Dopant transport

The emphasis changes in Electroactive Polymer Electrochemistry, Part 2 Methods and Applications, where methodology and applications is addressed. The volume begins (Chapter 5) with a contribution by Morton-Blake and Corish. These contributors have been very active in the area of atomistic simulation of matter transport phenomena in solid materials. In the present contribution they describe in a lucid manner the results of their recent work in applying the methodology of atomistic simulation to quantify dopant transport processes in electroactive polymers. The idea of simulation is continued in Chapter 6, where Cassidy carefully describes the application of digital simulation protocols to charge transport in... 

FIGURE 1.16. (a) Kinetic case diagrams for dopant transport and reaction in electronically conducting polymer films according to the Bartlett-Gardner model. Thick lines separate different approximate solutions to the transport/kinetic problem. Six distinct cases are noted, (b) Computed concentration profiles u x) and site occupancy functions 0 for each of the six cases, (c) Schematic representation of the moving boundary problem (Case 6). 

This case has also been considered by Kim and coworkers/ who derived a nonlinear partial differential equation of a form similar to that outlined in Eqn. 101. The problem was also considered by Hermans many years ago. The method of solution proposed by Bartlett and Gardner is perhaps the most comprehensive suggested to date, and it is based on the Neumann analysis of the phase transformation problem in a semiinfinite diffusion space described in the classic text written by Carlsaw and Jaeger. The reader is referred to the original paper for full details of the analysis. We note therefore that the process of dopant transport and reaction in a polymer matrix can be complex. 

In solid state materials, single-step electron transport between dopant species is well known. For example, electron-hole recombination accounts for luminescence in some materials [H]. Multistep hopping is also well known. Models for single and multistep transport are enjoying renewed interest in tlie context of DNA electron transfer [12, 13, 14 and 15]. Indeed, tliere are strong links between tire ET literature and tire literature of hopping conductivity in polymers [16]. 

In moleculady doped polymers, charge transport is carried out by the hole-transporting molecular dopants, usually aromatic amines. The polymer merely acts as a binder. The hole mobiUty is sensitive to the dopant concentrations. For example, the hole mobiUty of... 

At very high dopant concentrations, transport occurs direcdy between the dopant molecules. The polymer acts only as a binder in most cases. Taking TPD-doped PVK as an example, at low TPD concentrations the hole mobihty first decreases from 3 x 10 cm /Vs to 10 cm /Vs with increasing TPD concentration, because TPD molecules act as hole traps (48,49). At higher TPD concentrations, new direct transport channels between the TPD molecules open up and the hole mobihty increases to lO " cm /Vs for ca 60% TPD doping (Table 1, entries 9—11) (48,49). In this case, there is no evidence for unusual interaction between TPD and PVK that affects the hole transport process. 

Semiconducting Ceramics. Most oxide semiconductors are either doped to create extrinsic defects or annealed under conditions in which they become non stoichiometric. Although the resulting defects have been carefully studied in many oxides, the precise nature of the conduction is not well understood. Mobihty values associated with the various charge transport mechanisms are often low and difficult to measure. In consequence, reported conductivities are often at variance because the effects of variable impurities and past thermal history may overwhelm the dopant effects. 

Electrochemical polymeriza tion of heterocycles is useful in the preparation of conducting composite materials. One technique employed involves the electro-polymerization of pyrrole into a swollen polymer previously deposited on the electrode surface (148—153). This method allows variation of the physical properties of the material by control of the amount of conducting polymer incorporated into the matrix film. If the matrix polymer is an ionomer such as Nation (154—158) it contributes the dopant ion for the oxidized conducting polymer and acts as an effective medium for ion transport during electrochemical switching of the material. 

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. 

Fluorescent small molecules are used as dopants in either electron- or hole-transporting binders. These emitters are selected for their high photoluminescent quantum efficiency and for the color of their emission. Typical examples include perylene and its derivatives 44], quinacridones [45, penlaphenylcyclopenlcne [46], dicyanomethylene pyrans [47, 48], and rubrene [3(3, 49]. The emissive dopant is chosen to have a lower excited state energy than the host, such that if an exciton forms on a host molecule it will spontaneously transfer to the dopant. Relatively small concentrations of dopant are used, typically in the order of 1%, in order to avoid concentration quenching of their luminescence. 

Trilayer structures offer the additional possibility of selecting the emissive material, independent of its transport properties. In the case of small molecules, the emitter is typically added as a dopant in either the HTL or the ETL, near the interface between them, and preferably on the side where recombination occurs (see Fig. 13-1 c). The dopant is selected to have an cxciton energy less than that of its host, and a high luminescent yield. Its concentration is optimized to ensure exciton capture, while minimizing concentration quenching. As before, the details of recombination and emission depend on the energetics of all the materials. The dopant may act as an electron or hole trap, or both, in its host. Titus, for example, an electron trap in the ETL will capture and hold an election until a hole is injected nearby from the HTL. In this case, the dopant is the recombination mmo.-... 

SCHEME 3.1 Chemical structures of anthracene, a hole transport triarylamine, an electron transport and a green emitter Alq3, and a phosphorescent dopant PtOEP. 

A higher efficiency, yet simpler structure PPLED device fabricated with the same dopant and host materials was almost simultaneously reported by Yang and Tsutsui [35]. The highest EQE of their device ITO/PVK 5%Ir(ppy)3 /OXD-7/Mg Ag (where ITO is indium tin oxide) (using OXD-7 (7) as an electron-transporting layer (ETL), Chart 4.3) reached the value of 7.5%, which was the first reported PLED with external efficiency above 5%, an upper limit of the fluorescent PLEDs. The power efficiency was 5.8 lm/W at the luminance of 106 cd/m2. 

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