Polarons positive

Figure 3.5 Schematic of polaron (positive) and polarization effects after hole injection, (a) The hole is in the bulk, (b) The hole is nearthe interface between the gate insulator and organic semiconductor in OFET (see Figure 3.1). When the area of polarization is in (beyond) the unit...

Figure 8-16. A picture of the pholoexcilalion scenario in m-LPPP, see text for a discussion. Pv is a positively charged chain (polaron), while X- can be either a negatively charged chain or an electron acceptor, such as oxygen.

Figure 9-21. EL process in PLEDs. VB... valence band LB. ..conducting band V... potential M,M2... Mclal electrodes, U... bias voltage Z X2 —Interface luyers tK...bandgap P and Pr... positive and negative polarons /. Fermi energy, and 0... work I unclion.

The electrical conductivity in the solid state is determined by the product of the carrier concentration and the carrier mobility. In conjugated polymers both entities are material dependent and, i.e., are different for electrons and holes. Electrons or holes placed on a conjugated polymer lead to a relaxation of the surrounding lattice, forming so-called polarons which can be positive or negative. Therefore, the conductivity, o, is the sum of both the conductivity of positive (P+) and negative polarons (P ) ... 

The efficient formation of singlet excitons from the positive and negative charge carriers, which are injected via the metallic contacts and transported as positive and negative polarons (P+ and P ) in the layer, and the efficient radiative recombination of these singlet excitons formed are crucial processes for the function of efficient electroluminescence devices. 

Later we will describe both oxidation and reduction processes that are in agreement with the electrochemically stimulated conformational relaxation (ESCR) model presented at the end of the chapter. In a neutral state, most of the conducting polymers are an amorphous cross-linked network (Fig. 3). The linear chains between cross-linking points have strong van der Waals intrachain and interchain interactions, giving a compact solid [Fig. 14(a)]. By oxidation of the neutral chains, electrons are extracted from the chains. At the polymer/solution interface, positive radical cations (polarons) accumulate along the polymeric chains. The same density of counter-ions accumulates on the solution side. 

This almost distance independent hole transfer over (A T)n sequences where adenines are charge carriers is very surprising. Maybe the transfer of a positive charge between adenines of an (A T)n sequence is extremely fast, as recent calculations of M.D. Sevilla predicted [20], One could also speculate that the positive charge is delocalized over more than one A T base pair so that polaron hopping, which is discussed in this volume by G.B. Schuster as well as E.N. Conwell, might make the hole transport in oxidized (A T)n sequences very efficient. 

Fig. 4. Energy level diagrams showing possible electronic configurations for positively-charged polaron (a) and bipolaron (b) defects and (c) a schematic bipolaron band model. The negatively-charged polaron would carry three electrons and the bipolaron four. Also shown is the neutral polaron-exciton (d) which would decay to restore the chain structure.

The realization of the polaronic nature of polyene radical cations leads naturally to the question, to what extent the pronounced relaxation of polyenes upon ionization affects their excited-state energies. Such changes can be assessed by comparing the ionization energy differences I) —I] obtained from PE spectra with the positions of the band maxima in the radical cation s EA spectra which measure the same quantities at the radical cation... 

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