Transport polarons

CHARGED SPECIES AND THEIR TRANSPORT POLARONS AND BIPOLARONS... 

Because polarons are localized species, their natural transport mechanism is hopping. We shall now briefly describe the small polaron model, as developed by Holstein and Emin [26, 29, 46]. 

At very low temperatures, Holstein predicted that the small polaron would move in delocalized levels, the so-called small polaron band. In that case, mobility is expected to increase when temperature decreases. The transition between the hopping and band regimes would occur at a critical temperature T, 0.40. We note, however, that the polaron bandwidth is predicted to be very narrow ( IO Viojo, or lO 4 eV for a typical phonon frequency of 1000 cm-1). It is therefore expected that this band transport mechanism would be easily disturbed by crystal defects. 

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. 

The charge transport in a conjugated chain and the interchain hopping is explained in terms of conjugation defects (radical or ionic sites), called solitons and polarons. Several possible conjugation defects are demonstrated in Fig. 5.33 on the example of trans-polyacetylene. 

The electronic band structure of a neutral polyacetylene is characterized by an empty band gap, like in other intrinsic semiconductors. Defect sites (solitons, polarons, bipolarons) can be regarded as electronic states within the band gap. The conduction in low-doped poly acetylene is attributed mainly to the transport of solitons within and between chains, as described by the intersoliton-hopping model (IHM) . Polarons and bipolarons are important charge carriers at higher doping levels and with polymers other than polyacetylene. 

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. 

The Mechanism of Long-Distance Radical Cation Transport in Duplex DNA Ion-Gated Hopping of Polaron-Like Distortions... 

Keywords Long-distance charge transport DNA damage Polaron hopping Ion gated base sequence effects... 

Hopping Models Hole-Resting-Site and Phonon-Assisted Polaron Transport... 

Schuster GB, Landman U (2004) The Mechanism of Long-Distance Radical Cation Transport in Duplex DNA Ion-Gated Hopping of Polaron-Like Distortions. 236-. 139-161 Schwarz H, see Schroder D (2003) 225 129-148... 

Many other time parameters actually enter - if the molecule is conducting through a polaron type mechanism (that is, if the gap has become small enough that polarization changes in geometry actually occur as the electron is transmitted), then one worries about the time associated with polaron formation and polaron transport. Other times that could enter would include frequencies of excitation, if photo processes are being thought of, and various times associated with polaron theory. This is a poorly developed part of the area of molecular transport, but one that is conceptually important. 

Once the electrons and holes have been injected, they migrate into ETL and HTL to form excited states referred to as polarons by physicists or radical ions by chemists. These polarons or radical ions move, by means of a so-called charge-hopping mechanism, through the electron and hole transport materials (ETMs and HTMs), which typically possess good charge mobility properties, and eventually into the EML. 

However, one should be cautious about overinterpreting the field and temperature dependence of the mobility obtained from ToF measurements. For instance, in the analyses of the data in [86, 87], ToF signals have been considered that are dispersive. It is well known that data collected under dispersive transport conditions carry a weaker temperature dependence because the charge carriers have not yet reached quasi-equilibrium. This contributes to an apparent Arrhenius-type temperature dependence of p that might erroneously be accounted for by polaron effects. 

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