Efforts to identify and develop new superconducting materials continue apace, motivated by both fundamental science and the prospects for application. For example, several new superconducting material systems have been developed in the recent past, including calcium-intercalated graphite compounds, boron-doped diamond and-most prominently-iron arsenides such as LaO(1-x)F(x)FeAs (ref. 3). In the case of organic superconductors, however, no new material system with a high superconducting transition temperature (T(c)) has been discovered in the past decade. Here we report that intercalating an alkali metal into picene, a wide-bandgap semiconducting solid hydrocarbon, produces metallic behaviour and superconductivity. Solid potassium-intercalated picene (K(x)picene) shows T(c) values of 7 K and 18 K, depending on the metal content. The drop of magnetization in K(x)picene solids at the transition temperature is sharp (<2 K), similar to the behaviour of Ca-intercalated graphite. The T(c) of 18 K is comparable to that of K-intercalated C(60) (ref. 4). This discovery of superconductivity in K(x)picene shows that organic hydrocarbons are promising candidates for improved T(c) values.

New carbon-based superconductors are synthesized by intercalating metal atoms into the solid-phase hydrocarbons picene and coronene. The highest reported superconducting transition temperature, T(c), of a hydrocarbon superconductor is 18 K for K(3)picene. The physics and chemistry of the hydrocarbon superconductors are extensively described for A(x)picene (A: alkali and alkali earth-metal atoms) for x = 0-5. The theoretical picture of their electronic structure is also reviewed. Future prospects for hydrocarbon superconductors are discussed from the viewpoint of combining electronics with condensed-matter physics: modification of the physical properties of hydrocarbon solids is explored by building them into a field-effect transistor. The features of other carbon-based superconductors are compared to clarify the nature of hydrocarbon superconductors.

A field-effect transistor (FET) with thin films of picene has been fabricated on SiO2 gate dielectric. The FET showed p-channel enhancement-type FET characteristics with the field-effect mobility, mu, of 1.1 cm2 V-1 s-1 and the on-off ratio of >10(5). This excellent device performance was realized under atmospheric conditions. The mu increased with an increase in temperature, and the FET performance was improved by exposure to air or O2 for a long time. This result implies that this device is an air (O2)-assisted FET. The FET characteristics are discussed on the basis of structural topography and the energy diagram of picene thin films.

Ionic-liquid gates have a high carrier density due to their atomically thin electric double layer (EDL) and extremely large geometrical capacitance Cg. However, a high carrier density in graphene has not been achieved even with ionic-liquid gates because the EDL capacitance CEDL between the ionic liquid and graphene involves the series connection of Cg and the quantum capacitance Cq, which is proportional to the density of states. We investigated the variables that determine CEDL at the molecular level by varying the number of graphene layers n and thereby optimising Cq. The CEDL value is governed by Cq at n < 4, and by Cg at n > 4. This transition with n indicates a composite nature for CEDL. Our finding clarifies a universal principle that determines capacitance on a microscopic scale, and provides nanotechnological perspectives on charge accumulation and energy storage using an ultimately thin capacitor.

Picene is a phenacene-type aromatic hydrocarbon molecule with five benzene rings. We have fabricated picene single crystal (SC) field-effect transistors (FETs) with solid gate and ionic liquid gate dielectrics. Although the picene SC FET showed a large hole-injection barrier without any modification of interface between source/drain electrodes and picene SC, such a large hole-injection barrier could be effectively reduced by modifying the interface with tetracyanoquinodimethane (TCNQ). Picene SC FET with an HfO2 gate dielectric and TCNQ-coated electrodes shows p-channel characteristics with a smooth hole injection and a field-effect mobility more than 1 cm2 V–1 s–1 in two-terminal measurement. Picene SC FET could be operated even in bottom-contact structure by modifying the interface with octanethiol. Furthermore, picene SC FET operated with ionic liquid gate dielectric, [1-butyl-3-methylimidazolium][hexafluorophosphate], showing the field-effect mobility of 1.8 × 10–1 cm2 V–1 s–1 and low absolute value, 1.9 V, of threshold voltage.

Transport characteristics and trap states are investigated in picene thin film field-effect transistor under O2 atmosphere on the basis of multiple shallow trap and release (MTR) model. The channel transport is dominated by MTR below 300 K. It has been clarified on the basis of MTR model that the O2-exposure induces a drastic reduction in shallow trap density to increase both the field-effect mobility μ and on-off ratio. We also found that the O2-exposure never caused an increase in hole carrier density. Actually, a very high μ value of 3.2 cm2 V−1 s−1 is realized under 500 Torr of O2.

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.

We report electronic structure and physical properties of metal-doped picene as well as selective synthesis of the phase that exhibits 18 K superconducting transition. First, Raman scattering is used to characterize the number of electrons 2 transferred from the dopants to picene molecules, where a softening of Raman scattering peaks enables us to determine the number of transferred electrons.From this we have identified that three electrons are transferred to each picene molecule in the superconducting doped picene solids. Second, we report pressure dependence of T c in 7 K and 18 K phases of K 3 picene. The 7 K phase shows a negative pressure-dependence, while the 18 K phase exhibits a positive pressure-dependence which cannot be understood with a simple phonon mechanism of BCS superconductivity. Third, we report a new synthesis method for superconducting K 3 picene by a solution process with monomethylamine, CH 3 NH 2 . This method enables us to prepare selectively the K 3 picene sample exhibiting 18 K superconducting transition. The method for preparing K 3 picene with T c = 18 K found here may facilitate clarification of the mechanism of superconductivity.Corresponding author: Takashi Kambe, kambe@cc.okayama-u.ac.jp & Yoshihiro Kubozono, kubozono@cc.okayama-u.ac.jp 3 I. IntroductionRecently a new class of organic superconductors has been discovered in aromatic systems. They are solids of hydrocarbons that include picene, coronene, phenanthrene and 1,2:8,9-dibenzopentacene, 1-6 doped with metal atoms. Namely, the superconductivity was first discovered in potassium-doped picene, K 3 picene, which showed two different superconducting transition temperatures, one with T c = 7 K and the other as high as 18 K. 1 This has been followed by other studies, and the highest T c among these hydrocarbon superconductors to date attains 33 K observed in K 3.45 dibenzopentacene, 6 whose T c is much higher than the highest T c (14.2 K at 8.2 GPa 7 in β'-(BEDT-TTF) 2 ICl 2 ) in charge-transfer organic superconductors. Thus the hydrocarbon superconductors are very attractive from viewpoints of development of new high-T c superconductors as well as fundamental physics of superconductivity.Theoretical calculations for picene superconductors were also achieved, which suggests that the electron-phonon coupling is strong, 8,9 the conduction band comprises four bands arising from two LUMO orbitals, 10 and that strong hybridization between the dopants and molecules invalidates a rigid-band picture. 10The departure from the rigid-band picture was experimentally evidenced by photoemission spectroscopy. 11 This photoemission study clearly showed a metallic ground state for potassium-doped picene films. Our recent resistivity data also indicate a metallic behavior for the K 3 picene phase. 12 Further, a Pauli paramagnetic susceptibility was observed for a K 3 picene bulk sample. 1 These results support a metallic ground state for K 3 picene.The T c for the solid K 3 picene was found to be either 7 or 18 K, 1,2 while the T c of K 3 phenant...