Doping in polymers

D.B. Romero, M.Z. Schaer, B. Cesar, and B. Francois, Effects of doping in polymer light-emitting diodes, Appl. Phys. Lett., 67 1659-1661 (1995). 

Sensors based on the above reaction scheme have been developed for Al3+, Zn2+, Cu2+, Ca2+, Pb2+, Hg2"1", K+, Li+, etc. A polycation, protamine sensor has also been developed using 2/7/-dichlorofluorescein octadecyl ester (DCFOE) doped in polymer membranes. However, most of these sensors are pH dependent due to the pH dependence of the cation complexation reactions. The cation ion indicators can be immobilized on any solid support, such as silica, cellulose, ion-exchange resin, porous glass, sol-gel, or entrapped in polymer membranes. 

Fig. 20a.9. Response curve for calcium(II) of a calcium-organophosphate and dichlorofluorescein octadecyl ester doped in polymer films at pH 7.4. For more details see Ref. [49],...

The fourth type of mediator-based cation optical sensing is using potential sensitive dye and a cation selective ionophore doped in polymer membrane. Strong fluorophores, e.g. Rhodamine-B C-18 ester exhibits differences in fluorescence intensity because of the concentration redistribution in membranes. PVC membranes doped with a potassium ionophore, can selectively extract potassium into the membrane, and therefore produce a potential at the membrane/solu-tion interface. This potential will cause the fluorescent dye to redistribute within the membrane and therefore changes its fluorescence intensity. Here, the ionophore and the fluorescence have no interaction, therefore it can be applied to develop other cation sensors with a selective neutral ionophore. 

A certain kind of active carbon is an excellent support of HPAs to make HPAs insoluble [95]. It has been reported that proton transfer from HPAs to the carbon support tightens the binding [96], High activity was reported for HPAs supported on ion-exchangcd resin [97] and HPAs doped in polymers [98, 99]. 

The changes of microenvironments around the doped dye molecules have a strong correlation with the characters of matrix polymers such as steric hindrance for segmental motion, amount of free volume, and interchain hydrogen bonds. By the PHB measurements, we can detect both slight and large environmental change around the dyes doped in polymers at low temperatures. The PHB spectroscopy is expected to be extended to other polymer systems to study low-temperature relaxation properties of them. 

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 first use of ionic liquids in free radical addition polymerization was as an extension to the doping of polymers with simple electrolytes for the preparation of ion-conducting polymers. Several groups have prepared polymers suitable for doping with ambient-temperature ionic liquids, with the aim of producing polymer electrolytes of high ionic conductance. Many of the prepared polymers are related to the ionic liquids employed for example, poly(l-butyl-4-vinylpyridinium bromide) and poly(l-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide [38 1]. 

Pseudocapacitance is used to describe electrical storage devices that have capacitor-like characteristics but that are based on redox (reduction and oxidation) reactions. Examples of pseudocapacitance are the overlapping redox reactions observed with metal oxides (e.g., RuO,) and the p- and n-dopings of polymer electrodes that occur at different voltages (e.g. polythiophene). Devices based on these charge storage mechanisms are included in electrochemical capacitors because of their energy and power profiles. 

Hie electrochemical characteristics of overoxidation vary widely among polymers, solvents, and nucleophiles.129 Its rate depends on the degree of oxidation of the polymer (and therefore on the potential applied), and the concentration127 and reactivity of the nucleophile. Polypyrroles usually become overoxidized at lower potentials than polythiophenes because of their lower formal potentials for p-doping. In acetonitrile, the reactivity of the halides follows their nucleophilicity in aprotic solvents,... 

In principle, such propositions resemble the bipolaron model, which presents the physicist s view of the electronic properties of doped conducting polymers 53-159) The model was originally constructed to characterize defects in solids. In chemical terminology, bipolarons are equivalent to diionic spinfree states of a system (S = 0)... 

FIGURE 26.6 (a) p-doped conductive polymer in battery cell configuration (b) -doped... 

Laser ablation of polymer films has been extensively investigated, both for application to their surface modification and thin-film deposition and for elucidation of the mechanism [15]. Dopant-induced laser ablation of polymer films has also been investigated [16]. In this technique ablation is induced by excitation not of the target polymer film itself but of a small amount of the photosensitizer doped in the polymer film. When dye molecules are doped site-selectively into the nanoscale microdomain structures of diblock copolymer films, dopant-induced laser ablation is expected to create a change in the morphology of nanoscale structures on the polymer surface. 

As aforementioned, diblock copolymer films have a wide variety of nanosized microphase separation structures such as spheres, cylinders, and lamellae. As described in the above subsection, photofunctional chromophores were able to be doped site-selectively into the nanoscale microdomain structures of the diblock copolymer films, resulting in nanoscale surface morphological change of the doped films. The further modification of the nanostructures is useful for obtaining new functional materials. Hence, in order to create further surface morphological change of the nanoscale microdomain structures, dopant-induced laser ablation is applied to the site-selectively doped diblock polymer films. 

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