The tetratopic ligand tetrathiafulvalene-tetrabenzoate (H4TTFTB) is used to synthesize Zn2(TTFTB), a new metal-organic framework that contains columnar stacks of tetrathiafulvalene and benzoate-lined infinite one-dimensional channels. The new MOF remains porous upon desolvation and exhibits charge mobility commensurate with some of the best organic semiconductors, confirmed by flash-photolysis-time-resolved microwave conductivity measurements. Zn2(TTFTB) represents the first example of a permanently porous MOF with high charge mobility and may inspire further exploration of the electronic properties of these materials.
The reaction of MnCl2 with 2,5-disulfhydrylbenzene-1,4-dicarboxylic acid (H4DSBDC), in which the phenol groups in 2,5-dihydroxybenzene-1,4-dicarboxylic acid (H4DOBDC) have been replaced by thiophenol units, led to the isolation of Mn2(DSBDC), a thiolated analogue of the M2(DOBDC) series of metal-organic frameworks (MOFs). The sulfur atoms participate in infinite one-dimensional Mn-S chains, and Mn2(DSBDC) shows a high surface area and high charge mobility similar to that found in some of the most common organic semiconductors. The synthetic approach to Mn2(DSBDC) and its excellent electronic properties provide a blueprint for a potentially rich area of exploration in microporous conductive MOFs with low-dimensional charge transport pathways.
We have successfully designed the geometry of the microwave cavity and the thin metal electrode, achieving resonance of the microwave cavity with the metal-insulator-semiconductor (MIS) device structure. This very simple MIS device operates in the cavity, where charge carriers are injected quantitatively by an applied bias at the insulator-semiconductor interface. The local motion of the charge carriers was clearly probed through the applied external microwave field, also giving the quantitative responses to the injected charge carrier density and charge/discharge characteristics. By means of the present measurement system named field-induced time-resolved microwave conductivity (FI-TRMC), the pentacene thin film in the MIS device allowed the evaluation of the hole and electron mobility at the insulator-semiconductor interface of 6.3 and 0.34 cm2 V−1 s−1, respectively. This is the first report on the direct, intrinsic, non-contact measurement of charge carrier mobility at interfaces that has been fully experimentally verified.
The density of traps at semiconductor–insulator interfaces was successfully estimated using microwave dielectric loss spectroscopy with model thin-film organic field-effect transistors. The non-contact, non-destructive analysis technique is referred to as field-induced time-resolved microwave conductivity (FI-TRMC) at interfaces. Kinetic traces of FI-TRMC transients clearly distinguished the mobile charge carriers at the interfaces from the immobile charges trapped at defects, allowing both the mobility of charge carriers and the number density of trap sites to be determined at the semiconductor-insulator interfaces. The number density of defects at the interface between evaporated pentacene on a poly(methylmethacrylate) insulating layer was determined to be 1012 cm−2, and the hole mobility was up to 6.5 cm2 V−1 s−1 after filling the defects with trapped carriers. The FI-TRMC at interfaces technique has the potential to provide rapid screening for the assessment of interfacial electronic states in a variety of semiconductor devices.
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