Shino Hamao

Transistor application of alkyl-substituted picene

Field-effect transistors (FETs) were fabricated with a thin film of 3,10-ditetradecylpicene, picene-(C14H29)2, formed using either a thermal deposition or a deposition from solution (solution process). All FETs showed p-channel normally-off characteristics. The field-effect mobility, μ, in a picene-(C14H29)2 thin-film FET with PbZr0.52Ti0.48O3 (PZT) gate dielectric reached ~21 cm2 V−1 s−1, which is the highest μ value recorded for organic thin-film FETs; the average μ value () evaluated from twelve FET devices was 14(4) cm2 V−1 s−1. The values for picene-(C14H29)2 thin-film FETs with other gate dielectrics such as SiO2, Ta2O5, ZrO2 and HfO2 were greater than 5 cm2 V−1 s−1, and the lowest absolute threshold voltage, |Vth|, (5.2 V) was recorded with a PZT gate dielectric; the average |Vth| for PZT gate dielectric is 7(1) V. The solution-processed picene-(C14H29)2 FET was also fabricated with an SiO2 gate dielectric, yielding μ = 3.4 × 10−2 cm2 V−1 s−1. These results verify the effectiveness of picene-(C14H29)2 for electronics applications.

Fabrication of high performance/highly functional field-effect transistor devices based on [6]phenacene thin films

Field-effect transistors (FETs) based on [6]phenacene thin films were fabricated with SiO2 and parylene gate dielectrics. These FET devices exhibit field-effect mobility in the saturation regime as high as 7.4 cm(2) V(-1) s(-1), which is one of the highest reported values for organic thin-film FETs. The two- and four-probe mobilities in the linear regime display nearly similar values, suggesting negligible contact resistance at 300 K. FET characteristics were investigated using two-probe and four-probe measurement modes at 50-300 K. The two-probe mobility of the saturation regime can be explained by the multiple shallow trap and release model, while the intrinsic mobility obtained by the four-probe measurement in the linear regime is better explained by the phenomenon of transport with charge carrier scattering at low temperatures. The FET device fabricated with a parylene gate dielectric on polyethylene terephthalate possesses both transparency and flexibility, implying feasibility of practical application of [6]phenacene FETs in flexible/transparent electronics. N-channel FET characteristics were also achieved in the [6]phenacene thin-film FETs using metals that possess a small work function for use as source/drain electrodes.

An Extended Phenacene-type Molecule, [8]Phenacene: Synthesis and Transistor Application

A new phenacene-type molecule, [8]phenacene, which is an extended zigzag chain of coplanar fused benzene rings, has been synthesised for use in an organic field-effect transistor (FET). The molecule consists of a phenacene core of eight benzene rings, which has a lengthy π-conjugated system. The structure was verified by elemental analysis, solid-state NMR, X-ray diffraction (XRD) pattern, absorption spectrum and photoelectron yield spectroscopy (PYS). This type of molecule is quite interesting, not only as pure chemistry but also for its potential electronics applications. Here we report the physical properties of [8]phenacene and its FET application. An [8]phenacene thin-film FET fabricated with an SiO2 gate dielectric showed clear p-channel characteristics. The highest μ achieved in an [8]phenacene thin-film FET with an SiO2 gate dielectric is 1.74 cm2 V−1 s−1, demonstrating excellent FET characteristics; the average μ was evaluated as 1.2(3) cm2 V−1 s−1. The μ value in the [8]phenacene electric-double-layer FET reached 16.4 cm2 V−1 s−1, which is the highest reported in EDL FETs based on phenacene-type molecules; the average μ was evaluated as 8(5) cm2 V−1 s−1. The μ values recorded in this study show that [8]phenacene is a promising molecule for transistor applications.

Phenanthro[1,2-b:8,7-b’]dithiophene: a new picene-type molecule for transistor applications

A new picene-type molecule, phenanthro[1,2-b : 8,7-b’]dithiophene, has been synthesized for use in organic field-effect transistors (OFETs). The molecule consists of a phenanthrene core with two thiophene rings fused on the ends. This molecule can be recognized as a picene analogue. The electronic structure of the molecule was determined by its optical absorption spectrum together with a theoretical calculation based on density functional theory (DFT). The topological and electronic structures of thin films produced by direct thermal evaporation of the compounds and by deposition from a solution were characterized by optical imaging, X-ray diffraction, and atomic force microscopy. FET devices were fabricated with these thin films, and showed field-effect mobility as high as 10−1 cm2 V−1 s−1.

Synthesis of methoxy-substituted picenes: Substitution position effect on their electronic and single-crystal structures

A series of picenes having methoxy groups was synthesized through Pd-catalyzed Suzuki-Miyaura couplings or Wittig reaction/intramolecular cyclization sequences, and their physicochemical properties and single-crystal structures were evaluated. The substitution position effects between the outer 1,12-, 2,11-, and 4,9-position and the inner 3,10-position are quite different; the former showed the same electronic structure as that of picene, but the latter results in a HOMO geometry different from those of picene and other methoxy picenes. In addition, crystal structures of four types of methoxy-substituted picenes 4a-c,e strongly depend on their substitution position and number of methoxy groups, which dramatically changes the structures from the fully anisotropic 1D π-stacked structure to a unique 3D herringbone structure due to steric hindrance of methoxy groups. The calculations of transfer integrals based on their single-crystal structures reveal that the methoxy picenes have intermolecular overlaps less effective than that of the parent nonsubstituted picene. These results are attributed not only to the packing structure but also to electronic structures such as the HOMO distribution. The preliminary OFET of the representative 4c,e showed hole mobilities significantly lower than that of picene due to their less effective intermolecular overlaps, as predicted by the calculated transfer integrals.

Transistor application of new picene-type molecules, 2,9-dialkylated phenanthro[1,2-b: 8,7-b′]dithiophenes

Field-effect transistors (FETs) have been fabricated with thin films of a series of 2,9-dialkylated phenanthro[1,2-b:8,7-b′]dithiophene derivatives (Cn-PDTs). The FET characteristics of Cn-PDT thin-film FETs with an SiO2 gate dielectric as well as high-k gate dielectrics were recorded, and the dependence of the field-effect mobility, μ, on the number (n) of carbon atoms in the alkyl chains was investigated, showing that the 2,9-didodecylphenanthro[1,2-b:8,7-b′]dithiophene (C12-PDT) thin-film FET displays superior properties, with μs as high as 1.8 cm2 V−1 s−1 for the SiO2 gate dielectric and 2.2 cm2 V−1 s−1 for the HfO2 gate dielectric. The average μ values, 〈μ〉, reach 1.1(5) and 1.8(6) cm2 V−1 s−1, respectively, for the SiO2 and ZrO2 gate dielectrics. Low-voltage operation, showing an absolute average threshold voltage 〈|Vth|〉 of ∼11 V, was implemented, together with the above high 〈μ〉 of ∼2 cm2 V−1 s−1. Also, a flexible FET was fabricated with a parylene gate dielectric. The results of this study show the potential of the C12-PDT molecule for application in a high-performance transistor.

Synthesis and transistor application of the extremely extended phenacene molecule, [9]phenacene

Many chemists have attempted syntheses of extended π-electron network molecules because of the widespread interest in the chemistry, physics and materials science of such molecules and their potential applications. In particular, extended phenacene molecules, consisting of coplanar fused benzene rings in a repeating W-shaped pattern have attracted much attention because field-effect transistors (FETs) using phenacene molecules show promisingly high performance. Until now, the most extended phenacene molecule available for transistors was [8]phenacene, with eight benzene rings, which showed very high FET performance. Here, we report the synthesis of a more extended phenacene molecule, [9]phenacene, with nine benzene rings. Our synthesis produced enough [9]phenacene to allow the characterization of its crystal and electronic structures, as well as the fabrication of FETs using thin-film and single-crystal [9]phenacene. The latter showed a field-effect mobility as high as 18 cm2 V−1 s−1, which is the highest mobility realized so far in organic single-crystal FETs.

Recent progress on carbon-based superconductors.

This article reviews new superconducting phases of carbon-based materials. During the past decade, new carbon-based superconductors have been extensively developed through the use of intercalation chemistry, electrostatic carrier doping, and surface-proving techniques. The superconducting transition temperature T c of these materials has been rapidly elevated, and the variety of superconductors has been increased. This review fully introduces graphite, graphene, and hydrocarbon superconductors and future perspectives of high-T c superconductors based on these materials, including present problems. Carbon-based superconductors show various types of interesting behavior, such as a positive pressure dependence of T c. At present, experimental information on superconductors is still insufficient, and theoretical treatment is also incomplete. In particular, experimental results are still lacking for graphene and hydrocarbon superconductors. Therefore, it is very important to review experimental results in detail and introduce theoretical approaches, for the sake of advances in condensed matter physics. Furthermore, the recent experimental results on hydrocarbon superconductors obtained by our group are also included in this article. Consequently, this review article may provide a hint to designing new carbon-based superconductors exhibiting higher T c and interesting physical features.

Transition-metal-catalyzed facile access to 3,11-dialkylfulminenes for transistor applications.

Novel [6]phenacenes (fulminenes) with two long alkyl chains at the axis positions were synthesized. This short synthesis comprises the following three steps: (1) ruthenium-catalyzed direct C-H bond arylation; (2) conversion of directing groups by Wittig reaction; and (3) bismuth- or gold-catalyzed cyclization of vinyl ether. Organic field-effect transistor devices fabricated with a thin film of 3,11-di(tetradecyl)fulminene exhibited typical p-channel normally-off properties.

Transistors fabricated using the single crystals of [8]phenacene

Field-effect transistors (FETs) with single crystals of a new phenacene-type molecule, [8]phenacene, were fabricated and characterized. This new molecule consists of a phenacene core of eight benzene rings, with an extended π-conjugated system, which was recently synthesized for use in an FET by our group. The FET characteristics of an [8]phenacene single-crystal FET with SiO2 gate dielectrics show typical p-channel properties with an average field-effect mobility, 〈μ〉, as high as 3(2) cm2 V−1 s−1 in two-terminal measurement mode, which is a relatively high value for a p-channel single-crystal FET. The 〈μ〉 was determined to be 6(2) cm2 V−1 s−1 in four-terminal measurement mode. Low-voltage operation was achieved with PbZr0.52Ti0.48O3 (PZT) as the gate dielectric, and an electric-double-layer (EDL) capacitor. The 〈μ〉 and average values of absolute threshold voltage, 〈|Vth|〉, were 1.6(4) cm2 V−1 s−1 and 5(1) V, respectively, for PZT, and 4(2) × 10−1 cm2 V−1 s−1 and 2.38(4) V, respectively, for the EDL capacitor; these values were evaluated in two-terminal measurement mode. The inverter circuit was fabricated using [8]phenacene and N,N′-1H,1H-perfluorobutyldicyanoperylene-carboxydi-imide single-crystal FETs. This is the first logic gate circuit using phenacene molecules. Furthermore, the relationship between μ and the number of benzene rings was clarified based on this study and the previous studies on phenacene single-crystal FETs.