Kubozono2011 Metal Intercalated Aromatic Hydrocarbons A New Class of CARBON BASED SUPERCONDUCTORS

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Cite this: Phys. Chem. Chem. Phys., 2011, 13, 16476–16493
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Metal-intercalated aromatic hydrocarbons: a new class of
carbon-based superconductors
Published on 17 August 2011. Downloaded by Universiteit Utrecht on 27/10/2014 00:26:32.
Yoshihiro Kubozono,*ab Hiroki Mitamura,a Xuesong Lee,a Xuexia He,a

Yusuke Yamanari,c Yosuke Takahashi,c Yuta Suzuki,c Yumiko Kaji,a
Ritsuko Eguchi,a Koki Akaike,a Takashi Kambe,c Hideki Okamoto,d
Akihiko Fujiwara,e Takashi Kato,f Taichi Kosugigh and Hideo Aokig
Received 29th March 2011, Accepted 15th July 2011
DOI: 10.1039/c1cp20961b
New carbon-based superconductors are synthesized by intercalating metal atoms into the
solid-phase hydrocarbons picene and coronene. The highest reported superconducting transition
temperature, Tc, of a hydrocarbon superconductor is 18 K for K3picene. The physics and
chemistry of the hydrocarbon superconductors are extensively described for Axpicene (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.
1. The hydrocarbon superconductors—an outline Then came superconductivity in organic metals in 1980,
first discovered in tetramethyltetraselenafluvarene (TMTSF)
Superconductors with light elements such as B, C and Si compounds3 with Tc = 0.9 K under 12 kbar. This was
atoms (light-element superconductors; LEMs) are not only followed in 2003 by the bis(ethylenedithio)tetrathiafluvarene
interesting for their fundamental physics and chemistry, but (BEDT-TTF) family, for which Tc = 14.2 K under 82 kbar,4
important for future applications of superconductivity as the highest Tc, at that time, among the organic superconduc-
well, due to their abundance, low cost and lack of toxicity. tors. Another family is the doped fullerides, discovered5 in
In particular, carbon-based superconductors such as fullerene, 1991, with Tc = 18 K for K3C60 at ambient pressure, followed
organic molecular solids and graphite-related materials have by Cs2RbC60 with Tc = 33 K at ambient pressure6 and Cs3C60
attracted serious attention for their ease of design, flexibility with Tc E 40 K under 15 kbar,7 which is the highest Tc among
and light weight in addition to the inherent advantages of carbon-based materials; the exact Tc for Cs3C60 is described in
LEMs. Carbon-based superconductors have a long history Section 3. Generally, lower values of Tc in organics are under-
dating back to 1965 for the first discovery of superconductivity standable, since the electronic band width, which gives the basic
in graphite intercalation compounds (GICs),1 alkali-metal energy scale, is usually an order of magnitude smaller than in
doped AC8 (A = K, Rb, Cs), with transition temperatures inorganic materials. Thus the Tc in carbon-based superconduc-
of Tc o 1 K (recently increased to 11.5 K for CaC6).2 tors are still substantially lower than those in inorganic super-
conductors such as cuprates8 and iron-pnictides,9 for which Tc
a
Research Laboratory for Surface Science, Okayama University, reaches 133 K in the cuprate superconductor HgBa2Ca2Cu3O8,8
Okayama 700-8530, Japan. E-mail: kubozono@cc.okayama-u.ac.jp and 55 K in the iron-pnictide SmFeAsO1xFx.10 On the other
b
Research Centre for New Functional Materials for Energy hand, the discovery of unsuspected superconductivity in the
Production, Transport and Storage, Okayama University,
long-known intermetallic compound MgB2 with Tc = 40 K11
Okayama 700-8530, Japan
c
Department of Physics, Okayama University, Okayama 700-8530, may indicate the possibility of higher-Tc superconductors still
Japan hidden among common materials. As for mechanisms of
d
Department of Chemistry and Biochemistry, Okayama University, superconductivity, MgB2 is usually considered to be a BCS
Okayama 700-8530, Japan
e
Japan Synchrotron Radiation Research Institute, SPring-8, superconductor with an electron–phonon mechanism, with
Hyogo 679-5198, Japan two gap functions in a multiband structure. On the other hand,
f
Nagasaki Institute of Applied Science, Nagasaki 851-0121, Japan fullerene-based materials have strong electron–phonon and
g
Department of Physics, The University of Tokyo, Tokyo 113-0033, strong electron–electron interactions,12,13 so that both inter-
Japan
h
Nanosystem Research Institute, AIST, Umezono, Tsukuba 305-8568, actions may be involved in their superconductivity as some
Japan theories suggest.14,15
16476 Phys. Chem. Chem. Phys., 2011, 13, 16476–16493 This journal is c the Owner Societies 2011
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This view has led our group to the discovery of new carbon-
based superconductors exhibiting high Tcs. We have recently
produced superconductivity by incorporating alkali-metal
atoms into solids of an aromatic hydrocarbon, picene,16 whose
molecular structure is shown in Fig. 1(a). Two different Tcs are
observed at 7 and 18 K for K-doped picene, Kxpicene around
x = 3. Unmodified solid picene has a herringbone-like
arrangement of picene molecules (Fig. 1(b)), with the herring-
bone layers (ab-plane) stacked along the c-axis (Fig. 1(c)).
Thus, the system has a quasi-two dimensional (2D) structure,
which shares, interestingly, properties with most of the

other superconductors, i.e., GIC, MgB2, cuprates and iron-
pnictides. There is a theoretical suggestion that 2D systems are
more favourable than 3D ones for the electronic mechanism of
superconductivity by Arita et al.17 and by Monthoux and
Lonzarich.18 Solid picene can be doped with metal atoms,
and the resulting superconductivity is remarkable, since the
incorporation of metal atoms into solids of acenes, as exempli- Fig. 1 (a) Molecular structure of picene. Crystal structures of picene
fied by pentacene, has not led to superconductivity.19–21 viewed from (b) c-direction and (c) b-direction.
Yoshihiro Kubozono studied Hiroki Mitamura received

chemistry at Kyushu University his BS degree (Engineering)
(Japan) and received his PhD from Nagoya Institute of
in 1991 from the same Univer- Technology in 2009. He is
sity (Prof. Yasuhiko Gondo). currently pursuing his PhD at
He became a research associate Research Laboratory for
at Chemistry Department of Surface Science, Okayama
Okayama University (Japan). University (Prof. Yoshihiro
In 2007, he became a full Kubozono). His research
Professor of Research Labora- interests include superconduc-
tory for Surface Science of tivity in aromatic hydrocarbons,
Okayama University. His especially in alkali-metal doped
research interests include picene.
carbon based superconductivity,
Yoshihiro Kubozono organic electronics and nano- Hiroki Mitamura
scale science. He stayed at
Oxford University (1998) and at Swiss Federal Institute of
Technology, Zuerich (ETHZ) (2007), to work on metal inter-
calated C60 superconductors and organic electronics, respectively.
He is currently studying on metal intercalated organic super-
conductors and electrochemical doping with organic compounds
toward superconductivity.
Yosuke Takahashi received his Ritsuko Eguchi is an assistant

BSc in department of physics professor of Research Labora-
from Okayama University tory for Surface Science at
(Japan) in 2010. Currently Okayama University (Japan).
pursuing his Master course at She received her PhD in engi-
Okayama University under neering from the University of
the guidance of Prof. Takashi Tokyo in 2004 (Prof. Shik
Kambe, his research interests Shin). Her current research
include preparation of hydro- interests focus on studies of
carbon superconductors and the electronic structures in
its physical property including strongly-correlated transition
pressure effects. metal oxide and organic mate-
rials using photoemission and
inverse-photoemission spectro-
Yosuke Takahashi Ritsuko Eguchi scopies.
This journal is c the Owner Societies 2011 Phys. Chem. Chem. Phys., 2011, 13, 16476–16493 16477
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Previous studies of metal-doped pentacene crystals show only high stability even against O2 and H2O. [n]phenacenes as
a Pauli-like behaviour. large as [11]phenacene have been synthesized,22 while [9]acene
In the present article, we discuss the superconductivity of (nonacene) has been the largest acene obtained to date. This
metal-doped hydrocarbons with reference to the intercalation also suggests the higher stability of phenacenes. The stability
chemistry of carbon-based materials. The superconductivity in of phenacenes has been elaborated experimentally and
the present system will thus be compared with other carbon theoretically.23 At most two 6p-Kekule structures can be drawn
materials, graphite, C60 and diamond, and the features of for any acene, while n 6p-Kekule structures can be drawn for
superconductivity in hydrocarbon superconductors explored [n]phenacene. This provides a quantum chemical explanation
by comparing their physical properties with those of other for the stability of phenacene. That is, extensive delocalisation
carbon-based materials, from both experimental and theoretical of p-electrons takes place in phenacene molecules.
points of view. Finally, future prospects for hydrocarbon super- Phenacenes such as picene have attracted less attention than
conductors are considered, with emphasis on the realisation of acenes, such as pentacene, for use in organic electronic devices,
superconductivity with electrostatic carrier accumulations. because only a few efficient synthetic methods are currently
available for [n]phenacenes. The difficulty in obtaining large
quantities of phenacenes has delayed their application in
2. Features of aromatic hydrocarbon molecules
electronics. Synthetic pathways for picene so far reported are
We consider hydrocarbon molecules with structures that summarised in Fig. 2. It has been reported that 1,2-dinaphthyl-
include fused benzene rings. In one-dimensional (1D) extended ethane undergoes cyclisation to picene in the presence of a Lewis
hydrocarbons, [n]acene consists of a linear fusion of n benzene acid (Fig. 2, path a).24 However, this acid-promoted cyclisation
rings, while [n]phenacene consists of a zigzag fusion. Picene is has still not been reproduced in our own program. Photocycli-
thus represented as [5]phenacene. [n]phenacene molecules have sation of stilbene to phenanthrene has been established as an
lower reactivity than [n]acenes, where an [n]phenacene has effective procedure to construct the phenanthrene skeleton,25
Fig. 2 Synthesis routes for picene.
Takashi Kambe is an Associate Hideo Aoki is a Professor

Professor of Physics Depart- of Physics at the Department
ment, Okayama University of Physics, the University of
(Japan). He received his PhD Tokyo. He received his PhD
in physics from Tokyo institute in physics (1978) from the
of Technology (Tokyo Tech., University of Tokyo, became
Prof. Kazukiyo Nagata) in a research associate there. He
1994. He became a Research spent two years (1980–1982)
Associate in Physics Depart- at the Cavendish Laboratory,
ment of Okayama University University of Cambridge, UK,
in 1996, and he stayed at École as a visiting scholar. After an
Polytechnique Fe´de´rale de appointment at the University
Lausanne (Prof. László Forró, of Tsukuba, he became an
EPFL (Switzerland)) to study associate professor, Depart-
Takashi Kambe on high-pressure ESR for Hideo Aoki ment of Physics, University
carbon-based superconductors of Tokyo, then a full professor
(2000). His current research focuses a development of novel from 1998. His main interests are many-body effects in electron
organic superconductors/magnets including hydrocarbon super- systems, i.e., superconductivity, magnetism and topological
conductors and their physical properties. phenomena, with a materials design, and novel non-equilibrium
phenomena envisaged and proposed for correlated electron
systems.
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Polymorphs are often observed in molecular solids, and this

is also the case with aromatic hydrocarbons. Depending on
temperature, pressure, and sample preparation, the molecular
packing produces different crystal phases, or polymorphs.
Pentacene has four polymorphs, which are usually distin-
guished by their interlayer spacing along the c direction,
d(001).34 Mattheus et al. presented a model for reproducing
the interlayer spacing, in which the spacing can be tuned by
moving the molecules in opposite directions along the long
molecular axis in the layer.35 When the temperature is varied,
a structural phase transformation has been observed in penta-

cene at 463 K.36 Both the high-temperature (HT) and the
low-temperature (LT) structures are known to take layered
herringbone-forms, with different interlayer stacking. In the
HT structure, the long molecular axes of the adjacent mole-
cules across the interlayer almost overlap each other when
viewed along [110], as seen from Fig. 1 in ref. 36. The
LT-structure has also overlapping of long-molecular axes of
adjacent layers, but the molecular axes slightly moved towards
Fig. 3 Synthesis routes for [7]phenacene and [11]phenacene derivatives. [110]. The two structures explain the interlayer spacing of the
two main phases among the four polymorphs.
and this photoreaction was extended to a 1,2-dinaphthylethene The picene molecule crystallises in a herringbone structure,
system to produce picene (Fig. 2, path b). Photocyclisation was as described in the previous section, and the crystal lattice is
used to construct larger phenacene frameworks such as [7]- and monoclinic with space group P21. The lattice constants are
[11]phenacenes (Fig. 3).22,26 Intramolecular McMurry coupling reported to be a = 8.480(2), b = 6.154 (2), c = 13.515(3) in Å,
of bi(b-naphthyl) can also produce picene with a moderate yield and b = 90.46(1)1 from single-crystal X-ray diffraction
(Fig. 2, path c).27 [4 + 2] cycloaddition between benzyne and analysis.37 As mentioned below, the lattice constants are the
vinyl-substituted dihydrophenanthrene (Fig. 2, path d)28 and same as those determined for our sample. Two crystallo-
intramolecular Friedel–Crafts-type cyclisation (Fig. 2, path e)29 graphically equivalent molecules exist in this crystal lattice,
were used to prepare the picene framework in the 1990s. Very related to each other by a screw axis, 21, along b. The dihedral
recently, Pt-catalysed aromatisation of an ethynyl-substituted angle between these two molecules is 591, somewhat larger
terphenyl has been developed to synthesise a picene derivative than the 521 of pentacene. As seen from Fig. 1(c), the long axis
(Fig. 2, path f).30 The Pt-catalysed reaction is also effective of the picene molecule is aligned along [101] and is inclined by
to prepare [7]- and [11]phenacene derivatives (Fig. 3).31 We have 151 to the c-axis. The molecular packing form is different
recently developed a convenient one-step photochemical between picene and pentacene. In pentacene, the long mole-
synthesis of picene in which 1,2-dinaphthylethane was irradiated cular axes almost overlap with each other between adjacent
in the presence of sensitisers to afford picene (Fig. 2, path g).32 layers, while the molecular axis of the adjacent layer shifts
A picene sample synthesised via path g in Fig. 2 was used in towards b in picene (Fig. 1(c)). This may affect the interlayer
our study. Such planar hydrocarbon molecules crystallise in a hopping of carriers because of the different transfer integrals
layered structure in which the molecular packing in each layer between the molecules across the layers. To our knowledge, no
is affected by two important intermolecular interactions: the studies have reported on the polymorphs or structural phase
C–H interactions between adjacent molecules, and the C–C transitions in picene crystals.
interactions between molecules in adjacent layers. Desiraju Now we turn to coronene, for which the g-type packing is
and Gavezzotti classified the molecular-packing forms into shown in Fig. 4. The relatively large, disc-like shape of the
four groups (Fig. 2 in ref. 33).33 The simplest packing form is coronene molecule induces a large C–C interaction, which
the herringbone type, in which the C–H interactions between produces a molecular stacking along b, with an intermolecular
nearest-neighbour molecules dominate to produce a non-parallel distance along the b-axis as short as 3.42 Å. The lattice
arrangement.33 The packing of pentacene and picene molecules structure at room temperature is reported to be monoclinic
belongs to this group. with space group P21/a in which a = 16.094(9), b = 4.690(3),
When the C–C interaction or p–p interaction between out- c = 10.049(8) in Å and b = 111.79(2)1.38 Two crystallo-
of-plane p orbitals between neighbouring molecules increases, graphically equivalent molecules exist in the crystal, where the
the herringbone arrangement is flattened and the distance asymmetric unit is half a molecule because of a glide symmetry
between the molecules in the non-parallel form (Fig. 2 in along a, i.e., an inversion centre exists at special sites.
ref. 33) is increased. This is called a g-structure. Solid coronene Coronene crystals show pressure- and temperature-induced
takes this structure. A further increase in the C–C interaction structural phase transitions.39 Below 180 K and/or 140 K,
between the molecules produces a layer-like structure their polarised luminescence spectra clearly change, suggesting
(b-structure). Finally we arrive at a structure in which units a temperature-induced phase transition in this temperature
of two molecules form a herringbone arrangement called the region. In addition, at least three phase transitions exist at
‘‘sandwiched’’ herringbone structure. pressures below 2 GPa, and X-ray diffraction patterns suggest
Published on 17 August 2011. Downloaded by Universiteit Utrecht on 27/10/2014 00:26:32. View Article Online
Fig. 6 Energy diagram of pentacene, picene and [7]phenacene.
Fig. 4 (a) Molecular structure of coronene. Crystal structures of reactivity and high stability for phenacenes as compared with
coronene viewed from (b) c-direction and (c) b-direction. acenes. These values have been estimated under atmospheric
conditions.
monoclinic-to-orthorhombic structural phase transitions The electronic structures of picene and [7]phenacene have
under pressure.39 An orientational alternation of coronene been directly observed with photoemission spectroscopy (PES)
molecules is suggested as the origin of these structural phase and inverse-photoemission spectroscopy (IPES).43 PES is
transitions. To our knowledge, no reports on the polymorphs relevant to HOMO levels, IPES to LUMO levels. These experi-
of coronene crystals have been published. ments were performed under high vacuum, at 109–1010 Torr,
Fig. 5 shows the variation of optical absorption bands of as described below. The picene and [7]phenacene thin films
[n]acenes and [n]phenacenes as a function of the number of were evaporated onto Au/indium tin oxide (ITO) substrates in
benzene rings. The first absorption band, which originates high vacuum. The HOMO and LUMO levels relative to the
from the energy difference between the highest occupied Fermi level on Au films were determined by in-situ PES and
molecular orbital (HOMO) and the lowest unoccupied mole- IPES under high-vacuum conditions. The HOMO and LUMO
cular orbital (LUMO), shifts to longer wavelengths when the levels are 1.83 eV and +1.43 eV, respectively, in picene, while
number of benzene rings increases for acenes. This implies they are 1.68 eV and +1.44 eV in [7]phenacene, which means
that acene molecules with more benzene rings have smaller that the Fermi level on Au is located around the centre of the
HOMO–LUMO gaps. In contrast, the first absorption band HOMO–LUMO gap. This indicates an energy level scheme
of phenacenes hardly changes when the number of benzene quite different from those (Fig. 6) obtained by photoelectron
rings increases, and the HOMO–LUMO gap is located in the yield and optical absorption under atmospheric conditions.
UV region. This experimental result also supports the stability The major causes for the difference are the oxidation of picene
of phenacene molecules. Fig. 6 shows the energy level scheme and [7]phenacene under atmospheric conditions, i.e., p-doping
for pentacene, picene and [7]phenacene on a Si substrate, as to picene and [7]phenacene, and the interface dipole which
determined by photoelectron yield and optical absorption produces the vacuum level shift, induced in picene and
measured under atmospheric conditions. In pentacene [7]phenacene thin films on top of Au.
([5]acene), the HOMO–LUMO gap is 1.8 eV with the HOMO Several recent publications have reported experimental
level located at 5.1 eV,40 while the gap in picene is much determinations of the electronic structure of picene. Okazaki
larger, 3.3 eV, with the HOMO level at 5.5 eV.41 The et al. reported the PES of pristine and K-doped picene films.44
HOMO–LUMO gap of [7]phenacene is 3.2 eV and the HOMO The valence band of K-doped picene shows new states near
level is at 5.7 eV.42 These results also guarantee low the Fermi level, which can be ascribed to states derived from
the LUMO of pristine picene, but not to a rigid shift of the
LUMO of pristine picene. The experimental spectra are in
good agreement with molecular orbital calculations that take
account of the electron–intramolecular-vibration interaction.
Roth et al. investigated the occupied and unoccupied electro-
nic states using PES and electron energy-loss spectroscopy
(EELS). The electronic states were compared with the theore-
tical density of states, N(e), calculated with the local density
approximation (LDA) within the framework of the GW
approximation.45 They concluded that picene, as compared
with pentacene, shows a larger quasi-particle gap, a larger
exciton binding energy and a higher N(e) in unoccupied states
close to the Fermi energy.
Band dispersions in well-ordered organic thin films and
Fig. 5 Onset energy in optical absorptions of phenacenes and acenes. organic single crystals have been measured with angle-resolved
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ultraviolet photoemission spectroscopy (ARUPS). Pentacene

is a good target for ARUPS, because the pentacene FET has
high field-effect mobility.46–48 Koch et al. succeeded in obser-
ving the energy band dispersion in well-oriented pentacene
thin films formed on a highly oriented pyrolytic graphite
(HOPG) substrate, which showed a band width of 0.19 eV
at room temperature.49 Because of the importance of penta-
cene in organic electronics, other groups have also investigated
the energy dispersion in pentacene thin films using various
metal substrates, such as Cu (110), Bi (001) and O3 O3
Bi–Si(111), in order to obtain well-oriented pentacene thin

films.50–52
Machida et al. further succeeded in measuring ARUPS of
rubrene single crystals53 by exposing the crystals to a laser Fig. 7 Carbon network materials: (a) graphite, (b) C60, (c) diamond
beam of 405 nm so as to avoid the charging effect. In the G–Y and (d) graphene.
direction, along which the transfer integral becomes largest,
the band width was estimated to be 0.4 eV. By contrast, a but it has not proved easy to raise Tc in intercalated graphite
small dispersion was observed along G–X.53 These results compounds, because direct annealing of graphite and metals
reflect an anisotropy in the mobility of rubrene single crystals. tends to produce acetylides. A breakthrough came in 2005,
Subsequently, the band dispersion of rubrene single crystals when Ca-doped graphite, CaC6, was found to have Tc =
was also reported by Ding et al., also indicating dispersion, 11.5 K,2 which is remarkably high for a carbon-based super-
with a band width of 0.25 eV, larger along G–Y than along conductor. It was subsequently found that YbC6 shows
G–X.54 Tc = 6 K.62 The fact that the discovery of superconductivity
Studies of hydrocarbon molecules have so far primarily in CaC6 had to wait 40 years after the discovery of super-
concentrated on semiconductor device physics and application conductivity in KC8 indicates the difficulty of preparing CaC6,
to electronics. However, the recent finding of band dispersion which relates to the high melting point of Ca. To lower the
in highly-oriented hydrocarbon thin films and single crystals melting point, Emery et al. used a Ca/Li alloy that has a
testifies that organic solids can provide a stage for research in melting point as low as 620 K.2 The Ca/Li alloy then led to the
condensed matter physics and solid-state physical chemistry. fabrication of CaC6. The superconducting behaviour of CaC6
As a consequence, hydrocarbon molecules may be recognised is of interest for its peculiar pressure dependence, i.e., Tc
as attractive carbon-based network materials in that hydro- increases with the applied pressure.63 The pressure-coefficient
carbons can form 2D networks to provide controllable dTc/dp is positive, 0.42–0.48 K GPa1. The electronic struc-
electronic band structures. ture around the Fermi energy of metal-intercalated graphites is
known to have a large component of the so-called interlayer
states, whose amplitudes reside in between the graphene
3. Superconductivity in carbon-based materials
layers, giving a 3D character to the electronic structure.63,64
In this section we discuss the features of three types of carbon- This interlayer band is closely associated with its super-
based superconductors, i.e., those derived from graphite, C60 conductivity. Although the density of states on the Fermi
and diamond (Fig. 7(a)–(c)). Fig. 7(a) shows the structure of energy, N(eF), decreases with pressure in CaC6, a large soft-
graphite, which is a stack of honeycomb networks of carbon Å ening of an in-plane Ca vibration mode under pressure causes
atoms, namely graphene sheets (Fig. 7(d)). As seen from an increase in the electron––phonon coupling constant l which
Fig. 7(d), one might naively regard picene and pentacene is considered to overcome the reduction of eF leading to an
molecules as fragments of graphene. In the language of the enhanced Tc.63,64 Consistently, a positive pressure dependence
physics of graphene, picene has ‘‘armchair’’ edges, while of Tc is observed for CaC6.
pentacene has zigzag edges. It is known for graphene that The intercalation of alkali and alkali-earth metal atoms into
armchair edges are more stable than zigzag edges, which is C60 solids produces superconducting transitions at tempera-
again consistent with picene’s greater stability. Quantum tures up to 33 K under ambient pressure.6 The highest Tc of
chemically, however, we should be more precise, which is 33 K is realised for Cs2RbC60, as described in the previous
related to the problem of ‘‘aromaticity’’. section.6 The alkali metal atoms are intercalated into (1/4, 1/4,
Graphite can become superconducting when alkali-metal 1/4) and (1/2, 1/2, 1/2) sites in the face-centred cubic (fcc)
atoms are intercalated into the gaps between graphene sheets. crystal lattice of C60 molecules (space group Fm3% m).3–11 The
Superconductivity in K8C was first discovered in 1965,1 with a number of alkali metal atoms (C60) is 12 (4) in the unit cell of
Tc of 140 mK. Subsequently, other alkali-metal intercalated fcc crystals, with the unit formula A3C60 (A: alkali metal
graphites, LiC2, NaC2, NaC3, NaC4, KC3 and KC6, were also atom).12,65 Thus the metal atoms are intercalated into the
found to exhibit Tcs of 1.9–5 K.55–60 These compounds were special sites with a crystallographically high symmetry. The
synthesised under high pressure. Tc increased to 5 K for NaC2 N(eF)s for K3C60 (Tc = 18 K) and Rb3C60 (Tc = 29 K) are
with increased metal concentrations. An ambient-pressure 17 and 22 states eV1 spin1 C601, respectively,12,66 as
synthesis produced KTl1.5C4 with Tc = 2.7 K.61 Much effort determined from NMR measurements.12 N(eF) increases as
has been devoted to producing new graphite superconductors, the lattice constant increases (from a = 14.24 Å for K3C60,65
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a = 14.38 Å for Rb3C6067 to a = 14.43 Å for Rb2CsC6067), hole doping in a wide-gap semiconductor can produce super-
where Tc also increases.12 Thus a clear correlation between conductivity is rather suggestive, with important implications in
structural parameters and Tc was found in the initial stage of materials science.
research on metal-doped C60 superconductors.68 Details are Thus all of the carbon polymorphs (zero-dimensional C60,
summarised in ref. 12. Increasing the lattice constant or two-dimensional graphite and three-dimensional diamond)
volume, V, of the unit cell is an important key for improving can be made superconducting, despite their covalent bond
Tc in C60 superconductors. If we go further down the periodic forms (sp2/sp3, sp2 and sp3 respectively) being quite different.
table to examine Cs3C60, the material is not a superconductor Although this fact is significant, the procedures for inducing
under ambient pressure, although the lattice constant is superconductivity are different between sp2 and sp3 materials.
expected to be the largest among alkali-metal intercalated Superconductivity in materials with an sp2 structure is pro-
C60s, as it incorporates Cs, the largest alkali metal ion. duced by intercalation of metal atoms, and in those with
Theoretically, Capone et al. have suggested that a strong an sp3 character by substitution of other elements for C atoms.
electron–electron interaction is also at work in the lattice- Along this line, superconductivity may possibly be expected
constant dependence of superconductivity.69 when C is replaced by other elements, or by decorating
The crystal structures of A3C60 are not restricted to fcc, but the structure with some functional group as in ‘‘shuttlecock
can also be body-centred orthorhombic (bco) and simple cubic fullerene’’79 to incorporate some sp3 character. However,
(A15).7,70–74 In Cs3C60 crystals under pressure, for instance, no such materials have yet been synthesised and shown super-
the A15 and fcc phases show superconductivity with Tcs of conductivity. However, the fact does remain that carbon-
38 and 35 K, respectively.72–74 Cs3C60 cannot be prepared based materials provide an important and rich research stage
by annealing at high temperatures but by a solution process for superconductivity.
with NH3 at low temperatures,7 because Cs3C60 rapidly
decomposes into CsC60 and Cs4C60 at high temperatures. 4. Synthesis and physical properties of
The A15 phase of Cs3C60 is found to be an antiferro-
metal-intercalated picene and coronene
magnetic insulator from NMR and magnetic susceptibility
measurements at ambient pressure, and applying pressure to In this section, we fully describe the synthesis and physical
the A15 phase produces the superconducting phase.72,73 Anti- characterisation of solid-phase metal intercalated picene and
ferromagnetic ordering appears below 46 K, which defines the coronene, and their physical properties, including super-
Néel temperature TN. The highest Tc is 38 K at 7 kbar, above conductivity. The superconductivity of K3picene and Rb3picene
which the Tc decreases with increasing pressure.72,73 The fcc was first reported in a previous article.16 Here we elaborate on
phase of Cs3C60 is also found by NMR to be non-metallic.73 the superconductivity of alkali metal atom intercalated picene
In the case of fcc Cs3C60, magnetic ordering is observed below and other hydrocarbon superconductors.
TN = 2.2 K, and freezing of paramagnetic spin fluctuations is The electronic structure of picene can be modified by inter-
also found below 18 K. This phase is also a magnetic insulator, calating metal atoms such as K, Rb and Ca. Pristine solid picene
and applying pressure leads to superconductivity. The highest is a wide-gap semiconductor with a band gap of 3.3 eV, as
Tc for fcc Cs3C60, 35 K, is observed at 7 kbar.74 A plot of Tc described in Section 2. The colour of solid picene powder is
against the unit cell volume shows distinct dome-like relation- white, but it changes to black when annealed with metals in a
ships for both phases.74 The plots can be cast into a universal glass tube in vacuum. In this article, we use the chemical formula
curve if we replace V with U/W, where U and W are Coulomb Kxpicene, where x is the nominal value in the preparation of
repulsion and band width, respectively. A plot of Tc/Tc(max)– metal-intercalated picene solids, e.g., a sample with a molar ratio
(U/W)/(U/W)c then produces a universal curve, which indicates of 3 : 1 for K and picene is represented as K3picene. The
that Tc is controlled by the electron correlation (Mott physics), magnetic susceptibility, w, in Kxpicene changes with x, where w
independent of the packing of fullerene molecules in A15 or fcc, is obtained by dividing magnetisation M by applied magnetic
and where (U/W)c is the value of U/W at the Mott transition. field H. Temperature-independent behaviour of w is observed for
The maximum Tc (Tc(max)) occurs at (U/W)/(U/W)c = 0.87. As Kxpicene for x r 2.5, which indicates Pauli paramagnetism. At
a consequence, the superconducting Cs3C60 phase is close to the 2.6 r x r 3.3, the Pauli-like w drops suddenly at 7 or 18 K with
Mott transition, where the application of pressure overcomes the decreasing temperature, as fully described later. At x Z 3.3, a
magnetic order to elicit superconductivity.73,74 Curie-like behaviour is often observed, which suggests some
Diamond is a wide-gap semiconductor with a band gap of localised spins on picene molecules.
5.5 eV, and substitution of B atoms for C atoms in diamond Fig. 8(a) and (b) show the w–T plot for two different samples
produces superconductivity. In 2004, Ekimov et al. synthesised a of K3.3picene. The plot shows drastic drops at 7 and 18 K,
B-doped diamond using a high-pressure and high-temperature indicating superconducting transitions at two different tempera-
synthesis,75 by achieving a Tc of 4 K under ambient pressure. In tures. The shielding fractions at 2 K are 15 and 1.2% for the
a B-doped diamond, an increase in the B concentration changes 7 and 18 K superconductors, respectively. Superconductivity is
Tc, with 1022 cm3 of B doping producing the maximum Tc of observed for 2.6 r x r 3.3 in Kxpicene. More precisely,
7 K in (111) thin films.76 B-doped (100) single-crystal-like synthesis of Kxpicene by directly annealing picene with K metal
diamond thin films prepared by CVD show a lower Tc than at temperatures higher than 373 K led to different superconduct-
B-doped (111) diamond thin films.77 In B-doped diamond, the ing phases exhibiting Tc = 7 or 18 K, where the coexistence of
isotope effect on Tc was investigated to show the relevance of 7 and 18 K phases is scarcely observed. We further tried
electron–phonon coupling in superconductivity.78 The fact that to prepare Kxpicene by the solution method, as is used for
Fig. 8 w as a function of T for two K3.3picene samples: (a) 7 K and (b) 18 K superconductors. (c) w as a function of T for K3.1 picene made by
a solution process.
synthesis of Cs3C60.7,70–74 Picene and K metal were dissolved in defined to be the boundary for various values of H. The
monomethylamine [(CH3)NH2] at 220 K, and CH3NH2 was then H dependence of the w–T plot shows that the diamagnetic
removed in vacuum. Subsequently, the sample was heated at component decreases gradually with the application of H.
440 K for 72 h, and the w–T plot was measured for the K3.1picene The superconducting onset temperature, Tonset c , for the 18 K
sample, which displayed a clear drop at 18 K (Fig. 8(c)). This superconductor decreases to 17 K at 1000 Oe from 20 K at 20
method does not produce the 7 K superconducting phase but only Oe. Thus the superconducting phase is not completely broken
the 18 K phase, unlike the annealing method. The x values for weaker H o 1000 Oe, i.e., K3picene is a type-II super-
producing superconductivity by a solution process are confined conductor. For the 18 K superconductor the lower critical
to 2.9–3.1, namely, about three K atoms intercalated per picene field, Hc1, is 400 Oe at 0 K, while the upper critical field, Hc2,
molecule, or K3picene is a superconductor. The number of cannot be definitely determined from the plot (Fig. 9 and 10),
electrons per picene molecule was estimated to be 3 from Raman but a rough extrapolation gives Hc2 4 104 Oe. For the 7 K
data; the details for the estimation are described later. The lattice superconductor, Hc1 and Hc2 are estimated to be 300 and
constants are also almost consistent with those for K3picene 4104 Oe, respectively; the Hc1–T and Hc2–T plots are not
prepared by an annealing technique, which indicates the same shown in Fig. 10 but are shown in ref. 16. The coherence
crystal structure. Thus, the solution process with CH3NH2 can be length xGL and the penetration depth of magnetic field lL are
used to prepare the 18 K phase, but care should be taken in the estimated to be xGL E 18 nm and lL E 95 nm for the 7 K
experiment because 490 K annealing of the sample for removal of superconductor, while these values are 18 nm and 77 nm,
CH3NH2 produces the very toxic material, KCN. respectively, for the 18 K superconductor. We note that lL is
The H-dependence of the w–T plot for K3picene (7 and 18 K larger than the granule size, 14 nm, estimated from the X-ray
phases) is shown in Fig. 9. The plot is used to draw an H–T diffraction peak for these superconducting samples, which
diagram of K3picene for 7 and 18 K superconductors, respec- suggests that the shielding fraction of the superconducting
tively (Fig. 10), where the inflection point in the w–T plot is phase may be underestimated because of the penetration of
H into the granular samples. We also note that the value of lL
for K3picene is smaller by a factor of 2 than those for K3C60
and Rb3C60, which are 168 and 240 nm.12,80
Rb intercalation into solid picene also shows a supercon-
ducting transition at 7 K, as seen in Fig. 11(a), where the
nominal formula is Rb3.1picene. The shielding fraction is 10%
at 2 K, while Tonset
c is 7.2 K with the inflection point in the w–T
plot at 6.9 K. The H–T diagram for Rb3picene is shown in
Fig. 12(a); the diagram is determined from the inflection point
in the w–T plot for various values of H. We estimate xGL =
Fig. 9 H dependence of w–T plots: (a) 7 K and (b) 18 K superconductors 57 nm and lL = 130 nm from Hc1 = 80 Oe and Hc2 4 1000 Oe
(K3picene).
at 0 K; the Hc1 and Hc2 values at 0 K are taken from the Hc1–T
Fig. 10 H–T phase diagrams for (a) 7 K and (b) 18 K superconductors Fig. 11 w as a function of T for (a) Rb3.1picene and (b) Ca1.5picene
(K3picene). samples.
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Fig. 12 H–T phase diagrams for (a) Rb3picene and (b) Ca1.5picene.
and Hc2–T plots (not shown). We can go one step further to

alkali-earth metals, where Ca-doped Ca1.5picene also shows a
superconducting transition at 7 K, as displayed in Fig. 11(b),
where the shielding fraction is 1.25% at 2 K. It is interesting to
note that the intercalation of monovalent K and Rb produces
superconductivity at x E 3, while the intercalation of divalent
Ca produces superconductivity at x E 1.5. The H–T diagram of
Ca1.5picene is shown in Fig. 12(b); the diagram is determined
from the midpoint of the w–T plot at various H. We estimate
xGL = 57 nm and lL E 100 nm for Ca1.5picene from Hc1 =
150 Oe and Hc2 4 1000 Oe at 5 K (not shown). The w–T plot for
Ca1.5picene shows Pauli paramagnetism above Tc. As the grain
size of Rb3picene and Ca1.5picene are 32 and 8 nm, respectively,
their shielding fractions may also be underestimated owing to
the penetration of H, given the size of lL described above. It is Fig. 13 Raman scattering spectra for (a) Kxpicene and (b) Rbxpicene.
important to note that only the 7 K superconductive transition
is observed for Rb3picene and Ca1.5picene, in contrast with
K3picene, which shows Tcs at 7 and 18 K. theoretical values, while the experimental values are close to
The fact that Rb3picene and Ca1.5picene exhibit super- the theoretical values for the picene trianion i.e., A3picene. The
conductivity supports the idea that a roughly 3e electron Rb2picene samples show a superconducting transition, which
transfer to each picene molecule can lead to superconductivity. suggests that Rb2picene samples include some Rb3picene.
The energy difference between LUMO and LUMO + 1 is very Detailed investigation on the number of electrons per picene
small (estimated to be o0.1 eV). Thus three electrons are molecule based on experimental and theoretical Raman data is
supplied to the approximately two-fold degenerate LUMO reported in our recent paper.82
orbitals. As described in the theoretical section below, a As seen from Fig. 1, solid picene is a stack of layers along
first-principles (DFT) electronic structure calculation due to the c-axis, where each layer (ab-plane) has a herringbone
Kosugi et al. suggests that the conduction band of solid picene
derives from degenerate LUMO and LUMO + 1 orbitals,
which may play an important role in the superconductivity of
picene solids.81 To experimentally confirm the electron trans-
fer from alkali metal atoms to picene molecules, we have
measured the Raman scattering of Kxpicene and Rbxpicene
as shown in Fig. 13. A theoretical calculation for the picene
molecule shows a rapid softening of the peaks for molecular
vibrations with increasing x. The frequencies of Raman peaks,
denoted by arrows in Fig. 13, are plotted as a function of x in
Fig. 14, where the peak in pure picene can be assigned to the
n20 and n21 molecular vibrations; the observed Raman peak is
composed of two modes, n20 and n21, where the definitions of
n20 and n21 are shown in the caption of Fig. 14. The vibra-
tional modes for n20 and n21 are schematically shown in
Fig. 14(a). As seen from Fig. 14(b), the experimental Raman
frequencies of Kxpicene and Rbxpicene decrease with x, where
the frequencies are consistent with the theoretical n20 and n21,
which indicates that the nominal x value does not grossly Fig. 14 (a) Molecular vibration modes (n20 and n21) of picene
deviate from the actual number of alkali atoms intercalated molecule. (b)Theoretical Raman frequencies for n20 and n21 modes
into solid picene. However, the experimental Raman frequen- and the experimental frequencies for the corresponding Raman peak
cies for some Rb2picene samples deviate significantly from the (Kxpicene and Rbxpicene) as a function of x.
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as in the superconducting K3picene, suggests that the inter-

calation of metal atoms into the ab-layer may be closely
related to the appearance of superconductivity. The variation
of c saturates above x = 4 (not shown), for reasons yet to be
clarified. The V also expands up to x = 2 and decreases with
an increase in x, as seen from Fig. 15(b).
K/Rb metal intercalation into the ab-plane may produce a large
distortion of herringbone stacking because of the very small space
available in the herringbone stacking layer (ab-plane or ab-layer).
Indeed, the theoretical calculation81 for Kxpicene also indicates
that a lower energy state is obtained for structures with K atoms

intercalated within the ab-plane, where the three K atoms are
located above three benzene rings in each picene molecule, as
shown in Fig. 16(a). Theoretical work also shows that the angle
between the adjacent picene molecules in the herringbone structure
in a layer is substantially deformed upon insertion of the K atoms
(Fig. 16(b)).81 K atoms being inserted into the ab-plane is in sharp
contrast with the behaviour of Kxpentacene, in which alkali metal
atoms are experimentally confirmed to be intercalated into the
space between the ab-layers;83 the intercalation of metal atoms
into the ab-layer is theoretically predicted only in the high x region
of Kxpentacene.84 In the case of Rbxpentacene, Rb atoms are
also intercalated into the space between the ab-layers,20 while in
Csxpentacene, Cs atoms are intercalated into the space between
ab-layers while some of the Cs atoms are inserted into the
Fig. 15 x dependence of lattice constants in (a) Kxpicene and ab-layer.85
(b) Rbxpicene. It has been found that the Tc in K3picene decreases mono-
tonically with the pressure up to 1 GPa. The pressure coefficient
arrangement of molecules. Fig. 15(a) shows the lattice con- dTc/dp is 0.3 K GPa1, which is smaller by an order of
stants, a, b, c, and the volume V of Kxpicene against x, where
the lattice parameters of Kxpicene are determined based on
the model that assumes the monoclinic structure of solid
picene as maintained in Kxpicene solids. Contrary to the
simple prediction from the analogy with metal-intercalated
pentacene, that K atoms are intercalated in the space between
the layers with an expanded c, the experimental lattice para-
meters show that the c-axis actually shrinks monotonically
with x. On the other hand, the a-axis expands slightly while b
shrinks, which indicates the intercalation of K atoms within
the ab-plane. Here it is important to note that V decreased
with an increase in x in Kxpicene, where the decrease in V by K
intercalation to picene solids is contrary to expectation. The
change of orientation of picene molecules in the herringbone
arrangement, or distortion of picene molecules in the ab-layer
may lead to a reduction of V, as described later and also
suggested from theoretical structure. This contrasts with the
expansion of V in metal intercalated pentacene, where metal
atoms are intercalated to interlayer.83 As shown in the theore-
tical section below, a first-principles structure optimisation
also indicates the insertion of K atoms within each layer.81
Such behaviour is also found for Rbxpicene (Fig. 15(b)). To be
precise, the c in Rbxpicene expands slightly up to x = 2 and
shrinks drastically above x = 2. This small expansion for low
x contrasts with the behaviour of Kxpicene. The former may
suggest that Rb atoms are initially inserted into inter-layer
sites while further Rb metal atoms are incorporated intra-
layer. The behaviours of a and b in Rbxpicene are the same as Fig. 16 Crystal structure of K3picene optimized based on first-
that in Kxpicene. The result that the Rb metal atoms are at principle theoretical calculation. Viewed from (a) b-direction and
least in part intercalated into the ab-layer in Rb3picene, (b) c-direction. Large spheres represent K.
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magnitude than that, 7.8 K GPa1, of K3C60.86 The large electronic structure of solid picene through molecule–metal
negative pressure dependence in K3C60 may be interpreted with hybridisation and distortion. Thus the estimation of l
a model in which the width of the band that intersects the Fermi described above may be oversimplified because hybridisation
energy becomes larger with pressure, to reduce the N(eF). The Tc can strengthen the coupling. Therefore, we cannot at present
of metal-doped C60 decreases with pressure except for Cs3C60;12 conclude that picene superconductivity can be explained
which is a pressure-induced superconductor, with the highest by the BCS phononic mechanism. Further, the theoretical
Tc (= 35–38 K at B7 kbar) among C60 superconductors, as calculation also predicted that the Fermi surface, which is
mentioned in the previous section.72–74 The small pressure associated with the bands basically derived from the degen-
dependence of Tc in K3picene may originate from the tight erate LUMO and LUMO + 1 orbitals, exhibits a curious
(i.e., intra-layer) insertion of K atoms within solid picene, for coexistence of surfaces of differing spatial dimensionalities. So
which the band width is expected to change little because of the it is an interesting future problem to clarify which Fermi
tight stacking. This expectation is corroborated by the theore- surfaces are responsible for the superconductivity and whether
tical result that the wavefunction in the conduction band, which the multiband structure is relevant to the superconductivity.
originates from picene’s LUMOs, has considerable amplitude Fermiology has not yet been reduced to an experimental
on the metal atoms.81 Thus the small pressure dependence is discipline, but photoelectron spectroscopy of Kxpicene thin
consistent with the suggested insertion of K atoms into the films shows a clear peak at eF at 300 K, which confirms the
ab-plane. The fact that the Tc in the 7 K phase does not metallic character of Kxpicene.44 Photoelectron spectroscopy
appreciably change with chemical pressure, i.e., intercalating also suggests a breakdown of the rigid band picture in
metal atoms of different sizes in K3picene, Rb3picene and Kxpicene. The theoretical study of hydrocarbon superconduc-
Ca1.5picene, may also be consistent with the result for external tors is described in a subsequent section.
pressure on Kxpicene. Further studies of pressure dependence Now we turn to coronene (Fig. 4). This is important, since,
are now in progress. given the superconductivity of doped picene, an immediate
The mechanism of superconductivity is discussed experi- natural question is whether and how such superconductivity is
mentally here, with an aid of theoretical results. The N(eF) shared by other aromatic molecules. So we have inserted K
is estimated to be 1.2 states eV1 spin1 picene1 from the atoms into solid coronene to modify its electronic structure.
conduction ESR of K3picene (18 K superconductor).16 This One reason that coronene may be interesting is that the mole-
value is consistent with the N(eF), 2.2 states eV1 spin1 cule, with an inversion centre, has a much higher symmetry
picene187 estimated from the experimental Tc and theoretical than picene. A typical w–T plot for Kxcoronene is shown in
electron–phonon coupling l within the framework of BCS Fig. 17, where the Tc and shielding fractions are 7 K and
theory and also with the first-principles band structure B0.5%, respectively. While the precise value of x in this
calculation.81 Here it should be noted that the value of sample is not known, such samples are mostly obtained by
l E 200 meV, calculated for an isolated picene is so large that annealing K and coronene at a molar ratio of 3 : 1 at 105 Torr
the small N(eF) of 1–2 states eV1 spin1 picene1 produces a and 573 K, which provides the signature of a superconducting
Tc as high as C60 superconductors;87 the l is related to the transition. Further, some superconducting transitions are
dimensionless electron–phonon coupling constant l by found for K3coronene samples at Tc = 3.5, 7, 11 and 15 K
l = l N(eF). The N(eF) values for K3C60 and Rb3C60 are 17 (not shown), respectively. In fact, most Kxcoronene samples
and 22 states eV1 spin1 C601, respectively, as described in prepared with x = 2.5–3.5 show a signature of supercon-
Section 3.12,66 Thus, picene may be characterised as a super- ductivity, although the shielding fraction is still quite low.
conductor with large electron–phonon coupling. The l is Kxcoronene with x r 2.5 shows Pauli-type paramagnetism,
estimated by the DFT calculation of a picene molecule, and which indicates metallic behaviour. The crystal structure of
K atoms are regarded only as electron donors. The N(eF) for solid coronene (Fig. 4) is monoclinic (with a space group
K3picene (7 K superconductor) could not be estimated owing P21/a), and the lattice constants of a, b, c and b were deter-
to its very small conduction ESR, while that for Ca1.5picene mined to be 16.117(3), 4.7039(4), 10.099(2) Å, and 111.025(1)1,
(7 K superconductor) was estimated to be 0.5 states respectively, from the X-ray diffraction pattern of a pure
eV1 spin1 picene1. This result is consistent with the predic- coronene powder sample. The experimental X-ray diffraction
tion from BCS theory that the higher Tc superconductor has pattern of coronene is shown in Fig. 18 along with the pattern
the larger N(eF). For the electron–phonon coupling, we have to
estimate the coupling for doped solid picene rather than for an
isolated molecule, for a realistic estimate of Tc in the phonon
mechanism. Another interesting possibility is an electron
mechanism, as is mentioned in the theoretical section below.
Behind this observation is an important point regarding
the band structure of Kxpicene, for which a first-principles
calculation81 suggests a strong hybridisation between the
orbitals of K atoms and picene molecules. If we couple this
with the distortion of the herringbone structure upon doping,
the rigid band picture is invalidated in Kxpicene for two
reasons.81 The inserted metal atoms not only work as electron
donors but, as theoretically described below, also modify the Fig. 17 w as a function of T for Kxcoronene.
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undoped picene and K3picene, where not only the molecular

arrangement is modified by doping but the wavefunction is
also strongly deformed by strong hybridisation between the
molecular orbitals and alkali-metal orbitals.
In the theoretical study the atomic positions, including
hydrogen atoms, are first optimised with the lattice parameters
fixed at their measured values.37 The angle between the
inequivalent molecular planes turned out to be 611 in the
optimised geometry, which is close to the measured 581. Each
molecule deviates slightly from planarity due to the molecular
overcrowding, as seen experimentally.37 The calculated elec-

tronic band structure in Fig. 19 shows that the system is,
electronically, quasi-two dimensional, since the dispersion
Fig. 18 Experimental and calculated X-ray diffraction patterns of along the c* axis is much smaller those along a*b*. The
coronene solids. undoped system is an insulator with a band gap of 2.36 eV,
while the experimental value is 3.3 eV.41 Such an underestima-
calculated for the above lattice. These values are consistent tion is generally seen in LDA. We can also note that the band
with those determined previously with single crystals of dispersions along kb* = 1/2 are doubly degenerate, unlike
coronene,38 as described in Section 2. The solid comprises a those of triclinic crystalline tetracene or pentacene. The den-
stack (along c) of layers (in the ab-plane), each consisting of sity of electrons, displayed in Fig. 20, spreads over each
coronene molecules arranged in a herringbone pattern, so that molecule basically uniformly, with no significant dimerisation.
the layered herringbone structure is similar to those in picene The valence band comprises four bands, two of which mainly
and pentacene. reflect the character of the HOMOs of the picene molecule.
The comparison of the experimental Raman scatterings of
Kxcoronene with the theoretical prediction allows one to
determine the number of electrons; preliminary investigation
shows a good consistency between the experimental and theo-
retical Raman frequencies (not shown), indicating that the
nominal x value is close to the actual number of electrons.82
Thus superconducting coronene materials are likely to be
doped with three electrons per coronene molecule. Experi-
mental studies of the positions of metal atoms in the crystals
and their electronic structure are now in progress for Kxcoronene.
The theoretical electronic structure is also now being obtained,
and the theoretical band structure of solid coronene shows that
the conduction band again exhibits a multiband structure.88
Recently, it was also found that Rb-intercalated coronene is
a superconductor. Subsequently, a Chinese research group
discovered superconductivity in K3phenanthrene,89 in which
phenanthrene is a phenacene-type molecule with three
benzene rings (see Fig. 5). The Tc is B5 K and the maximum
shielding fraction of K3phenanthrene reaches B20%. Further,
interesting positive pressure dependence is observed for
K3phenanthrene. This discovery clearly shows a diversity of
hydrocarbon superconductor.
5. Theoretical approach to hydrocarbon

superconductors
A first-principles electronic structure calculation was first
performed by Kosugi et al.,81 in the density functional theory
(DFT) with the local-density approximation (LDA) for both
pristine and doped solid picene. Of particular interest for solid
aromatic molecules are the main characters of the conduction
bands in terms of the relevant molecular orbitals. Kosugi et al.
have shown that the conduction band comprises four bands,
and that the transfer energies, hence the band structure, Fig. 19 (a) First-principles band structure of undoped solid picene.
reflect both the herringbone arrangement of molecules and The conduction band (comprising four branches, CB1–CB4) is shaded.
the stacking of the herringbone layers. This applies to both (b) A blow-up of the conduction band along with the density of states.
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reproduces the DFT-LDA band dispersion (Fig. 21(b)).

The transfer integrals, tij = hwl,h(ri)|HKS|wl,h(rj)i, are defined
as the matrix elements of the Kohn–Sham Hamiltonian
HKS between the WO’s. As seen in Fig. 20, the LUMO
(LUMO + 1) are antisymmetric (symmetric) with respect
to the plane that bisects the long molecular axis, and wl,h
(BLUMO (LUMO + 1)) are nearly mirror images of each
other, with a slight polarisation from the centre of the
molecule. The transfer integrals with significant magnitudes
are depicted in Fig. 21(c).
The matrix element of the Kohn–Sham Hamiltonian HKS

between the LUMO and LUMO + 1 in the crystal is approxi-
mately given by |hf LUMO|HKS|f LUMO+1i| D (ehel)/2 D
11.3 meV, where eh,l tii(0). This is not negligible against
the gap of 67.8 meV between the LUMO and LUMO + 1
calculated for the molecule, which leads to the hybridisation of
Fig. 20 Top panels depict calculated Bloch wave functions for con-
the LUMO and (LUMO + 1) derived bands. This contrasts
duction band (CB1–CB4) at G in undoped solid picene crystals as
with pentacene, for which the calculated gap in the molecule
compared with LUMO and LUMO + 1 orbitals of an isolated picene
molecule. Lines represent bonding and antibonding combinations (see
between the LUMO and LUMO + 1 is as high as 1.28 eV, and
text). Bottom panels depict the valence bands (VB1, VB2) along with the bands derived from them do not hybridise.
the HOMO. In doped solid picene, carriers are electrons, in contrast to the
case of BEDT-TTF or TMTSF. The measured lattice para-
More precisely, in each layer in the crystal, the HOMO (f) of meters16 of K2.9picene are a = 8.707, b = 5.912, c = 12.97 in Å
each molecule splits into bonding (wl) and antibonding (wh) with b = 92.771. One conspicuous feature is that the c-axis
states due to the hopping to the four adjacent inequivalent shrinks while the a-axis expands upon doping. This contrasts
molecules as confirmed in Fig. 20 (bottom panels). The other with crystalline pentacene, where significant expansions of
two valence bands are mainly HOMO 1 in character, so the c-axis are known to occur when doped with alkali
that all four valence bands mainly derive from HOMO and elements83,85,90–93 as a result of the intercalants being accom-
HOMO 1. modated in the interlayer region. This suggests that in the case of
If we turn to the conduction band, they comprise four bands picene, the dopants may not be wholly inserted into the inter-
over a width of 0.39 eV. A similar analysis shows that they layer region.
mainly derive from LUMO and LUMO + 1, as summarised Another point of interest is whether the ‘‘interlayer states’’
in Fig. 20 (top panels). Kosugi et al.81 have built a tight- occurring in GIC can be relevant. A body of studies, both
binding model from the first-principles electronic structure via experimental94 and theoretical,64 indicate that the interlayer
the maximally localised Wannier orbitals (WOs; Fig. 21(a)), states of graphite that reside in the space between the carbon
where the band structure in the tight-binding model accurately layers affect the electronic structure in general and super-
conductivity in particular in GIC. Namely, the interlayer
states, located above the Fermi level in pristine graphite,
strongly hybridise with the valence states of the intercalant
atoms, thereby making the electronic bands arising from the
hybridised states pulled down to intersect the Fermi level. In
solid picene, we have found that, while there exist analogues of
the interlayer state (where we define a layer as the array of
molecules in the ab plane), they sit 1.5 eV above the conduc-
tion band bottom. Even when doped, the dopant atoms,
which are expected to be accommodated within the layer as
suggested above, should experience little hybridisation with
the interlayer states.
A rough search for lower-energy configurations shows that
the energies of the intralayer insertions (Fig. 22(a)) are indeed
about 0.2 eV lower in energy per molecule than those of the
interlayer insertions. The angle between the molecular planes
Fig. 21 (a) Maximally localised Wannier orbitals (lower-energy wl
obtained is an obtuse 1141 for the doped case, which is due to
and higher-energy wh) constructed for the conduction band. (b) Tight-
the expanded a and contracted b axes. The distortion from a
binding fit (curves) as compared with the DFT–LDA band structure
(dots) for the conduction band. (c) The tight-binding model deduced planar molecular structure also increases with doping. The
from the downfolding is represented in terms of transfer integrals electronic band structure significantly differs from those in
(arrows; only those greater than 25 meV displayed) between the intra- pristine picene, so that the rigid band assumption is indeed
layer molecules, with ellipses representing the associated Wannier invalid. The band structure for a geometry with the K atoms
orbitals and overlaps representing the difference in the c-axis height. removed but the other atoms and the doping level fixed differs
Fig. 23 Clar structures of hydrocarbons. For the definition of Clar

sextets (circles) and arrows, see text.
an interesting possibility. The optimised structure, Fermi sur-

face and electronic band structures of K3coronene are also
shown in Fig. 22(b) and the feature of the Fermi surface is
similar to that of K3picene but with a different topology.88
Finally, let us say a few words about the aromaticity of
molecules in general and its relevance to picene and coronene.
The definition of aromaticity in aromatic hydrocarbons has
been a big issue in quantum chemistry. The simplest definition,
as depicted in Fig. 23, is in terms of the ‘‘Clar structure’’
proposed in the 1960s.95,96 For a given aromatic molecule,
we can draw a Clar sextet, which is defined as a resonating
benzene ring. The rules are: (1) Clar sextets must not share an
Fig. 22 Optimised geometries (large spheres: K), Fermi surfaces and edge. (2) Draw the largest possible number of sextets. There
electronic band structures of (a) K3picene and (b) K3coronene. The may be more than one realisation, which should then be
origins of energy are set to their Fermi levels. The geometry of indicated with arrow(s). (3) When the Clar sextets exhaust
K3picene was obtained with the experimental lattice parameters for all the chemical bonds (i.e., with no other double bonds), then
K2.9picene, while that of K3coronene with the experimental lattice
the structure is called ‘‘fully benzenoid’’, which defines, in this
parameters for pristine structure.
scheme, the most aromatic case. There are more recent studies
on this picture from quantum chemical calculations.97 In
from the true one. So the rigid band picture is broken for two the Clar picture, picene is not fully benzenoid. Neither is
reasons: structural change and hybridisation with K, where coronene, for which there are two Clar structures. These differ
the former effect is stronger. The Bloch states near the Fermi from straight arrays of benzene rings such as pentacene, for
level, however, still retain the character of the LUMO and which there are as many Clar realisations as the number of
LUMO + 1. In Fig. 22(a) we have displayed the band rings. We can summarise (Fig. 23) that for zigzag benzene
structure and the Fermi surface for the experimental lattice rings: (a) odd number of rings (picene, phenanthrene etc.) are
parameters. We can see that we have again four branches for non-fully benzenoid (with each molecule having a unique Clar
the conduction band. The Fermi surface for the doped system structure), while (b) even numbers of rings (chrysene etc.) are
in Fig. 22(a) consists of multiple surfaces, which contain also non-fully benzenoid (with each having multiple Clar
warped, interwoven one-dimensional (planar) surfaces and a structures). Straight benzene rings (tetracene, pentacene etc.)
three-dimensional (pocket) surface, some of which involve are non-fully benzenoid (each having many Clar structures).
hopping between MOs via K atoms. Future problems include Conversely, (a) Fully benzenoid (highest aromaticity) mole-
the implications of the features of the Fermi surface on the cules include graphene, and its fragments such as triphenylene.
mechanisms of superconductivity. An electron mechanism is (b) Non-fully benzenoid (moderate aromaticity) molecules
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include those with unique Clar structures (phenanthrene, but several tens of volts are required for the operation of
picene, coronene) and those with multiple Clar structures organic FETs with an SiO2 gate dielectric. However, low-
(tetracene, pentacene, chrysene). So one interesting future voltage operation of FETs is important in view of the
problem is whether and how these properties affect the elec- practical applications of organic FETs.
tronic structure when these molecules are crystallised. Picene thin film FETs were firstly fabricated with a thick SiO2
gate dielectric (400 nm) and the field-effect mobility as high as
1 cm2 V1 s1 was obtained under O2 atmosphere.41,98 The FET
6. Accumulation of electrostatic carriers in picene has an O2 gas sensing property which corresponds to a drastic
crystals—a prospect increase in mobility and switch-on drain current under an O2
atmosphere. The large hysteresis in the transfer curve was also
Chemical doping of alkali and alkali-earth metal atoms into observed owing to bias stress effect, but the hysteresis completely
the hydrocarbons picene and coronene has been performed to disappeared if we use hydrophobic parylene gate dielectric.99
modify their electronic structures to produce superconducting The mobility also reached 1.1 cm2 V1 s1 in the hysteresis-free
behaviour. Until recently, only electron-doping of hydro- picene thin film FET. Furthermore, the relatively high mobility
carbons had succeeded. Another way to dope hydrocarbons of 0.75 cm2 V1 s1 was obtained for [7]phenacene thin film
is to modify their electronic structures by the accumulation of FET with a thick SiO2 gate dielectric (400 nm).42
electrostatic carriers. An important advantage of this method Subsequently, we have already succeeded in realising a
is that the technique can potentially accumulate not only low-voltage operation in picene and [7]phenacene FETs with
electrons but also holes into hydrocarbons. Further, this high ex gate dielectrics such as Hf O2, Ta2O5 and ZrO2 as well
technique may not cause any significant changes in crystal as a thin SiO2 gate dielectric (40 nm thick).42,100 Effective
structures, which facilitates study of the correlation between carrier accumulation at a low bias voltage is indispensable for
the electronic structure and superconductivity. Electrostatic low-voltage FET operations, but the carriers necessary for
carrier accumulation can be achieved by use of a field-effect FET operation are at most 1/10 carrier per molecule.
transistor (FET) structure. An FET is an electronic device in Here it should be noticed that at least one electron (or hole)
which the carriers accumulate in a semiconductor along an per organic molecule is required to control the physical
interface in the FET geometry when a gate voltage is applied properties of organic semiconductors. The carrier density
to the semiconductor across the interface with a dielectric accumulated by applying a gate voltage VG is expressed as
insulator, as shown in Fig. 24(a).
Organic FETs have been fabricated in which organic thin Co VG e0 ex VG
n¼ ¼ ; ð1Þ
films are used as active layers, with solid gate dielectrics such e de
as SiO2, Al2O3, HfO2, Ta2O5, ZrO2, BaxSr1xTiO3 (BST) or where n is the density of accumulated carriers, and e the
polymers. The capacitance per area Co (= e0ex/d) is defined by elementary charge. Actually, we have to consider the break-
the thickness d and dielectric constant ex of the gate insulator; down voltage Vbreak of gate dielectrics, which corresponds to
e0 is the permittivity, 8.85418 1014 F cm1 in vacuum. the maximum gate voltage that can be applied to the gate
Generally, 1012–1013 carriers per cm2 are accumulated into the dielectrics, Vmax
G . V
break
can be empirically given as
active layers of FETs with solid gate dielectrics because of
2 107
their low ex values: ex = 3.9 for SiO2, B10 for Al2O3, 20–25 Vmax
G ¼V
break
¼ Ebreak d ¼ pffiffiffiffi d; ð2Þ
for Hf O2, Ta2O3 and ZrO2, B300 for BST, and 3.0 for ex
parylene (polymer). The density 1012–1013 cm2 implies where Ebreak, in units of V cm1, is the electric field at the
1/100–1/10 of a carrier per molecule. Well-defined FET char- breakdown point of the gate dielectrics. Thus the maximum
acteristics have been observed with these gate dielectrics, carrier density nmax that can be accumulated by the use of gate
dielectrics is derived with eqn (1) and (2) as
pffiffiffiffi
e0 ex max e0 ex 2 107 2 107 e0 ex
nmax ¼ VG ¼ pffiffiffiffi d ¼ : ð3Þ
ed ed ex e
As seen from this, nmax depends only on ex of the gate dielectric.

If we use a BST gate dielectric with ex = 300, the nmax amounts
to 1.9 1014 cm2 from eqn (3). Here, the carriers are
substantially accumulated in the first layer of organic semi-
conductor at the interface with the gate dielectric. The number
of carriers per picene molecule is estimated to be at most
0.5 since 3.8 1014 picene molecules exist in the first layer of
organic semiconductors. This suggests that an organic FET
with a solid gate dielectric cannot produce enough carriers to
control the physical properties of organic molecules.
Recently, FET devices with an electric double layer (EDL)
Fig. 24 Device structures of picene FET with (a) solid gate and capacitor have attracted serious attention because of their large
(b) ionic liquid gate dielectrics. (c) Schematic representation for ionic Co value. Ueno et al. have in fact succeeded in observing a field-
liquid applied negative bias voltage. induced superconductivity in SrTiO3 (STO).101 It has been known
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that, while STO is an insulator, a bulk SrNbxTi1xO3 (x = 0.002) gate insulators, in order to accumulate more carriers with a
is a superconductor with Tc = 0.4 K.102 They fabricated a STO large Co. Furthermore, FETs with single crystals of organic
single-crystal FET with a polymer-electrolyte liquid gate- molecules are also of importance for effective carrier-
dielectric (polyethylene oxide containing KClO4), for which accumulation in the valence/conduction band because thin
the temperature dependence of the sheet resistance, rs, in VG = 3 V films have numerous trap centres that capture the accumulated
shows a rapid drop at 0.4 K, i.e., the electron accumulation in carriers. We have already succeeded in operating a picene
STO and the resulting field effect produced a superconducting single-crystal FET with a solid gate and ionic liquid
phase. Subsequently, Ye et al. produced a superconducting dielectrics.106 Actually, the most serious problem is that
transition at 15.2 K in ZrNCl single crystals by using an FET field-induced carrier accumulation in picene has been achieved
structure with an ionic liquid (IL), N,N-diethyl-N-(2-methhoxy- only for holes, i.e., the picene FET operates only in the
ethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide p-channel. Since we now know that superconductivity in bulk

(demeTFSI), as the gate dielectric.103 It is further reported that picene solids occurs with a three-electron donation to the
the field-induced superconducting transition has a 2D nature. picene molecule, an n-channel picene FET device must be
The Co of demeTFSI is 9.2 mF cm2, a value larger than that of fabricated to produce superconductive picene. We recently
the polyethylene electrolyte, where the large sizes of anion and confirmed weak n-channel operation in a picene thin film FET
cation in demeTFSI should prevent the penetration of ions into with an IL gate dielectric, which may lead to stable n-channel
single crystals. Thus IL may have significant advantages when operation and effective electron accumulation in the picene
used in FETs. active layer. However, according to the band structure calcu-
A schematic representation of an EDL with ILs is shown in lation, the valence band also has a multi-band structure
Fig. 24(b). The anion and cation in the IL are distinguished by (basically arising from HOMO and HOMO 1),81 so that it
the application of voltage to the gate electrode (Fig. 24(c)). If a is an interesting problem to consider the possibility of super-
negative voltage is applied to the electrode, the anions conductivity with hole doping. To obtain novel phenomena
approach the active layer to form a very thin (1 nm) EDL. such as metal-insulator and superconducting transitions by
The EDL can produce a large Co to accumulate a high density modifying the electronic structure, further studies are now in
of carriers in the active layer. We have fabricated picene and progress. One focus is to make a high-mobility and trap-free
[7]phenacene EDL FETs with two ILs, 1-ethyl-3-methyl- single-crystal FET to effectively accumulate carriers, another
imidazoriumbis(trifluoromethanesulfonyl)imide (emimTFSI) is to look for new high-capacitance IL gate dielectrics to
and 1-butyl-3-methylimidazorium hexafluorophosphate generate high carrier densities that can reach three electrons
(bmim[PF6]).104,105 The Co is B10 mF cm2, which is larger per picene molecule.
by three orders of magnitude than that, B10 nF cm2, of
400 nm thick SiO2. If all the induced holes are injected into the
7. Summary and concluding remarks
valence band by applying a VG of 3 V to the gate electrode,
0.5 holes are donated to each picene molecule. Actually, the The discovery of hydrocarbon superconductors is an exciting
holes may be partly captured by the trap centres in the picene new development in the search for carbon-based superconduc-
thin films. The drain current ID against VG for a picene FET tors. The strong electron–phonon coupling of the hydrocarbon
with emimTFSI is shown in Fig. 25. The threshold voltage VTH molecule may produce high Tcs, comparable to those of C60
that corresponds to the VG necessary for the FET’s operation is superconductors. Due to the multiband character of the con-
as low as 1 V. Thus low-voltage operation is completely duction and valence bands, interesting electron correlation
achieved in this FET, but the accumulated carriers are not effects including electron mechanisms of superconductivity
numerous enough to control the physical properties. We have may also be expected. Hydrocarbon molecules, especially
to remember that, while the carrier concentration necessary for aromatic compounds, are most typical of organic compounds,
modification of the electronic structures of STO and ZrNCl is so that the discovery of superconductivity in metal-doped
smaller than 0.05, the picene molecule requires 3 electrons for aromatic molecules opens a new and promising field of
superconductivity. research. We have already discovered superconductivity in
To realise the electrostatically induced superconductivity in K3picene, Rb3picene, and Ca1.5picene, as well as K3coronene.
an organic molecule, it may be indispensable to use ILs as the The highest Tc is 18 K for K3picene, which exceeds the highest
Tc, 14.2 K, for bis(ethylenedithio)tetrathiafulvalene (BEDT-
TTF) organic superconductors.107 To date, superconductivity
has been observed in the region of x = 2.6 to 3.5 in Kxpicene,
Rbxpicene and Kxcoronene. It is not clear whether and why
the composition of x = 3 is magic for their superconductivity.
The shifts of Raman scattering peaks accompanying metal
insertion into these hydrocarbon solids confirm the electron
donation from the metal atoms to the hydrocarbon molecules.
The lattice constants determined from X-ray diffraction
patterns show that the metal atoms are inserted within the
herringbone layers, and the distance between the layers shrinks
Fig. 25 Transfer curves for picene FET with ionic liquid gate with the insertion of metal atoms. We have also reviewed
dielectric (emim[TFSI]) in (a) liner and (b) logarithmic scales. theoretical aspects of these metal-doped hydrocarbon solids,
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where the obtained first-principles band structures indicate 12 M. S. Dresselhaus, G. Dresselhaus and P. C. Ekulund, Science of
that the conduction (valence) bands arise from more than fullerenes and carbon nanotubes, Academic Press, San Diego,
1996.
one LUMOs (HOMOs) of the constituent molecule. The Fermi 13 S. L. Bud’ko, G. Larertot, C. Petrovic, C. E. Cunningham,
surface of the multiband structure is found to exhibit a N. Anderson and P. C. Canfield, Phys. Rev. Lett., 2001, 86, 1877.
suggestive coexistence of surfaces having different spatial 14 Y. Takada, J. Phys. Soc. Jpn., 1996, 65, 1544.
dimensionalities, which applies to both doped picene and 15 M. Tezuka, R. Arita and H. Aoki, Phys. Rev. Lett., 2005,
95, 226401.
doped coronene. 16 R. Mitsuhashi, Y. Suzuki, Y. Yamanari, H. Mitamura,
In conclusion, while superconductivity has now been T. Kambe, N. Ikeda, H. Okamoto, A. Fujiwara, M. Yamaji,
observed in different hydrocarbons, picene and coronene, the N. Kawasaki, Y. Maniwa and Y. Kubozono, Nature, 2010,
464, 76.
search for hydrocarbon superconductors has only just begun.
17 R. Arita, K. Kuroki and H. Aoki, Phys. Rev. B: Condens. Matter,
Detailed studies, both experimental and theoretical, will be 1999, 60, 14585.
indispensable for the unambiguous characterisation and 18 P. Monthoux and G. G. Lonzarich, Phys. Rev. B: Condens.
clarification of the mechanism of superconductivity in these Matter, 1999, 59, 14598.
19 T. Minakata, M. Ozaki and H. Imai, J. Appl. Phys., 1993,
new hydrocarbon superconductors, which constitute a new 74, 1079.
class of carbon-based superconductor. 20 Y. Matsuo, S. Sasaki and S. Ikehata, Phys. Lett. A, 2004, 321, 62.
21 Y. Kaneko, T. Suzuki, Y. Matsuo and S. Ikehata, Synth. Met.,
2005, 154, 177.
Acknowledgements 22 F. B. Mallory, K. E. Butler, A. C. Evans, E. J. Brondyke,
C. W. Mallory, C. Yang and A. Ellenstein, J. Am. Chem. Soc.,
The authors are indebted to Hiroki Tsutakawa, Keiko Ogawa, 1997, 119, 2119.
and Nobuyuki Kawai for their kind assistance with alkali- 23 G. Portella, J. Poater, J. M. Bofill, P. Alemany and M. Solà,
J. Org. Chem., 2005, 70, 2509.
metal doping of picene and FET fabrication. The experimental 24 N. P. Buu-Hoı̈ and N. Hoán, J. Org. Chem., 1949, 14, 1023.
study is partly supported by Grant-in-aid (22244045 and 25 F. B. Mallory and C. W. Mallory, Org. React., 1984, 30, 1.
22013012) from MEXT, Japan, and by Scientific Research 26 F. B. Mallory, K. E. Butler, A. Bérubé, E. D. Luzik, Jr.,
Project ‘New Functional Materials for Energy Production, C. W. Mallory, E. J. Brondyke, R. Hiremath, P. Ngo and
P. J. Carroll, Tetrahedron, 2001, 57, 3715.
Storage and Transport’ supported from Okayama University 27 S. Some, B. Dutta and J. K. Ray, Tetrahedron Lett., 2006,
and MEXT, Japan. TK and HA wish to thank Takashi 47, 1221.
Miyake, Shoji Ishibashi, and Ryotaro Arita for their 28 L. Minuti, A. Taticchi, E. Gacs-Baitz and A. Marrocchi,
Tetrahedron, 1998, 54, 10891.
collaboration in the theoretical studies. RE wishes to thank 29 R. G. Harvey, J. Pataki, C. Cortez, P. Di Raddo and C. X. Yang,
Yukiaki Ishida, Kenji Koizumi, and Shik Shin for their J. Org. Chem., 1991, 56, 1210.
collaboration in PES study. The present work is partially 30 Y. Nakano, M. Saito and H. Nakamura, PCT Int. Appl. WO,
supported by the Next Generation Supercomputer Project 2010016511 A1, 2010.
31 T.-A. Chen, T.-J. Lee, M.-Y. Lin, S. M. A. Sohel, E. W.-G. Diau,
from MEXT, Japan, and by Scientific Research on Priority S.-F. Lush and R.-S. Liu, Chem.–Eur. J., 2010, 16, 1826.
Areas ‘‘New Materials Science Using Regulated Nano 32 H. Okamoto, Y. Kubozono, M. Yamaji and M. Goda, Jpn. Kokai
Spaces’’ under Grant No. 19051016 from MEXT, Japan. Tokkyo Koho JP 2010143895, 2010.
33 G. R. Desiraju and A. Gavezzotti, Acta Crystallogr., Sect. B:
Struct. Sci., 1989, 45, 473.
References 34 C. C. Mattheus, A. B. Dros, J. Baas, A. Meetsma, J. L. de Boer
and T. T. M. Palstra, Acta Crystallogr., Sect. C: Cryst. Struct.
1 N. B. Hannay, T. H. Geballe, B. T. Matthias, K. Abndres, Commun., 2001, 57, 939.
F. Schmidt and D. MacNair, Phys. Rev. Lett., 1965, 14, 225. 35 C. C. Mattheus, G. A. de Wijs, R. A. de Groot and T. T. M.
2 N. Emery, C. Herold, M. d’Astuto, V. Garcia, Ch. Bellin, Palstra, J. Am. Chem. Soc., 2003, 125, 6323.
J. F. Mareche, P. Lagrange and G. Loupias, Phys. Rev. Lett., 36 T. Siegrist, C. Besnard, S. Haas, M. Schiltz, P. Pattison,
2005, 95, 078003. D. Chernyshov, B. Batlogg and C. Kloc, Adv. Mater., 2007,
3 D. Jerome, A. Mazaud, M. Ribault and K. Bechgaard, J. Phys. 19, 2079.
Lett. (Paris), 1980, 41, L95. 37 A. De, R. Ghosh, S. R. Roychowdhury and P. Roychowdhury,
4 H. Taniguchi, M. Miyashita, K. Uchiyama, K. Satoh, N. Mori, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1985, 41, 907.
H. Okamoto, K. Miyagawa, K. Kanoda, M. Hedo and 38 T. Echigo, M. Kimata and T. Maruoka, Am. Mineral., 2007,
Y. Uwatoko, J. Phys. Soc. Jpn., 2003, 72, 468. 92, 1262.
5 A. F. Hebard, M. J. Rosseinsky, R. C. Haddon, D. W. Murphy, 39 T. Yamamoto, S. Nakatani, T. Nakamura, K. Mizuno, A. H.
S. H. Glarum, T. T. M. Palstra, A. P. Ramirez and A. R. Kortan, Matsui, Y. Akahama and H. Kawamura, Chem. Phys., 1994,
Nature, 1991, 350, 600. 184, 247.
6 K. Tanigaki, T. W. Ebbesen, S. Saito, J. Mizuki, J. S. Tsai, 40 T. Yasuda, T. Goto, K. Fujita and T. Tsutsui, Appl. Phys. Lett.,
Y. Kubo and S. Kuroshima, Nature, 1991, 352, 222. 2004, 85, 2098.
7 T. T. M. Palstra, O. Zhou, Y. Iwasa, P. E. Sulewski, 41 H. Okamoto, N. Kawasaki, Y. Kaji, Y. Kubozono, A. Fujiwara
R. M. Fleming and B. R. Zegarski, Solid State Commun., 1995, and M. Yamaji, J. Am. Chem. Soc., 2008, 130, 10470.
93, 323. 42 H. Sugawara, Y. Kaji, K. Ogawa, R. Eguchi, S. Oikawa,
8 N. Plakida, High-temperature cuprate superconductors in solid- H. Gohda, A. Fujiwara and Y. Kubozono, Appl. Phys. Lett.,
state sciences, ed. M. Cardona, P. Fulde, K. Von Klitzing, 2011, 98, 013303.
R. Merlin, H.-J. Queisser and H. Stormer, Springer, Berlin, 2010. 43 R. Eguchi, Abstract of 7th International Conference on Organic
9 Y. Kamihara, T. Watanabe, M. Hirano and H. Hosono, J. Am. Electronics, Roma, June 2011. R. Eguchi, K. Akaike, Y. Kaji,
Chem. Soc., 2008, 130, 3296. Y. Ishida, K. Koizumi, S. Shin, K. Kanai, A. Fujiwara, T. Kambe
10 Z. Ren, W. Lu, J. Yang, W. Wei, X. L. Shen, Z. Lin, G. Che, and Y. Kubozono, unpublished.
X. Dong, L. Sun, F. Zhou and Z. Zhao, Chin. Phys. Lett., 2008, 44 H. Okazaki, T. Wakita, T. Muro, Y. Kaji, X. Lee, H. Mitamura,
25, 2215. N. Kawasaki, Y. Kubozono, Y. Yamanari, T. Kambe, T. Kato,
11 J. Nagamatsu, N. Nakagawa, T. Muranaka, Y. Zenitani and M. Hirai, Y. Muraoka and T. Yokoya, Phys. Rev. B: Condens.
J. Akimitsu, Nature, 2001, 410, 63. Matter, 2010, 82, 195114.
View Article Online
45 F. Roth, M. Gatti, P. Cudazzo, M. Grobosch, B. Mahns, 74 A. Y. Ganin, Y. Takabayashi, P. Jeglic, D. Arcon, A. Ptotocnik,
B. Büchner, A. Rubio and M. Knupfer, New J. Phys., 2010, P. J. Barker, Y. Ohishi, M. T. McDonard, M. T. Tzirakis,
12, 103036. A. McLennan, G. R. Darling, M. Takata, M. J. Rosseinsky
46 O. D. Jurchescu, J. Baas and T. T. M. Palstra, Appl. Phys. Lett., and K. Prassides, Nature, 2010, 466, 221.
2004, 84, 3061. 75 E. A. Ekimov, V. A. Sidorokov, E. D. Bauer, N. N. Mel’nik,
47 T. W. Kelley, P. F. Baude, C. Gerlach, D. E. Ender, D. Muyres, N. J. Curro, J. D. Thompson and S. M. Stishov, Nature, 2004,
M. A. Haase, D. E. Vogel and S. D. Theiss, Chem. Mater., 2004, 428, 542.
16, 4413. 76 Y. Takano, T. Takenouchi, S. Ishii, S. Ueda, T. Okutsu,
48 N. Karl, Synth. Met., 2003, 133, 649. I. Sakaguchi, H. Umezawa, H. Kawarada and M. Tachiki,
49 N. Koch, A. Vollmer, I. Salzmann, B. Nickel, H. Weiss and Diamond Relat. Mater., 2007, 16, 911.
J. P. Rabe, Phys. Rev. Lett., 2006, 96, 156803. 77 Y. Takano, J. Phys.: Condens. Matter, 2009, 21, 253201.
50 H. Yamane, E. Kawabe, D. Yoshimura, R. Sumii, K. Kanai, 78 V. A. Sidorov and E. A. Ekimov, Diamond Relat. Mater., 2010,
Y. Ouchi, N. Ueno and K. Seki, Phys. Status Solidi B, 2008, 19, 351.
245, 793. 79 S. Okada, R. Arita, A. Oshiyama, Y. Matsuo, E. Nakamura and

51 H. Kakuta, T. Hirahara, I. Matsuda, T. Nagao, S. Hasegawa, H. Aoki, Chem. Phys. Lett., 2004, 399, 157.
N. Ueno and K. Sakamoto, Phys. Rev. Lett., 2007, 98, 80 K. Holczer and R. L. Whetten, Carbon, 1992, 30, 1261.
247601. 81 T. Kosugi, T. Miyake, S. Ishibashi, R. Arita and H. Aoki,
52 M. Ohtomo, T. Suzuki, T. Shimada and T. Hasegawa, Appl. J. Phys. Soc. Jpn., 2009, 78, 113704.
Phys. Lett., 2009, 95, 123308. 82 T. Mitamura, X. He, R. Eguchi, T. Takahashi, T. Kato,
53 S. Machida, Y. Nakayama, S. Duhm, Q. Xin, A. Funakoshi, T. Kambe, A. Fujiwara and Y. Kubozono, to be submitted.
N. Ogawa, S. Kera, N. Ueno and H. Ishii, Phys. Rev. Lett., 2010, 83 T. Ito, T. Mitani, T. Takenobu and Y. Iwasa, J. Phys. Chem.
104, 156401. Solids, 2004, 65, 609.
54 H. Ding, C. Reese, A. J. Mäkinen, Z. Bao and Y. Gao, Appl. 84 A. Hansson, J. Bohlin and S. Stafstrom, Phys. Rev. B: Condens.
Phys. Lett., 2010, 96, 222106. Matter Mater. Phys., 2006, 73, 184114.
55 I. T. Belash, O. V. Zharikov and A. V. Pal’nichenko, Solid State 85 Y. Matsuo, T. Suzuki, Y. Yokoi and S. Ikehata, J. Phys. Chem.
Commun., 1987, 63, 153. Solids, 2004, 65, 619.
56 I. T. Belash, A. D. Bronnikov, O. V. Zharikov and A. V. 86 G. Sparn, J. D. Thompson, S.-M. Huang, R. B. Kaner,
Pal’nichenko, Solid State Commun., 1987, 64, 1445. F. Diederich, R. L. Whetten, G. Grüner and K. Holczer, Science,
57 I. T. Belash, O. V. Zharikov and A. V. Palnichenko, Synth. Met., 1991, 252, 1829.
1989, 34, 47. 87 T. Kato, T. Kambe and Y. Kubozono, Phys. Rev. Lett., in press.
58 I. T. Belash, O. V. Zharikov and A. V. Palnichenko, Synth. Met., 88 T. Kosugi, T. Miyake, S. Ishibashi, R. Arita and H. Aoki, Phys.
1989, 34, 455. Rev. B: Condens. Matter, 2011, 84, 020507(R).
59 I. T. Belash, A. D. Bronnikov, O. V. Zharikov and A. V. 89 X. F. Wang, R. H. Liu, G. Gui, Y. L. Xie, Y. J. Yan, J. J. Ying,
Pal’nichenko, Solid State Commun., 1989, 69, 921. X. G. Luo and X. H. Chen, Condens. Matter, arXiv:1102.4075v1.
60 I. T. Belash, A. D. Bronnikov, O. V. Zharikov and A. V. 90 T. Minakata, I. Nagoya and M. Ozaki, J. Appl. Phys., 1991,
Pal’nichenko, Synth. Met., 1990, 36, 283. 69, 7354.
61 B. Outti and P. Lagrange, C. R. Acad. Sci., Paris Ser. II, 1991, 91 T. Minakata, H. Imai and M. Ozaki, J. Appl. Phys., 1992, 72, 4178.
313, 1135. 92 Y. Matsuo, S. Sakai and S. Ikehata, Phys. Lett. A, 2004, 321, 62.
62 M. H. Upton, T. R. Forrest, A. C. Walters, C. A. Howard, 93 B. Fang, H. Zhou and I. Homma, Appl. Phys. Lett., 2005,
M. Ellerby, A. H. Said and D. F. McMorrow, Phys. Rev. B: 86, 261909.
Condens. Matter, 2010, 82, 134515. 94 A. Koma, K. Miki, H. Suematsu, T. Ohno and H. Kamimura,
63 J. S. Kim, L. Boeri, R. K. Kremer and F. S. Razavi, Phys. Rev. B: Phys. Rev. B, 1986, 34, 2434.
Condens. Matter, 2006, 74, 214513. 95 E. Clar, Polycyclic Hydrocarbons, Academic Press, London, 1964.
64 G. Csányi, P. B. Littlewood, A. H. Nevidomskyy, C. J. Pikard 96 E. Clar, The Aromatic Sextet, Wiley, London, 1972.
and B. D. Simons, Nat. Phys., 2005, 1, 42. 97 K. Periya, et al., New J. Chem., 2010, 34, 2132.
65 P. W. Stephens, L. Mihaly, P. L. Lee, R. L. Whetten, 98 N. Kawasaki, Y. Kubozono, H. Okamaoto, A. Fujiwara and
S.-M. Huang, R. Kaner, F. Deiderich and K. Holczer, Nature, N. Yamaji, Appl. Phys. Lett., 2009, 94, 043310.
1991, 351, 632. 99 N. Kawasaki, W. L. Kalb, T. Mathis, Y. Kaji, R. Mitsuhashi,
66 R. Tycko, G. Dabbagh, M. J. Rosseinsky, D. W. Murphy, H. Okamoto, Y. Sugawara, A. Fujiwara, Y. Kubozono and
A. P. Ramirez and R. M. Fleming, Phys. Rev. Lett., 1992, B. Batlogg, Appl. Phys. Lett., 2010, 96, 113305.
68, 1912. 100 Y. Kaji, N. Kawasaki, X. Lee, H. Okamoto, Y. Sugawara,
67 K. Tanigaki, I. Hirosawa, T. W. Ebbesen, J. Mizuki, S. Oikawa, A. Ito, H. Okazaki, T. Yokoya, A. Fujiwara and
Y. Shimakawa, Y. Kubo, J. S. Tsai and S. Kuroshima, Nature, Y. Kubozono, Appl. Phys. Lett., 2009, 95, 183302.
1992, 356, 419. 101 K. Ueno, S. Nakamura, H. Shimotani, A. Ohtomo, N. imura,
68 R. M. Fleming, A. P. Ramirez, M. J. Rosseinsky, D. W. Murphy, T. Nojimaa, H. Aoki, Y. Iwasa and M. Kawasaki, Nat. Mater.,
R. C. Haddon, S. M. Zahurak and A. V. Makhija, Nature, 1991, 2008, 7, 855.
352, 787. 102 J. F. Schooley, W. R. Hosler, E. Ambler and J. H. Becker, Phys.
69 M. Capone, et al., Rev. Mod. Phys., 2009, 81, 943. Rev. Lett., 1965, 14, 305.
70 Y. Yoshida, Y. Kubozono, S. Kashino and Y. Murakami, Chem. 103 J. T. Ye, S. Inoue, K. Kobayashi, Y. Kawahara, H. T. Yuan,
Phys. Lett., 1998, 291, 31. H. Shimotani and Y. Iwasa, Nat. Mater., 2009, 9, 125.
71 S. Fujiki, Y. Kubozono, S. Emura, Y. takabayashi, S. Kashino, 104 K. Ogawa, Y. Kaji, R. Eguchi, A. Fujiwara, T. Kambe,
A. Fujiwara, K. Ishii, H. Suematsu, Y. Murakami, Y. Iwasa, Y. Kubozono, unpublished data.
T. Mitani and H. Ogata, Phys. Rev. B: Condens. Matter, 2000, 105 Y. Kaji, K. Ogawa, R. Eguchi, A. Fujiwara, T. Kambe and
62, 5366. Y. Kubozono, Org. Electron., submitted.
72 A. Y. Ganin, Y. Takabayashi, Y. Z. Khinyak, S. Margadonna, 106 N. Kawai, K. Ogawa, Y. Kaji, R. Eguchi, A. Fujiwara,
A. Tamai, M. J. Rosseinsky and K. Prassides, Nat. Mater., 2008, T. Kambe, Y. Kubozono, to be submitted.
7, 367. 107 J. E. Schirber, D. L. Overmer, K. D. Carlson, J. M. Williams,
73 Y. Takabayashi, A. Y. Ganin, P. Jeglic, D. Arcon, T. Takano, A. M. Kini, H. H. Wang, H. A. Chaelier, B. J. Love,
Y. Iwasa, Y. Ohishi, M. Takata, M. Takeshita, K. Prassides and D. M. Watkins and G. A. Yaconi, Phys. Rev. B: Condens. Matter,
M. J. Rosseinsky, Science, 2009, 323, 1585. 1991, 44, 4666.

Kubozono2011 Metal Intercalated Aromatic Hydrocarbons A New Class of CARBON BASED SUPERCONDUCTORS

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Cite this: Phys. Chem. Chem. Phys., 2011, 13, 16476–16493

Yoshihiro Kubozono,*ab Hiroki Mitamura,a Xuesong Lee,a Xuexia He,a

which shares, interestingly, properties with most of the

Yoshihiro Kubozono studied Hiroki Mitamura received

Yosuke Takahashi received his Ritsuko Eguchi is an assistant

Fig. 2 Synthesis routes for picene.

Takashi Kambe is an Associate Hideo Aoki is a Professor

Polymorphs are often observed in molecular solids, and this

a structural phase transformation has been observed in penta-

Fig. 6 Energy diagram of pentacene, picene and [7]phenacene.

ultraviolet photoemission spectroscopy (ARUPS). Pentacene

Bi–Si(111), in order to obtain well-oriented pentacene thin

and Hc2–T plots (not shown). We can go one step further to

as in the superconducting K3picene, suggests that the inter-

that a lower energy state is obtained for structures with K atoms

undoped picene and K3picene, where not only the molecular

overcrowding, as seen experimentally.37 The calculated elec-

5. Theoretical approach to hydrocarbon

reproduces the DFT-LDA band dispersion (Fig. 21(b)).

The matrix element of the Kohn–Sham Hamiltonian HKS

Fig. 23 Clar structures of hydrocarbons. For the deﬁnition of Clar

an interesting possibility. The optimised structure, Fermi sur-

As seen from this, nmax depends only on ex of the gate dielectric.

ethyl)-N-methylammonium bis(triﬂuoromethylsulfonyl)imide p-channel. Since we now know that superconductivity in bulk

245, 793. 79 S. Okada, R. Arita, A. Oshiyama, Y. Matsuo, E. Nakamura and

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