We report structural and electrical transport properties of a family of π-stacking soluble organic semiconductors, N,N‘-dialkyl-3,4,9,10-perylene tetracarboxylic diimides (alkyl − pentyl [1], octyl [2], and dodecyl [3]). The structures of evaporated polycrystalline films of 1−3 were studied using X-ray diffraction and atomic force microscopy. Films of 1−3 pack similarly with the direction of π−π overlap in the substrate plane. Organic thin film transistors (OTFTs) based on 1−3 deposited on SiO2 gate dielectric showed linear regime electron mobilities of 0.1, 0.6, and 0.2 cm2/(V s), respectively, corrected for contact resistance. OTFTs of 2 had saturation electron mobilities as high as 1.7 cm2/(V s) with on-to-off current ratios of 107. Variable temperature measurements were used to examine the charge transport kinetics in the range 80−300 K and revealed (1) thermally activated electron mobilities with activation energies dependent on gate voltage and (2) the presence of well-defined isokinetic points, i.e., temperatures at which Arrhenius plots at different gate voltages intersect for a given film. Isokinetic points indicate a common charge transport mechanism and can be explained in terms of the multiple trapping and release (MTR) transport model. MTR assumes trap-limited band transport, and quantum chemical calculations were used to verify that delocalized transport is likely in 1−3; a conduction bandwidth of 0.58 eV was calculated for 1. Using MTR, the trap concentrations were estimated to be ∼1012 cm-2 for deep traps, and ∼6 × 1013 cm-2 for shallow traps. However, a nonmonotonic dependence of the electron mobility on gate voltage was also observed, which is not predicted by MTR and suggests that the transport mechanism is more complicated, perhaps due to the discrete layered structure of these materials. The high values for the electron mobility and on-to-off current ratio suggest that substituted perylene diimides represent a promising class of n-channel conductors for OTFTs.

We report structural and electrical properties in thin films of an n-channel organic semiconductor, N,N′-dipentyl-3,4,9,10-perylene tetracarboxylic dimide (PTCDI–C5). The structure of polycrystalline thin films of PTCDI–C5 was studied using x-ray diffraction and atomic force microscopy. Films order with single crystal-like packing, and the direction of π-π overlap is in the substrate plane. Organic thin film transistors (OTFTs) based on PTCDI–C5 were fabricated on hydrophobic and hydrophilic substrates. OTFTs showed effective mobility as high as 0.1 cm2/V s. Contact resistance of operating OTFTs was studied using resistance versus length plots and a four-probe method for three different contact metals (Au, Ag, Ca). Typical OTFTs had a specific contact resistance of 8×104 Ω cm at high gate voltage. There was no dependence of contact resistance with contact metal. Variable temperature measurements revealed that film resistance in the OTFT was activated in the temperature range 100–300 K, with typical activation energies of 60–80 meV. Contact resistance showed similar activated behavior, implying that the Schottky barrier at the contact is not the limiting resistance for the contact. Film resistance data showed a Meyer–Neldel relationship with characteristic energy EMN=20–25 meV, for various samples. The common TFT instability of threshold voltage shift (TVS) was observed in PTCDI–C5 OTFTs. A model is proposed to explain positive TVS in gate bias stress and oxygen exposure experiments. The model is based on the formation of a metastable complex between PTCDI–C5 and oxygen, which creates a deep acceptor-like trap state.

We describe variable temperature contact resistance measurements on pentacene organic thin-film transistors via a gated four-probe technique. The transistors consist of Au source and drain electrodes contacting a pentacene film deposited on a dielectric/gate electrode assembly. Additional voltage sensing leads penetrating into the source-drain channel were used to monitor potentials in the pentacene film while passing current between the source and drain electrodes during gate voltage sweeps. Using this device structure, we investigated contact resistance as a function of film thickness (60–3000Å), deposition temperature (25 or 80°C), gate voltage, electrode geometry (top or bottom contact), and temperature. Contact resistance values were approximately 2×103–7×106Ωcm, depending on film thickness. In the temperature range of 77–295K, the contact resistance displayed activated behavior with activation energies of 15–160meV. Importantly, it was observed that the activation energies for the source and drain resistances were nearly identical for all device configurations. Contact resistance was found to be dependent on the film mobility in a power law fashion with exponents in the range of −0.58 to −1.94. The activation energy and the dependence of resistance on mobility suggest that contact resistance is not determined by a barrier at the metal-pentacene interface, but rather, drift/diffusion of carriers near the metal-pentacene interface. Two-dimensional device modeling of gated four-probe structures was performed to examine the validity of the source and drain resistance determination.

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