Doping trapping effect

The activation energy for oxide ion conduction in the various zirconia-, thoria- and ceria-based materials is usually at least 0.8 eV. A significant fraction of this is due to the association of oxide vacancies and aliovalent dopants (ion trapping effects). Calculations have shown that the association enthalpy can be reduced and hence the conductivity optimised, when the ionic radius of the aliovalent substituting ion matches that of the host ion. A good example of this effect is seen in Gd-doped ceria in which Gd is the optimum size to substitute for Ce these materials are amongst the best oxide ion conductors. Fig. 2.11. 

From these experiments the effects of doping on radiolysis are explained in terms of the trapping effects of anion vacancies. That is, electrons and holes created by the radiation have a smaller recombination probability if the concentration of anion vacancies (electron traps) is high. Assuming the rate of decomposition is proportional to the concentration of neutral azide ions, via... 

The picture presented above for confinement of the excitons within the device is for the EM layer sandwiched between the HTL and ETL. The EM need not be a discrete layer in the OLED, however, for exciton confinement to occur. Alternatively, the EM can consist of a luminescent molecule doped (- 1%) into a polymeric or molecular host material (40,41,54,55). So long as the energy gap (or band gap) of the host is higher than that of the EM dopant, excitons will be effectively trapped or confined on the dopant molecules leading to improved EL efficiency. An example of such a dopant-based device... 

Using a stable dopant as the emissive dye has been shown to greatly enhance the lifetime of small molecule LEDs. Rubrene doped into the Alq, electron transport layer ] 184] or into the TPD hole transport layer 1185] can extend the lifetime by an order of magnitude. Similarly, dimclhylquinacridone in Alq has a beneficial effect ]45 ]. The likely mechanism responsible for this phenomenon is that the dopant acts as a trap for the excilon and/or the charge. Thus, molecules of the host maLrix are in their excited (cationic, anionic or cxcitonic) states for a smaller fraction of the time, and therefore have lower probability to undergo chemistry. 

---