Electron-transporting films

Responses of Electron-Transporting Films, Including Hydroxylated Island Overlayers... 

A compound which is a good choice for an artificial electron relay is one which can reach the reduced FADH2 active site, undergo fast electron transfer, and then transport the electrons to the electrodes as rapidly as possible. Electron-transport rate studies have been done for an enzyme electrode for glucose (G) using interdigitated array electrodes (41). The following mechanism for redox reactions in osmium polymer—GOD biosensor films has... 

The huge literature on the electronic conductivity of dry conducting polymer samples will not be considered here because it has limited relevance to their electrochemistry. On the other hand, in situ methods, in which the polymer is immersed in an electrolyte solution under potential control, provide valuable insights into electron transport during electrochemical processes. It should be noted that in situ and dry conductivities of conducting polymers are not directly comparable, since concentration polarization can reduce the conductivity of electrolyte-wetted films considerably.139 Thus in situ conductivities reported for polypyrrole,140,141 poly thiophene,37 and poly aniline37 are orders of magnitude lower than dry conductivities.15... 

In situ electron transport measurements on conducting polymers are commonly made by using a pair of parallel-band electrodes bridged by the polymer [Fig. 9(A)].141142 Other dual-electrode techniques in which the polymer film is sandwiched between two electrodes [Fig. 9(B)],139,140 rotating-disk voltammetry [Fig. 9(C)],60,143 impedance spectroscopy,144,145 chronoamperometry,146 and chronopotentiometry147 have also been used. 

Figure 9. Schematic diagrams of (A) parallel-band electrode,141 142 (B) sandwiched electrode,139 140 and (C) rotating-disk voltammetry60 143 methods for making in situ electron transport measurements on polymer films.

It was reabzed early on that because of their high electron transport rates, the charging rates of conducting polymer films would be controlled predominantly by the rate at which charge-compensating ions [Eq.(l)] could be extracted from, or ejected into, the bathing electrolyte solution.160,161 However, these and some other studies employing chronoam-... 

Theoretical aspects of mediation and electrocatalysis by polymer-coated electrodes have most recently been reviewed by Lyons.12 In order for electrochemistry of the solution species (substrate) to occur, it must either diffuse through the polymer film to the underlying electrode, or there must be some mechanism for electron transport across the film (Fig. 20). Depending on the relative rates of these processes, the mediated reaction can occur at the polymer/electrode interface (a), at the poly-mer/solution interface (b), or in a zone within the polymer film (c). The equations governing the reaction depend on its location,12 which is therefore an important issue. Studies of mediation also provide information on the rate and mechanism of electron transport in the film, and on its permeability. 

If the film is nonconductive, the ion must diffuse to the electrode surface before it can be oxidized or reduced, or electrons must diffuse (hop) through the film by self-exchange, as in regular ionomer-modified electrodes.9 Cyclic voltammograms have the characteristic shape for diffusion control, and peak currents are proportional to the square root of the scan speed, as seen for species in solution. This is illustrated in Fig. 21 (A) for [Fe(CN)6]3 /4 in polypyrrole with a pyridinium substituent at the 1-position.243 This N-substituted polypyrrole does not become conductive until potentials significantly above the formal potential of the [Fe(CN)6]3"/4 couple. In contrast, a similar polymer with a pyridinium substituent at the 3-position is conductive at this potential. The polymer can therefore mediate electron transport to and from the immobilized ions, and their voltammetry becomes characteristic of thin-layer electrochemistry [Fig. 21(B)], with sharp symmetrical peaks that increase linearly with increasing scan speed. 

Electron Transport in and Electrocatalysis with Polymeric Films of Metallotetraphenylporphyrins... 

The above mechanistic aspect of electron transport in electroactive polymer films has been an active and chemically rich research topic (13-18) in polymer coated electrodes. We have called (19) the process "redox conduction", since it is a non-ohmic form of electrical conductivity that is intrinsically different from that in metals or semiconductors. Some of the special characteristics of redox conductivity are non-linear current-voltage relations and a narrow band of conductivity centered around electrode potentials that yield the necessary mixture of oxidized and reduced states of the redox sites in the polymer (mixed valent form). Electron hopping in redox conductivity is obviously also peculiar to polymers whose sites comprise spatially localized electronic states. 

The discovery of the use of A1Q3 as an electron-transport-emitting layer is undoubtedly the most significant achievement in the research that led to the development of stable OLEDs.180,181 It is very stable and can be sublimed without decomposition at 350 °C,188 and its thin-film PL quantum efficiency at room temperature is about 32%, independent of film thickness between 10 nm and 1,350 nm.189... 

A typical multilayer thin film OLED is made up of several active layers sandwiched between a cathode (often Mg/Ag) and an indium-doped tin oxide (ITO) glass anode. The cathode is covered by the electron transport layer which may be A1Q3. An emitting layer, doped with a fluorescent dye (which can be A1Q3 itself or some other coordination compound), is added, followed by the hole transport layer which is typically a-napthylphenylbiphenyl amine. An additional layer, copper phthalocyanine is often inserted between the hole transport layer and the ITO electrode to facilitate hole injection. 

Regarding the question of the rate of electron transport through polymer films, it is not yet clear what ultimate rate can be achieved. In solar energy applications the important issue is whether the rate can be high enough so that the net electron transfer rate is light intensity limited. 

Holmlin RE, Haag R, Chabinyc ML, Ismagilov RF, Cohen AE, Terfort A, Rampi MA, Whitesides GM (2001) Electron transport through thin organic films in metal-insulator-metal junctions based on self-assembled monolayers. J Am Chem Soc 123 5075-5085... 

Holmlin RE, Ismagilov RF, Haag R, Mujica V, Ratner MA, Rampi MA, Whitesides GM (2001) Correlating electron transport and molecular structure in organic thin films. Angew Chem Int Ed 40 2316-2320... 

In the early 1970s, Spear and coworkers (Spear, 1974 Le Comber et al., 1974), although unaware of the presence of hydrogen, demonstrated a substantial reduction in the density of gap states (with a corresponding improvement in the electronic transport properties) in amorphous silicon films that were deposited from the decomposition of silane (SiH4) in an rf glow discharge. 

---