Very high-mobility organic transistors are fabricated with purified rubrene single crystals and high-density organosilane self-assembled monolayers. The interface with minimized surface levels allows carriers to distribute deep into the crystals by more than a few molecular layers under weak gate electric fields, so that the inner channel plays a significant part in the transfer performance. With the in-crystal carriers less affected by scattering mechanisms at the interface, the maximum transistor mobility reaches 18cm2∕Vs and the contact-free intrinsic mobility turned out to be 40cm2∕Vs as the result of four-terminal measurement. These are the highest values ever reported for organic transistors.
We report high-mobility rubrene single-crystal field-effect transistors with ionic-liquid (IL) electrolytes used for gate dielectric layers. As the result of fast ionic diffusion to form electric double layers, their capacitances remain more than 1μF∕cm2 even at 0.1MHz. With high carrier mobility of 1.2cm2∕Vs in the rubrene crystal, pronounced current amplification is achieved at the gate voltage of only 0.2V, which is two orders of magnitude smaller than that necessary for organic thin-film transistors with dielectric gate insulators. The results demonstrate that the IL/organic semiconductor interfaces are suited to realize low-power and fast-switching field-effect transistors without sacrificing carrier mobility in forming the solid/liquid interfaces.
The terahertz and infrared frequency vibration modes of room-temperature ionic liquids with imidazolium cations and halogen anions were extensively investigated. There is an intermolecular vibrational mode between the imidazolium ring of an imidazolium cation, a halogen atomic anion with a large absorption coefficient and a broad bandwidth in the low THz frequency region (13–130 cm−1), the intramolecular vibrational modes of the alkyl-chain part of an imidazolium cation with a relatively small absorption coefficient in the mid THz frequency region (130–500 cm−1), the intramolecular skeletal vibrational modes of an imidazolium ring affected by the interaction between the imidazolium ring, and a halogen anion with a relatively large absorption coefficient in a high THz frequency region (500–670 cm−1). Interesting spectroscopic features on the interaction between imidazolium cations and halogen anions was also obtained from spectroscopic studies at IR frequencies (550–3300 cm−1). As far as the frequency of the intermolecular vibrational mode is concerned, we found the significance of the reduced mass in determining the intermolecular vibration frequency.
Infrared spectroscopy was performed on ionic liquids (ILs) that had imidazolium cations with different alkyl chain lengths and various halogen or molecular anions with and without a small amount of water. The molar concentration normalized absorbance due to C-H vibrational modes in the range of 3000 to 3200 cm was nearly identical for ILs that had imidazolium cations with different alkyl chain lengths and the same anions. A close correlation was found between the red-shifted C-H vibrational modes, the chemical shift ofC(2)-H proton, and the energy stabilization of the hydrogen-bonding interaction. The vibrational modes of the water molecules interacting with anions in the range between 3300 and 3800 cm was examined. The correlation between the vibrational frequencies of water, the frequencies of C-H vibrational modes, and the center frequency of intermolecular vibrational modes due to ion pairs was discussed.
The terahertz- and infrared-frequency vibrational modes of various room-temperature imidazolium-based ionic liquids with molecular anions were examined extensively. We found that the molar-concentration-normalized absorption coefficient spectra in the low-wavenumber range for imidazolium cations with different alkyl-chain lengths were nearly identical for the same anion. Regarding the overall view of a wide range of imidazolium-based ionic liquids, we found that the reduced mass of the combination of an imidazolium-ring cation and the anion and the force constant play significant roles in determining the central frequency of the broad absorption band. In addition to these findings, we also discuss the correlation between the (+)C-H stretching vibrational modes in the 3000-3300 cm(-1) range of the infrared spectra and the intermolecular vibrational band in the low-wavenumber range. Finally, we describe some interesting characteristics of the intermolecular vibrational band observed in a wide range of imidazolium-based ionic liquids.
High-mobility organic transistors are fabricated on both surfaces of approximately 1-μm-thick rubrene crystals, molecularly flat over an area of 10×10μm2. A thin platelet of 9,10-diphenylanthracene single crystal and surface-passivated SiO2 are used for the gate insulators. Because of the minimized densities of hole-trapping levels at the interfaces and in the rubrene crystal, the field-induced carriers do not necessarily reside near the interface but are distributed in the bulk of the semiconductor by adjusting the two gate voltages. Making use of the highly mobile carriers in the inner crystal, the mobility is maximized to ∼43cm2∕Vs.
The microscopic mechanisms behind the very high mobility in rubrene single-crystal transistors achieved by interface treatments with self-assembled monolayers (SAMs) have been clarified by using field-induced electron spin resonance (FI-ESR). Clearly observed FI-ESR signals exhibit extremely narrow linewidths owing to the very high carrier mobility. The precise angular dependence of FI-ESR g values shows that crystallinity in the semiconductor channel is unchanged by the SAM treatments. The trapping time of charge carriers at the interface directly evaluated from the ESR linewidth greatly decreases from ∼700 to ∼60 ps concomitant with the remarkable improvement in mobility because of the SAM treatments.
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