Comprehensive Approach to Intrinsic Charge Carrier Mobility in Conjugated Organic Molecules, Macromolecules, and Supramolecular Architectures

Si-based inorganic electronics have long dominated the semiconductor industry. However, in recent years conjugated polymers have attracted increasing attention because such systems are flexible and offer the potential for low-cost, large-area production via roll-to-roll processing. The state-of-the-art organic conjugated molecular crystals can exhibit charge carrier mobilities (mu) that nearly match or even exceed that of amorphous silicon (1-10 cm(2) V-1 s(-1)). The mean free path of the charge carriers estimated from these mobilities corresponds to the typical intersite (intermolecular) hopping distances in conjugated organic materials, which strongly suggests that the conduction model for the electronic band structure only applies to mu > 1 cm(2) V-1 s(-1) for the translational motion of the charge carriers. However, to analyze the transport mechanism in organic electronics, researchers conventionally use a disorder formalism, where mu is usually less than 1 cm(2) V-1 s(-1) and dominated by impurities, disorders, or defects that disturb the long-range translational motion. In this Account, we discuss the relationship between the alternating-current and direct-current mobilities of charge carriers, using time-resolved microwave conductivity (TRMC) and other techniques including field-effect transistor, time-of-flight, and space-charge limited current. TRMC measures the nanometer-scale mobility of charge carriers under an oscillating microwave electric field with no contact between the semiconductors and the metals. This separation allows us to evaluate the intrinsic charge carrier mobility with minimal trapping effects. We review a wide variety of organic electronics in terms of their charge carrier mobilities, and we describe recent studies of macromolecules, molecular crystals, and supramolecular architecture. For example, a rigid poly(phenylene-co-ethynylene) included in permethylated cyclodextrin shows a high intramolecular hole mobility of 0.5 cm(2) V-1 s(-1), based on a combination of flash-photolysis TRMC and transient absorption spectroscopy (TAS) measurements. Single-crystal rubrene showed an ambipolarity with an isotropic charge carrier transport along each crystal axis on the nanometer scale. Finally, we describe the charge carrier mobility of a self-assembled nanotube consisting of a large pi-plane of hexabenzocoronene (HBC) partially appended with an electron acceptor. The local (intratubular) charge carrier mobility reached 3 cm(2) V-1 s(-1) for the nanotubes that possessed well-ordered pi-stacking, but it dropped to 0.7 cm(2) V-1 s(-1) in regions that contained greater amounts of the electron acceptor because those molecules reduced the structural integrity of pi-stacked HBC arrays. Interestingly, the long-range (intertubular) charge carrier mobility was on the order of 10(-4) cm(2) V-1 s(-1) and monotonically decreased when the acceptor content was increased. These results suggest the importance of investigating charge carrier mobilities by frequency-dependent charge carrier motion for the development of more efficient organic electronic devices.