-1,2-dimethoxy-ethenylene) 102 has been documented by Geise and co-workers and its synthesis is outlined in Scheme 1-32 [133]. Thiophene-2,5-dicarboxaldehyde 99 is polymerized using a benzoin condensation the polyacyloin precursor 100 was treated with base to obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102, which is soluble in solvents such as chloroform, methanol, and DMF. The molar mass of the polymer obtained is rather low (M = 1010) and its band gap ( ,.=2.13 eV) is substantially blue-shifted relative to PTV itself. Despite the low effective conjugation, the material is reasonably conductive when doped with l2 (cr=0.4 S cm 1). 

The systems discussed in this chapter give some examples using different theoretical models for the interpretation of, primarily, UPS valence band data, both for pristine and doped systems as well as for the initial stages of interface formation between metals and conjugated systems. Among the various methods used in the examples are the following semiempirical Hartree-Fock methods such as the Modified Neglect of Diatomic Overlap (MNDO) [31, 32) and Austin Model 1 (AMI) [33] the non-empirical Valence Effective Hamiltonian (VEH) pseudopotential method [3, 34J and ab initio Hartree-Fock techniques. 

The other way to produce EL devices is based on a pin junction [47]. A pin junction with conjugated polymers was realized by electrochemical doping of the... 

One idea to realize a pin junction with conjugated polymers is to create it in situ by electrochemical doping. By using the conjugated polymer in a solid slate electrochemical cell, the production of bipolar light-emitting pin junction devices can be realized [69, 70]. 

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-... 

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