Journal of the Physical Society of Japan 81 (2012) 011004 SPECIAL T OPICS

DOI: 10.1143/JPSJ.81.011004 Recent Developments in Superconductivity

Recent Topics of Organic Superconductors

Arzhang ARDAVAN, Stuart BROWN1 , Seiichi KAGOSHIMA2 , Kazushi KANODA3 , Kazuhiko KUROKI4 ,
Hatsumi MORI5 , Masao OGATA6 , Shinya UJI7;8 , and Jochen WOSNITZA9
Clarendon Laboratory, Department of Physics, University of Oxford, OX1 3PU, U.K.
1
Department of Physics and Astronomy, UCLA, Los Angeles, CA 90095-1547, U.S.A.
2
Deaprtment of Physics, Meiji University, Tama-ku, Kawasaki 214-8571, Japan
3
Department of Applied Physics, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
4
Department of Engineering Science, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan
5
Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan
6
Department of Physics, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
7
National Institute for Materials Science, Tsukuba, Ibaraki 305-0003, Japan
8
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan
9
Hochfeld-Magnetlabor Dresden, Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden, Germany
(Received October 24, 2011; accepted November 28, 2011; published online December 26, 2011)
Recent developments in research into superconductivity in organic materials are reviewed. In the epoch-defining
quasi-one-dimensional TMTSF superconductors with Tc
1 K, Tc decreases monotonically with increasing pressure,
as do signatures of spin fluctuations in the normal state, providing good evidence for magnetically-mediated pairing.
Upper critical fields exceed the Zeeman-limiting field by several times, suggesting triplet pairing or a transition to an
inhomogeneous superconducting state at high magnetic fields, while triplet pairing is ruled out at low fields by NMR
Knight-shift measurements. Evidence for a spatially inhomogeneous superconducting state, Fulde–Ferrel–Larkin–
Ovchinnikov state, which has long been sought in various superconducting systems, is now captured by
thermodynamic and transport measurements for clean and highly two-dimensional BEDT-TTF and BETS
superconductors. Some of the layered superconductors also serve as model systems for Mott physics on anisotropic
triangular lattice. For example, the Nernst effect and the pseudo-gap behavior in NMR relaxation are enhanced near to
the Mott transition. In the case of increasing spin frustration, the superconducting transition temperature is depressed,
and antiferromagnetic ordering is eliminated altogether in the adjacent Mott insulating phase. There is an increasing
number of materials exhibiting superconductivity in competition or cooperation with charge order. Theoretical studies
shed light on the role of spin and/or charge fluctuations for superconductivity appearing under conditions close to those
of correlation-induced insulating phases in the diversity of organic materials.
KEYWORDS: organic superconductors, pairing symmetry, spin density wave, Mott transition, spin fluctuations, charge
order, charge fluctuations, Nernst effect, Fulde–Ferrel–Larkin–Ovchinnikov state

properties.3–5) TTF-TCNQ and similar materials attracted

1. Introduction
A centennial research on superconductivity proved that it
appears in a variety of materials and has both universal
features and some variations in its nature depending on the
material. Organic superconductors provide distinctive play-
grounds for superconductivity research because of its unique
crystal and electronic structures. In this article, the authors
report on the intensively studied issues of current interest on
the physics of superconductivity in organic charge-transfer
salts based on donor molecules such as TMTSF, TMTTF,
BEDT-TTF, BEDT-TSeF (BETS), and some TTF deriva-
tives.
1.1 Brief history of the researches on organic
superconductivity
1.1.1 The circumstances leading up to the discovery of
organic superconductors
Since the success of synthesizing conducting organic
material, perilene bromine complex, in 1954,1) various types
of organic semiconductors were developed and studied
intensively. It is to be noted that a theoretical prediction was
made to realize high temperature superconductors by
organic chemical synthesis.2)
Intensive studies of physics of organic conductors started
in 1970’s as focusing on the metal–insulator (M–I) transition
of TTF-TCNQ having highly one-dimensional, metallic
011004-1
broad attention because (1) they were made by chemical
synthesis and, therefore, much more materials were expected
to give novel phenomena and (2) Little’s model had
suggested possible superconductivity at 1,000 K in synthetic
linear chain conductors.2) The mechanism of the M–I
transition was found to be the Peierls instability due to
electron–phonon interactions accompanied by the formation
of charge-density waves (CDW). Physics of CDW was fully
elucidated.6) Studies of conducting polymers also started
at nearly the same time. The synthesis of poly-acetylene,
(CH)x , films paved a way to rich applications.7) The
inorganic crystalline polymer, (SN)x , having quasi-one-
dimensional nature, was found to show superconductivity
at 0.3 K.8) This was the first superconductivity realized in
research activities of synthesizing novel superconductors
without using metal elements.
1.1.2 The superconductivity found in (TMTSF)2 PF6 and
succeeding many organic conductors
In 1979, superconductivity was first found in an organic
crystalline material, (TMTSF)2 PF6 and the first paper was
published in 1980.9) This material showed quasi-one-
dimensional properties at ambient pressure down to 12 K
followed by a M–I transition due to the instability of the
Fermi surface to form spin-density waves. This suggested an
important role of the on-site Coulomb interaction, U,
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
between conduction electrons in the M–I transition. The
superconductivity was found under a critical hydrostatic
pressure, Pc , of 0.5–0.6 GPa. The superconducting critical
temperature, Tc , was about 0.9 K and was found to decrease
with increasing pressures above Pc . After (TMTSF)2 PF6 ,
superconductivity was found in many members of
(TMTSF)2 X, where X denotes an anion having the valence
of 1. Among them, the salt with X ¼ ClO4 showed the
superconductivity at ambient pressure with Tc of about
1.4 K.10) In the 1990’s and 2000’s, the sulfur analog,
(TMTTF)2 X, was also found to show superconductivity
when pressures of several GPa were applied.11,12) Sometimes
TMTSF and TMTTF are simply called TMTCF, where C
means a chalcogen. One may say that these materials belong
to the first generation of organic superconductors having the
quasi-one-dimensional nature and Tc of the order of 1 K.
The second generation of organic superconductors began
to appear in the middle of 1980’s. They have a quasi-two-
dimensional nature and Tc of the order of 10 K. The first one
was -(BEDT-TTF)2 ReO4 which became superconducting
under pressure of 0.4 GPa with Tc of 2 K.13) Then, -(BEDT-
TTF)2 I3 showed superconductivity at ambient pressure with
Tc of 1.5 K.14) This is called the ‘‘low-Tc ’’ state because, in
the regime above about 0.05 GPa, the ‘‘high-Tc ’’ state with
Tc of about 8 K coexists with the low-Tc one.15,16) This
coexistence is related to the onset of a superstructure below
175 K at ambient pressure.17–19) -(BEDT-TTF)2 I3 with
‘‘high-Tc ’’ opened the way to realize the higher-temperature
superconductivity. -(BEDT-TTF)2 Cu(NCS)2 , having Tc of
10.4 K at ambient pressure was synthesized in 1986.20) Salts
with a wide variety of anions showing superconductivity
were synthesized. They had diverse types of arrangement of
BEDT-TTF molecules in the conducting layers and provided
a rich variety of novel electronic properties.
Modification of TMTSF and BEDT-TTF molecules gave
many kinds of organic superconductors.21–25) The combina-
tion of half of a TMTSF and half of a BEDT-TTF molecule
leads to the DMET molecule. Its salts with anions showed
electronic properties in between TMTSF and BEDT-TTF
salts depending on the anion species. Replacement of S with
O gave the BO molecule and replacing some of the eight S
atoms with Se provided BEDT-TSeF (BETS), BESe-TTF,
and ESET-TTF molecules. When one of two terminal six-
member rings is either removed or modified, or both,
one obtains TMET-STF, MDT-TS, MDT-ST, MDT-TSF,
MDSe-TSF, MDT-TTF, and EDT-TTF molecules. Using
TTP unit, one obtains BDA-TTP and DTEDT molecules
whose salts show as well superconductivity. One of the
modifications of BEDT-TTF, DODHT is a non-planar
molecule. It enlarged the intermolecular spacing to reduce
the conduction-band width, which served to realize the
superconductivity. DIETS having two terminal iodine atoms
forms a supra molecular coupling between two conducting
layers across the anion ones. Uniaxial compression of
-(DIETS)2 [Au(CN)4 ] perpendicular to the conducting plane
induces superconductivity. Another type of molecule,
M(dmit)2 where M denotes Ni or Pd, produced several salts
showing superconductivity when they are combined with
cations such as TTF and (CH3 )4 N. The most recent molecule
reflecting superconductivity is picene composed of five
benzene-like rings. Compared to other molecules described
011004-2
A. ARDAVAN et al.
above, picene is unique because of the absence of chalcogen
atoms. It is composed of only C and H. K3 picene was found
to show superconductivity at ambient pressure with Tc of
18 K.26)
1.2 Structural and electronic properties characteristic of
organic superconductors
1.2.1 Basic properties
Organic superconductors have a large anisotropy and low
symmetry in their crystal structures. Most of the crystals
are composed of columns or layers of conducting organic
molecules. They are soft to suffer a large structural
modification under low or moderate pressures. In addition,
it is relatively easy to design a new molecule or a new
arrangement of molecules. One may ascribe these character-
istics to the nearly planar shape of organic molecules and to
the weak molecular coupling by the van der Waals force.
In their electronic properties, organic superconductors
are characterized by their low-dimensional nature, narrow
bandwidth and the large Coulomb correlation among
conduction electrons. Nearly planar molecules form a
columnar or layered structure resulting in a low-dimensional
conduction band. Usually the kinetic energy represented by
the bandwidth, W, is smaller than or nearly equal to the
Coulomb interaction energy between conduction electrons.
It is due to the large intermolecular distance compared to
conventional inorganic conductors. With increasing inter-
molecular distance, the transfer integral of the conduction
electrons decreases more rapidly than the Coulomb interac-
tion energy. The low-dimensional nature provides cylind-
rical or planar Fermi surfaces where electrons can show
novel behaviors under magnetic fields.
The following parameters give a rough clue to compare
organic superconductors with inorganic ones:24) A bandwith
is of the order of 0.5 eV while that of inorganic conductors
is several eV. The Debye temperature is 100–200 K while
several hundred to 1000 K in inorganic conductors. The
importance of the Coulomb interaction is estimated by the
parameter U=W, where U denotes the effective on-site
Coulomb interaction energy. Organic superconductors
seem to have U=W of the order of 10 and that of oxide
superconductors is usually several times larger. The lattice
compressibility and the thermal expansion coefficient are ten
times larger than those of inorganic materials. These lattice
properties make high-pressure experiments useful and
require careful analyses of the temperature dependence of
physical quantities measured at a constant pressure. It is
to be noted that the so-called chemical-pressure effects
are conveniently used in experiments to precisely modify
intermolecular distances. The most popular method is the
deuteration for a C–H bond, which reduces the bond length.
1.2.2 Roles of the Coulomb interaction in
superconductivity
Most of the organic superconductors are found near
magnetic or charge-localized states due to the Coulomb
interaction between conduction electrons. This infers
possible roles of the Coulomb interaction in the super-
conductivity. The magnitude of the Coulomb interaction
is parameterized by the on-site Coulomb energy U and the
long-range one V .
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
U dominates the electronic properties when the charge
density is 1/site because the Mott transition leads to charge
localization. (TMTCF)2 X and (BEDT-TTF)2 X have the
formal charge density of 0.5 electron/molecule. However,
all TMTCF salts and some salts of BEDT-TTF have a
certain magnitude of dimerization of TMTCF or BEDT-TTF
molecules to make effectively the charge density 1/site and
are prone to Mott localization. Spins of localized electrons
usually undergo an antiferromagnetic transition or a spin-
Peierls transition into a non-magnetic state. Precise mod-
ification of the bandwidth can be made by chemical pressure
and conventional gas-pressure methods to examine the
possible quantum phase transitions between insulating
antiferromagnetic and the superconducting states at very
low temperature. When the spin–lattice is triangular as in
-(BEDT-TTF)2 Cu2 (CN)3 , the localized spins suffer from
frustration against ordering and can form a spin-liquid state
without conventional orderings. Application of uniaxial
strain or hydrostatic pressure to the triangular spin–lattice
removes the frustration leading to a superconducting state
in -(BEDT-TTF)2 Cu2 (CN)3 . The relation between Mott
localization and superconductivity will be discussed later in
x4.1 and x4.2.
When V is important, not only the charge localization but
also the charge disproportionation and its ordering can lead
to an insulating state. Systematic analyses were made on the
phase diagram of temperature vs dihedral angle of -(BEDT-
TTF)2 X.27) The electronic states thus viewed will be
discussed in x5.1. In a regime of small dihedral angle,
where the bandwidth W is expected to be relatively large,
a superconducting state was found in -(BEDT-TTF)2 I3 .
1.2.3 Mechanisms of superconductivity
The symmetry of the pair potential or the wave function
of a Cooper pair of organic superconductors has been
extensively studied. In several kinds of organic super-
conductors, gap nodes are found on the Fermi surface
suggesting an anisotropic nature of the superconductivity.
NMR, STM spectra, the Nernst effects and some other
measurements have provided evidences for this. The Nernst
effect and its related phenomena will be discussed in x4.3.
This anisotropic nature is ascribed to the Coulomb correla-
tion among conduction electrons. The Cooper pair seems to
have d-wave symmetry in the singlet spin state. There is as
well evidence for a nodeless gap structure from e.g., specific
heat data.28) However, a possibility is discussed on the triplet
spin state having either the p- or f-wave state. This problem
will be discussed in x2.
The Cooper-paring mechanism is still not yet clear.
Measurements of the isotope effects failed to give a clear
answer for the phonon mechanism. The most plausible
mechanism is spin-fluctuation mediated pairing because the
conduction electrons have a considerable magnitude of
Coulomb interaction between them and the Cooper pair has
possibly d-wave symmetry. However, a discussion can be
made also on the possibility of charge fluctuations, besides
the conventional phonon mechanism, because, in some salts,
a CDW state but not a SDW one was found near the
superconducting state in the phase diagram. The possible
pairing mechanism in organic superconductors will be
discussed in x4.4 and x5.2.
011004-3
A. ARDAVAN et al.
In the layered structure realized in many types of organic
conductors, the Lorentz orbital effect is largely suppressed
by magnetic fields applied precisely parallel to the conduct-
ing layer. Under this condition, the Zeeman effect at high
magnetic fields possibly causes the inhomogeneous super-
conductivity proposed by Fulde and Ferrel, and Larkin
and Ovchinnikov.29,30) It is called FFLO state, where the
Cooper pairs have a finite momentum and, in real space,
alternate stripes of superconducting and non-superconduct-
ing state can be formed. This problem will be considered in
x2 and x3.
1.2.4 Experiments to reveal the nature of organic
superconductors
Compared to inorganic materials, organic conductors
impose restrictions against some measurements. This is
because one has to use as-grown crystals having irregular
shape. Cutting, grinding and polishing of samples are almost
impossible because organic crystals are fragile and possibly
damaged at high temperatures. Also some glues and solvents
for sample handling damage organic samples. In spite of
these difficulties, precise measurements were made on STM
spectra and the Nernst effect to examine the symmetry of the
superconductivity and the fluctuation effect, where the
sample surface and its orientation was crucial for obtaining
reliable results. Experiments under high pressures, physi-
cally or chemically induced ones, and high magnetic fields
lead to the finding of novel phenomena. Precise controls of
gas pressure or chemical composition allowed to investigate
the physics of quantum phase transitions between the Mott-
insulating and superconducting states. The application of
uniaxial strain provided another way to artificial modifica-
tions of the crystal and electronic structures.31) This method
made possible the discussions on the relation between the
spin liquid and the superconducting states,32) and among the
mass-less Dirac electronic, the charge-ordered and super-
conducting states.33) Application of high magnetic fields
leads to the finding of the superconducting state by the
Jaccarino–Peter mechanism, where the quasi-two-dimen-
sional layered structure presumably provided a favorable
condition for this. Also the possible FFLO state was
discussed in highly two-dimensional materials. Effects of
high magnetic fields to the superconducting state will be
discussed in x3.
This paper is organized as follows: In x2, the super-
conductivity of TMTSF salts is discussed and x3 is devoted
to discussions of the superconductivity under high magnetic
fields. Sections 4 and 5 deal with the superconductivity near
the Mott transition and charge ordering, respectively. It is
uncertain what is the maximum critical temperature, and
what kinds of novel superconducting properties are found
in future studies. Moreover, the superconductivity may be
possibly realized in quite different types of organic materials
including conducting polymers in the near future. These
perspectives of future studies will be presented in x6.
2. Superconductivity of TMTSF Salts
The observation of metallic-like conductivity in com-
pounds such as TTF-TCNQ4,5) set the stage for the 1979
discovery of superconductivity in (TMTSF)2 PF6 .9) The
density wave ground state characterizing the former is a
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
natural outcome of the quasi-one-dimensional bands, but
with larger donor orbitals (e.g., as in TMTSF) and greater
interstack contact, electronic anisotropy is reduced and
Peierls instabilities suppressed. In (TMTSF)2 PF6 , a phase
transition to a fully-gapped density wave state occurs only at

12 K. Pressure eliminates what turned out to be a uniaxial
spin density wave (SDW) ground state by worsening the
nesting conditions, and superconductivity is stabilized at
pressures greater than Pc ¼
0:6 GPa. The remanent anti-
ferromagnetic spin fluctuations (SF) nevertheless persist for
P > Pc . Significantly, the Bechgaard salts, as the broader
family of compounds (TMTSF)2 X came to be called, are
among the first known example of superconducting pairing
linked to antiferromagnetic SF (superconductivity in the
heavy-fermion compound CeCu2 Si2 was reported at about
the same time34)). Following the discovery of superconduc-
tivity in the X ¼ PF6 salt, superconductivity was sub-
sequently observed in many others, including those with
centrosymmetric anions such as AsF6 , SbF6 , TaF6 , as well
as systems with non-centrosymmetric anions, for example
ClO4 , BF4 , and FSO3 .22,24)
Following the discovery of superconductivity in the
TMTSF compounds, a large number of superconducting
molecular solids were synthesized and characterized, and
reports of higher transition temperatures were common.24,25)
Nevertheless, the physical properties of the Bechgaard salts
are a remarkable set and completely unique. Observed
ground states are not limited to the two mentioned but
include symmetry-broken states such as field-induced spin
density waves, spin-Peierls states, anion ordering, charge-
ordering, and antiferromagnetism. Tuning between them is
accomplished experimentally using pressure or magnetic
field, and the emergent behavior serves as a reminder of the
important role of correlations in the broader family of highly
anisotropic molecular conductors.
In spite of strong evidence for the association of SF with
superconductivity in the Bechgaard salts, the detailed nature
of the ground state has been revealed only very slowly. An
important factor is a shorter list of effective experimental
probes than what has been applied to many inorganic
compounds. For instance, magnetic neutron scattering,
photoemission spectroscopy, and tunnelling techniques have
been applied sparingly if at all. In what follows, we describe
more fully the starting point for the electronic structure,
some details and remaining questions regarding the super-
conducting state, as well as the manifestations of correla-
tions in the normal state.
2.1 Crystal structure, band structure, and phase diagram
of TMTSF salts
 crystal structure of (TMTSF)2 PF6 is
The triclinic (P 1)
shown in Fig. 1(a).35) The donors assemble in stacks along
the viewing direction (a-axis, also the high-conductivity
direction as a result of molecular-orbital overlap with
substantial selenium pz character). The PF6  counterions
are singly charged, and consequently there is a single band at
the Fermi energy. The ratio of calculated transfer integrals
for the full 1/4-filled band (4ta : 4tb Þ
ð500 meV :
50 meV)36) are consistent with the conductivity anisotropy
measured by dc methods,37–39) and angular magnetotransport
measurements.40) Strictly speaking, a small dimerization of
011004-4
A. ARDAVAN et al.
(a)
(b)
Fig. 1. (Color online) (a) Crystal structure of (TMTSF)2 PF6 , with
selenium ions yellow and carbon blue. PF6  counterions are centered at
the corners of the unit cell. (b) Temperature/pressure phase diagram,
showing the suppression of the spin density wave ground state with
pressure, and the emergence of a superconducting state. A phase diagram
like this one appeared in ref. 41 for (TMTSF)2 AsF6 .
interdonor distances along a folds the band, producing an
equivalent 1/2-filled system.
The familiar temperature/pressure phase diagram for
(TMTSF)2 PF6 appears in Fig. 1(b). NMR experiments
indicate that the ground state is an incommensurate spin
density wave, arising from imperfect nesting conditions.
Pressure increases overlap, in turn worsening the nesting
conditions. The Peierls temperature TSDW ¼ 12:1 K is
reduced smoothly to T ¼ 0 at a critical value of Pc
0:6
GPa. For P > Pc , superconductivity is observed at Tc

1:2 K, with the transition temperature slowly and mono-
tonically decreasing as the pressure increases beyond Pc .
Replacing the PF6 counterion with other centrosymmetric
ions, such as AsF6 or SbF6 gives similar results. Super-
conductivity is also found in salts with non-centrosymmetric
counterions, such as ClO4 and FSO3 . In the case of ClO4 , it
is necessary to slowly cool through an ion ordering transition
at 24 K to observe the superconducting ground state.
Near to Pc , the phase boundary separating normal and
SDW states is first order,42) and there is microscopic
evidence for phase segregation.43) Not surprisingly, super-
conductivity is detected at pressures P < Pc . A proposal that
the inhomogeneities are actually mesoscopic in scale, and
associated with the formation of solitonic (anti-phase)
domain walls44) is interpreted consistent with details of the
phase diagram.45) In addition, 1 H NMR lineshapes recorded
at similar pressures cannot be accounted for using a simple
macroscopic phase segregation scenario.46)
Lower effective pressures are realized in the isostructural
TMTTF salts, for which the anisotropy is greater and
correlations more important. For example, (TMTTF)2 PF6
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

and (TMTTF)2 AsF6 are Mott insulators and undergo charge- 6

ordering phase transitions47,48) typically attributed to near-
neighbor repulsive interactions (V ) in what is treated as a 5 μ0H //b’

magnetic field μ0H (T)

1/4-filled quasi-one-dimensional system.49) A second, dis- (TMTSF)2PF6
4
tinct route to an insulating state occurs even when V is less P=0.6GPa
important, where strong bond alternation along the stacks
3
leads to the so-called Dimer–Mott state. Sufficiently high
pressure applied to the isostructural charge-ordered TMTTF
2 μ H //a μ H
systems, made with counter anions such as PF6 ,11) AsF6 , or 0 0 P
SbF6 ,50) stabilizes superconductivity at similar transition 1
temperatures as the Bechgaard salts. Taken together, there μ H //c*
0
is widespread acceptance of the universality of the sequence 0
0 0.5 1 1.5
of phases exhibited by the two families of salts on increasing temperature (K)
the pressure: Mott physics ! density waves ! super-
conductivity. Fig. 2. (Color online) 0 Hc2 for (TMTSF)2 PF6 , determined resistively
and with the field parallel to the high-conducting planes (a-, b0 -directions),
2.2 The superconducting state; pairing symmetry and and orthogonal to the planes (c ). (After ref. 57.)
high-field properties
Initially, the physical properties of the superconducting
state were considered conventional, as for an s-wave order 40 0.4
−1 −1
parameter. Over time, experimental results presented a (T T)
1
(s−K) , H //b’
challenge for consistent interpretation. For example, the
−1
−1 −1
30 6×(T1T) (s−K) , H //a 0.3
(s−K)
rapid suppression of the critical temperature by non- Rzz

(Ω)
magnetic impurities suggested the order parameter changed
20 0.2
sign over the Fermi surface.51,52) This, and the proximity to a
−1

zz
[ T1T ]

R
spin density wave led to the suggestion of p-wave pairing.53)
Constraining further the gap structure were the 1 H NMR 10 0.1
77

relaxation rates, which indicated the presence of lines of gap

zeroes.54,55) Later, however, results of thermal conductivity
measurements were interpreted as evidence for a fully-
gapped order parameter.56)
Substantial interest in the superconducting state of the
Bechgaard salts was generated by the highly anisotropic
field/temperature phase diagram reported for the PF6 salt,57)
and similarly for ClO4 .58) The upper critical field, shown in
Fig. 2, was determined using resistivity measurements,
which revealed the survival of superconductivity to fields
significantly greater than the Pauli-limiting field 0 HP

2:5 T,59) for applied fields aligned along the a and b0 axes.
Evidently, orbital suppression of superconductivity is
substantially avoided for in-plane fields, and especially so
for fields aligned orthogonal to the stacks.
Under the circumstances, associating such large 0 Hc2
values with the stabilization of an inhomogeneous super-
conducting state (FFLO), as first proposed by Fulde and
Ferrell29) and independently by Larkin and Ovchinnikov,30)
naturally follows. FFLO formation is a consequence of the
quasiparticle Zeeman interaction in clean, Pauli-limited
superconductors, and should exhibit a greater range of
stability in layered systems. However, with 0 H k b0 there is
no sign of Pauli-limiting behavior even from low fields, and
therefore, (TMTSF)2 PF6 was instead considered a candidate
for a spin-triplet pairing state.59,60)
Knight-shift measurements appear to rule out triplet
pairing at low fields. Reported in ref. 61 is 77 Se NMR
spectroscopy in fields less than 1 T and temperatures down to
100 mK. Under these conditions, at least half of the normal
state spin susceptibility is absent. What remains could be
attributed to triplet pairing,62) but even the Zeeman shifts
of the quasiparticle states near to gap nodes provide a
mechanism for non-zero spin polarization in a magnetic
011004-5
0 0
0 1 2 3 4 5
magnetic field μ H (T)
0
Fig. 3. (Color online) 77 Se ½T1 T 1 vs field, in the limit T ! 0,
normalized to the normal state, and contrasted to the interlayer resistance
Rzz ð0 HÞ. The recovery of the NMR relaxation toward the normal state is
observed to occur at much smaller fields than the resistance.
field.63) Therefore, the experimental results are taken as
evidence in support of singlet pairing, with lines of zeros
over the Fermi surface. All of these features, as well as the
normal-state properties, are consistent with pairing mediated
by interchain antiferromagnetic spin fluctuations.64)
Magnetic-field effects on the superconducting state
relaxation rates are substantial. Specifically, ½T1 T 1 is a
field-dependent constant in the limit T ! 0. As shown in
Fig. 3, ½T1 T 1 approaches what is observed for the normal
state very rapidly at fields in the range 1.5–2 T, while the
interlayer resistance Rzz remains negligible. The nature of
the superconductivity at higher fields (above 2.0–2.5 T) is
unclear. For example, the possibility for a field-induced
transition to a triplet superconducting state has been
proposed,65–67) and recent results from magnetotransport
experiments68) were discussed in the context of an FFLO
state. Nevertheless, neither of these proposals is clearly
supported by the NMR T1 measurements, or by results of
recent specific-heat measurements.69) Specifically, for the
case of the NMR measurements in the high-field regime, the
observation of a relaxation rate indistinguishable from the
expected result for the normal state may be inconsistent with
either a triplet pairing state or an FFLO phase.
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
150
P (GPa) 0.45
0.53
0.60
0.68
0.78
100 0.95
1.15
T −1 (s−1)
50
0
0 5 10 15 20 25 30
temperature T (K)
Fig. 4. (Color online) 77 Se NMR spin lattice relaxation rate vs
temperature, for applied pressures greater than, and less than Pc ¼
0:6 GPa. T11 tends to diverge on approach to TSDW (P). For higher
pressures the ground state is superconducting. Nevertheless, the
enhancement of T11 from AF SF remains significant.
2.3 The normal state; enhanced AF fluctuations and
anomalous transport
The normal-state properties of the TMTSF salts lend
credibility to the proposal that superconducting pairing is
associated with antiferromagnetic spin fluctuations. Clear
signatures of the SF are exhibited in the 77 Se nuclear spin
lattice relaxation rate, and a very interesting manifestation is
present in the transport experiments. The former is inferred
from the data shown in Fig. 4, which shows T11 vs T in
(TMTSF)2 PF6 for a range of pressures covering both sides of
Pc ¼ 0:6 GPa. At lower pressures and upon cooling, T11
increases and tends to diverge, as would occur for critical
slowing down on approach to the SDW ordering tempera-
ture. For P > Pc , there is no divergence; instead, there
appears a range of temperatures over which, T11 varies
little, and moreover is significantly enhanced relative to
expectations based on the Korringa relation. What could be
interpreted as a crossover to generic Fermi-liquid behavior is
observed as T ! 0, with ½T1 T 1 ! constant.
Closer inspection reveals the relaxation data for the
Bechgaard salts are well-described by a Curie–Weiss (CW)
relation T1 T
T þ , with  monotonically increasing
with pressure61,70) (Fig. 5). The behavior is reminiscent of
two-dimensional spin fluctuations,71,72) for which scaling
gives ½T1 T 1
ðQÞ; with ðQÞ1
T þ . Notably,
interest in the phenomenology was driven by similar
observations made for the cuprates, e.g., ref. 73. However,
with the Bechgaard salts, there is no indication for
pseudogap behavior, and significantly, the Curie–Weiss
behavior is uninterrupted to temperatures significantly less
than Tc .61) That is, as would occur if the SF correlation
length increases nonsingularly without saturating to the
lowest temperatures measured (
0:1Tc ).
Juxtaposed with the relaxation rate dominated by spin
fluctuations is a temperature dependent resistivity of the
form ðT Þ ¼ 0 þ T . A recent comprehensive magneto-
transport study correlated the magnitude of the intrinsic
linear-T contribution with the superconducting transition
011004-6
A. ARDAVAN et al.
45
40 (TMTSF) PF
2 6
35 P =0.9GPa μ0 H =4.91T//b’
30
Se T −1 (s−1)
25
0.8 T1T (s−K)
1
20
0.6
77
15 0.4
10 0.2
T (K)
0
5 0 10 20 30
0
0 5 10 15 20 25 30
temperature T (K)
Fig. 5. (Color online) Normal state 77 Se T11 vs T in the regime at
P ¼ 0:9 GPa. The red line follows a Curie–Weiss form, T1 T
ðT þ Þ.
The data is replotted as T1 T vs T in the inset.
temperature.74,75) Furthermore, similar behaviors were ob-
served for pnictide and cuprate superconductors.76) As for
the relaxation rate, the linear-T resistivity persists to
T  Tc .
These observations are provided some context by the
results of renormalization group calculations.64,77) Scattering
amplitudes from particle–hole and particle–particle channels
are included; the effect of the pairing interaction on the SF is
to suppress the saturation of the correlation length, just as
implied by the experiments. In addition, at temperatures
greater than the characteristic energy scale for the SF, linear
resistivity results. The behavior is a consequence of the
highly nested Fermi surface, a proximity to a (experimen-
tally inaccessible) quantum critical point near to Pc , and the
interference between electron–electron and electron–hole
scattering. Evidently, the interference fundamentally modi-
fies the physical properties within some range of the SDW
critical point to much lower temperatures. The modifications
are non-singular, so that the parameter  appearing in the
CW form for the relaxation indicates some distance from the
critical point even while the resistivity takes the form
commonly associated with criticality. On the other hand, the
SF correlation length saturates within the framework of
the self-consistent renormalized theory,72) which does not
include the interference. Coinciding with the saturation is a
crossover to FL behavior manifested in the departure from
the CW form for the relaxation along with a quadratic
variation in resistivity. Whether the results apply more
broadly to other materials is unclear. Certainly, the
observations of qualitatively similar physical properties in
some cuprates and pnictides invite comparisons, as does
the strictly quadratic-T variation of the low temperature
resistivity of the quasi-two-dimensional -(BEDT-TTF)2 X
superconductors.78)
3. Exotic Superconductivity at High Magnetic Fields
Organic superconductors with almost perfect two-dimen-
sional electronic band structures will be ideal candidates for
the study of spin-dominated physics in their superconducting
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

properties. In case an external magnetic field is aligned

exactly parallel to the conducting layers, orbital effects are
largely suppressed and eventually only the Zeeman energy at
high-enough fields may compete with internal energy scales.
Consequently, such exotic phenomena as magnetic-field-
induced superconductivity79) as well as strong indications for
the existence of the FFLO29,30) have been observed. In the
following, we will briefly review on the latter phenomenon.

3.1 Thermodynamic evidence for the FFLO state in

-(BEDT-TTF)2 Cu(NCS)2
In a number of organic superconductors, different
experimental techniques revealed indications for the ex-
istence of FFLO states.80) In most of these experiments,
however, no thermodynamic proof was given. Only recently,
specific-heat experiments showed evidence for a narrow
intermediate superconducting state.81) This phase is most Fig. 6. (Color online) Temperature dependence of the electronic part of
probably a realization of the long-time predicted FFLO state. the specific heat of -(BEDT-TTF)2 Cu(NCS)2 at low temperatures for
different magnetic fields applied parallel to the layers. Data taken in 14 T
-(BEDT-TTF)2 Cu(NCS)2 with Tc ¼ 10:4 K is one of the applied perpendicular to the layers were used to separate the phonon
most studied two-dimensional organic superconductors. In contribution. The inset shows the data taken at 22 T for up and down
this superconductivity, the strong electron correlation plays temperature sweeps. See ref. 81 for more details.
an important role, which will be discussed in the next
section. The band calculation as well as optical and transport
measurements show the presence of two-dimensional energy
bands with in-plane transfer integrals tb
16 meV and tc ¼
22 meV.82,83) The transfer integral in the interlayer direction
ta
0:04 meV is much smaller than the above values.83) The
specific heat of high-quality single crystals of -(BEDT-
TTF)2 Cu(NCS)2 was measured by use of a miniaturized
relaxation technique in static fields in Geneva up to 14 T and
in the Grenoble High Magnetic Field Laboratory up to 28 T.
As this technique is capable to record data during heating
and cooling, it allows to resolve hysteresis effects close to
first-order transitions. In the experiments, it was very
important to align the sample in the best possible way for
parallel-field orientations. In line with the predictions for
the FFLO phase in layered superconductors, the features
described below only appeared for accurate in-plane field
alignment.81)
For such field orientation, spike-like anomalies in the
Fig. 7. (Color online) Phase diagram of -(BEDT-TTF)2 Cu(NCS)2 for
specific heat are observed for fields above 21 T and fields applied parallel to the superconducting layers. The solid line
temperatures below 3 K. In Fig. 6, only the electronic represents the calculated Hc2 using the known band-structure parameters.
contribution to the specific heat, Ce , divided by temperature
is shown. For that, the phonon contribution, measured in a
magnetic field of 14 T applied perpendicular to the layers, for the chosen field orientation parallel to the layers.
has been subtracted.81) Above 21 T, a sharpening of the Towards higher fields, Hc2 levels off towards saturation at
specific-heat anomaly in Ce occurs. This indicates the first- lower temperatures. This reflects the critical-field limitation
order nature of the phase transition from the normal into the caused by Pauli paramagnetism of singlet superconductivity.
superconducting state. For higher fields, a second very sharp The Pauli limit, HP , can be determined quite reliably from
anomaly appears within the superconducting state, giving the known superconducting-gap value, 0 , extracted in
evidence for the existence of an additional thermodynamic earlier specific-heat studies.84,85) Using 0 =kB Tc ¼ 2:4,85) it
phase. The transition at lower temperatures shows a well- is obtained that 0 HP ¼ 23 T which agrees very well with
resolvable hysteresis, while the main superconducting the observed limitation of Hc2 towards low temperatures.
transition reveals a smaller hysteresis (inset of Fig. 6). Indeed, the emergence of the clear first-order transition at
Above 23 T, the transitions left the temperature window Hc2 is a further sign that the Pauli limit is reached (Fig. 6).
accessible in the experiment. Above HP , the slope of the Hc2 line clearly becomes
From the specific-heat data the magnetic phase diagram steeper again. At the same time, the second phase transition
shown in Fig. 7 was determined. At low fields, a very steep appears. This agrees well with the theoretical expectations
initial increase of the critical field is seen. From that, an for the existence of an FFLO state. A comparison with the
orbital critical field of about 130 T can be estimated. This calculated phase diagram is shown by the solid line in Fig. 7.
large value results from the strongly reduced orbital currents For this calculation, -(BEDT-TTF)2 Cu(NCS)2 was mod-
011004-7 #2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004
(a)
Fig. 8. (Color online) (a) Magnetic-torque data of -(BEDT-TTF)2 Cu(NCS)2 at various temperatures for in-plane magnetic fields aligned along the b
direction. For T ¼ 1:7 K, data for both up and down field sweeps, otherwise only down sweeps are shown. The vertical arrows at about 21 T mark the small
steps, which are ascribed to the transitions to the FFLO state. (b) Phase diagram deduced from the data shown in (a). The Pauli limit (dotted line) obtained
experimentally is slightly lower than the calculated one (23 T).
eled by a stack of two-dimensional superconducting planes
with negligibly small conductivity perpendicular to the
planes, the well-known Fermi surface and effective masses
derived from dHvA experiments were used, and s-wave
superconductivity has been assumed.84–86) The latter, how-
ever, is not an essential ingredient. The calculation and the
experimental data agree very well except at lower tempera-
tures. This as well as the unexpected small area of the FFLO
phase might have been caused by a small sample misalign-
ment in the specific-heat experiment. In addition, the
theoretical description might be improved when more
detailed information on the electronic parameters is taken
into account.
Recently, further evidence for the existence of the FFLO
state has been gathered for -(BEDT-TTF)2 Cu(NCS)2 . The
results from magnetic-torque studies for fields aligned
along the in-plane b-direction are shown in Fig. 8.87,88)
With decreasing temperature the magnetic torque, which is
proportional to the magnetization, shows an increasingly
sharp transition at Hc2 . Such a behavior points to a
discontinuous first-order transition. This is further confirmed
by a small hysteresis that is illustrated by the arrows in the
data taken at 1.7 K. Apart from that, the main features in the
data are reversible and do not depend on the field-sweep
direction. The sharpened phase transition at Hc2 indicates
that the Pauli limit is reached. Nevertheless, superconduc-
tivity survives even beyond this field for lower temperatures,
where the transition into the normal state broadens again.
In addition, a small additional step [marked by arrows in
Fig. 8(a)] appears in the torque signal below Hc2 , signaling
the evolution of the FFLO phase. The magnetic phase
electrons. Recent heat-
diagram constructed from the torque data is shown in
Fig. 8(b).88) These results nicely confirm the specific-heat
spins
data for the Hc2 line. There are, however, some obvious
differences in the extension of the FFLO phase. This might
S PECIAL TOPICS A. ARDAVAN et al.
(b)
be explained by the much better in-plane alignment of the
magnetic field in the torque measurements which was made
possible by an in-situ rotation of the torque platform. The
alignment in the specific-heat experiment is estimated to be
not better than about 1 deg.
Additional torque measurements have been performed
after rotating the crystal by 45 degrees and aligning the
magnetic field along the b–c direction. In case of a d-wave
superconducting order parameter a pronounced anisotropy
in the transition from the FFLO to the normal state is
expected.89) In the experiments, however, only a minor
anisotropy well within error bars is found.88) Furthermore, in
tilting the magnetic field out of the highly conducting layer
the torque feature signaling the FFLO transition remains at
constant fields around HP . At angles larger than only about
1.2 degrees the superconducting state does not reach the
Pauli limit anymore and no FFLO state is observed.88)
3.2 Transport evidence for the FFLO state in
-(BETS)2 FeCl4
In -(BETS)2 FeCl4 ,90) the planar BETS molecules are
stacked along the a- and c-axes, and form two dimensional
energy bands with the in-plane transfer integrals ta
50
meV and tc
100 meV.91,92) The transfer integral in the
interlayer direction tb is estimated as only 0.3–0.03 meV.92)
The magnetic FeCl4 anions with large 3d spins (S ¼ 5=2)
form insulating layers, which are intercalated between
the BETS layers. This layered structure makes the b axis
the least-conducting direction. At zero magnetic field,
-(BETS)2 FeCl4 shows a M–I transition around 8 K due to
strong correlations between the
capacity measurements show that the M–I transition is
associated with the antiferromagnetic order of the
(S ¼ 1=2).93) The antiferromagnetic insulating phase is
removed by the application of a field of about 10 T, and
011004-8 #2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

then a paramagnetic metallic phase is recovered.94) Below (a)

1 K, when a magnetic field is applied parallel to the
conducting ac planes, superconductivity is induced in the
field range 17 to 42 T.79,95,96) This field-induced super-
conducting phase does not appear for fields applied normal
to the two-dimensional conducting layers. The overall
feature of the field-induced superconducting phase96,97) is
well understood by the Fischer theory98) based on the
Jaccarino–Peter (JP) compensation mechanism.99) Because
of a strong negative exchange interaction J between the

electron spins on the BETS molecules and the 3d mo-

ments on the Fe ions, the
spins experience a strong internal
field (0 Hint ¼ 32 T) created by the 3d moments,100,101)
whose direction is antiparallel to the external field H.
Therefore, for H ¼ Hint , the Zeeman effect is completely
suppressed, and superconductivity can be stabilized at
around Hint . (b)
The observation of Shubnikov–de Haas oscillations veri-
fies that the electronic state is highly two dimensional, and
that the superconductivity is in the clean limit.92) The
superconducting phase induced only by in-plane field shows
that the orbital field is quite high; the orbital effect is
quenched. The phase diagram analysis actually gives the
orbital critical field of about 50 T,96) which is much larger
than the Pauli limit (13 T). Angular-dependent magnetore-
(c)
sistance oscillations show the presence of low-dimensional
Fermi surfaces92) which can lead to a nesting instability. All
these features are preferable to the FFLO phase and the
possibility of the FFLO phase has been theoretically
discussed.102,103)
The interlayer resistance (I k b ) in fields parallel to the
c axis [Fig. 9(a)] shows successive dip structures in the
superconducting transitions at low temperatures.104) In the
second-derivative curves, the dip positions in the low- and
high-field regions are well defined [Fig. 9(b)]. For in-plane
current (I k c), such dip structures are not observable over
the entire temperature region.95) The dip structures are Fig. 9. (Color online) Interlayer resistance (I k b ) at various temper-
smeared out with increasing temperature and are not atures in -(BETS)2 FeCl4 . (a) The field-induced superconducting phase
observable above 1.5 K. The dip positions are almost appears above 17 T for H k c at low temperatures. In the superconducting
temperature independent. When the field is tilted away transitions, anomalous features (dips) are evident. (b) Second derivative
from the c axis by one degree, the superconducting phase curves of the interlayer resistance d 2 R=dH 2 . At 2.0 K, the broad peaks and
dips (dotted arrows) correspond to the two crossings of Hc2 through the
is strongly suppressed by the orbital effect and the dips superconducting transition. At 1.0 and 0.7 K, sharp dips (solid arrows)
completely disappear [Fig. 9(c)]. The dip positions are superposed on the broad structure are observed. (c) Resistive transitions at
independent of the current density. For H k a0 , the dip different field angles for T ¼ 0:95 K.
structures are strongly suppressed.
When the field is parallel to the layers, the magnetic flux
lines penetrate the insulating layers only (not the super- ðrÞ ¼ o cosðq  rÞ;
conducting layers) and form Josephson vortices (JVs). Since
the JVs are generally weakly pinned in the insulating layers, where the vector q ( FFLO ¼ 2
=q) is the center-of-mass
they can be easily driven by the Lorentz force for sufficiently momentum of the Cooper pairs. In Fig. 10, the q vector is
large interlayer current. Such JV motion, which is probably assumed to be oriented along the a0 axis. In the FFLO phase,
collective motion of the JV lattice at low temperatures, will the Josephson-coupling strength between the layers, which
cause a large energy dissipation, a finite resistance. The dip determines the Josephson-current density, periodically
structures in the resistive transitions show that the JVs varies with space because of the order-parameter oscillation.
are relatively strongly pinned at characteristic fields. This The JVs will be likely pinned at the positions where the
behavior is interpreted in term of a commensurability effect Josephson current is absent. The repulsive forces between
(Fig. 10) between the JV lattice constant l and the the JVs will produce an equally spaced array (JV lattice) in
wavelength of the order parameter oscillation FFLO of the the insulating layers. It should be noted that the size of the
FFLO state as explained below.104,105) JV (
15 nm) is comparable to or less than FFLO . When the
The periodic structure of the order parameter n ðrÞ can be ratio m ¼ l= FFLO is given by a simple integer number
written as (commensurate case), the JV lattice will be strongly pinned.
011004-9 #2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
(a)
(b)
Fig. 10. (Color online) Schematic picture of the Josephson vortices (JVs)
and order parameter oscillation. (a) Under in-plane field, all the magnetic
flux lines lie in the insulating layers and then JVs (arrows) are formed. Here,
the q vector of the oscillatory order parameter n ðrÞ is assumed to be along
the a0 axis. (b) JV lattice in the insulating layer and the oscillating order
parameter for a commensurate case (l= FFLO ¼ 2), where the JV lattice is
collectively pinned by the periodic structure of the order parameter.
This commensurability effect is observed only when the field
H is almost perpendicular to q. The JV lattice constant
is given by l ¼ 0 =sH, where 0 and s are the magnetic
flux quantum and the insulating layer spacing (
0:5 nm),
respectively. Since both l and FFLO change with field,106)
the strong pinning, leading to resistance dips, will happen at
some specific fields.
For isotropic three-dimensional systems, the above
commensurability effects are not expected because the
optimum q vector is parallel to H. This might be the case
for CeCoIn5 , whose high-field superconducting phase was
assigned to the FFLO phase.107,108) However, in two
dimensional systems such as -(BETS)2 FeCl4 where the
orbital effect is strongly quenched, the optimum q vector
strongly depends on the anisotropy of the two-dimensional
Fermi surface. Although it is difficult to calculate the
optimum q vector from the Fermi-surface structure, the
elongated cross-section of the two-dimensional Fermi sur-
face suggests that q is roughly parallel to the a0 axis. This
is consistent with the fact that the dip structure is evident
for H k c but is highly suppressed for H k a0 . The
commensurability fields should be independent of current
density, which is also consistent with the experimental
results. In the homogeneous superconducting phase, no
strong pinning mechanism is expected.
Figure 11 presents the temperature–field phase diagram,
where the insulator–metal transition field HIM , the critical
field (onset of superconductivity) Hc2 , and the dip positions
are plotted. No dips between 24 and 38 T at 0.7 K even for
larger current densities suggest that there exist boundaries
between the FFLO state and the homogeneous super-
conducting state at around 24 and 38 T.
011004-10
A. ARDAVAN et al.
Fig. 11. (Color online) Magnetic phase diagram for H k c. The triangles,
solid circles, open circles, and squares show the insulator–metal transition
field HIM , the critical field (the onset of the superconductivity) Hc2 , dip
positions, and the estimated l values at 0.7 K, respectively. The commen-
surate ratio m ¼ l= FFLO is also indicated. Inside the superconducting
phase, the phase boundary between the FFLO state and homogeneous
superconducting state is theoretically expected to be present (dotted lines).
S: superconducting phase, PM: paramagnetic metallic phase, AFI:
antiferromagnetic insulating phase.
The wavelength FFLO can be estimated under a few
reasonable assumptions.104)
(1) The ratio m ¼ l= FFLO is given by a simple integer
number at the resistance-dip fields.
(2) FFLO is of the order of the coherence length 
(
20 nm) near Hc2 .
(3) m
1 at the phase boundaries between the FFLO and
homogeneous superconducting phases (at around 24
and 38 T).
FFLO is infinite (m ¼ 0) in the homogeneous superconduct-
ing phase. The estimated FFLO and m values for T ¼ 0:7 K
are also shown in Fig. 11. An important tendency, FFLO
rapidly increases as the field reaches the homogeneous
superconducting phase, is seen. Theories predicts that the
FFLO state is generally stabilized only at low temperatures
T < 0:6Tc .102,103) In fact, the dips are evident only in the low-
temperature region of the superconducting phase (Fig. 11).
In the above discussion, a single q vector case is considered.
However, FFLO states with multiple q vectors may be
realized as theoretically suggested,109,110) whose stability
depends on the detailed structure of the Fermi surface.
As the field is tilted away from the conducting plane, the
FFLO phase is strongly suppressed by the orbital effect.
Assuming an in-plane isotropy of the electronic state,
Houzet et al.102) calculated the phase boundaries of the
homogeneous superconducting and FFLO phases for Tc ¼
4:3 K (Fig. 12). The dotted line shows Tc for the pure two-
dimensional case in parallel field (no orbital effect). The
FFLO phases appear below
2:2 K in the low- and high-
field regions. As the field is tilted from the layers, the orbital
effect increases and then the FFLO phase is suppressed. The
general solutions of the order parameter in the presence of
the orbital effect are expressed as the Landau-level functions,
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

t’

Fig. 12. (Color online) The theoretical phase diagram for different field
angles  for an isotropic 2D Fermi surface. The dashed line shows Tc in
parallel field (no orbital effect). The FFLO phases appear below
2:2 K in
the low and high field regions. The blue and red curves show the transitions
to the N ¼ 0 state (homogeneous S phase) and to the N > 1 states (FFLO
phase), respectively. For  ¼ 1 , successive FFLO transitions (N ! N þ 1)
take place in the low-field region, giving a kinked phase boundary.
Fig. 13. (Color online) In-plane structure of BEDT-TTF layers in
-(BEDT-TTF)2 X. The dimer lattice is modeled into an isosceles
triangular lattice as described in x4.4. The t and t0 stand for inter-dimer
transfer integrals, which construct a model of anisotropic triangular lattice
as depicted in Fig. 18.

characterized by the quantum number N. The N ¼ 0 and

N > 0 states correspond to the homogeneous superconduct-
ing and FFLO phases, respectively. When the field is slightly
tilted, the N ¼ 0 (homogeneous superconducting phase)
transitions (blue curves) are evident at high temperatures,
but the N > 0 (FFLO phase) transitions (red curves) appear
at lower temperatures. An interesting feature is the
successive transitions (N ! N þ 1), giving a kinked phase
boundary. This provides a sharp contrast to the case of no
orbital effect (two-dimensional case in parallel field), which
gives the smooth phase boundary (dashed curve in Fig. 12).
As the field is further tilted, only the N ¼ 0 transitions
appear in the whole field region: the FFLO phase is
completely suppressed by the orbital effect. For the N ¼ 0
phase, the vortices are expected to form a triangular
Abrikosov lattice in the layers under the perpendicular field.
The number of zeros of the order parameter coincides with
that of the vortices. However, in the FFLO phases (N > 1),
the number of the zeros is larger than that of the vortices:
only a fraction of the zeros are occupied by vortices. This
situation will lead to novel vortex lattices.102)
4. Superconductivity near the Mott Transition
Fig. 14. (Color online) Conceptual phase diagram of -(BEDT-TTF)2 X
In organic conductors, superconductivity mostly appears and related dimeric compounds.
in the vicinity of correlation-induced insulating phases.24,25)
Among them, Mott physics and its relevance to super-
conductivity are clearly illustrated in the family of layered 4.1 Antiferromagnetic order, spin liquid and
systems -(BEDT-TTF)2 X systems, whose in-plane struc- superconductivity competing around Mott transition
ture as depicted in Fig. 13 is modeled to an anisotropic The series of -(BEDT-TTF)2 X can be placed in the
triangular lattice of ET dimers with a half-filled band. The conceptual phase diagram of Mott transition as shown in
anisotropy and band width are characterized by two kinds of Fig. 14, where Mottness, namely U=W, is varied with X.
transfer integrals, t and t0 , which are varied by anion X, as U is the on-site (on-dimer) Coulomb interaction and W
discussed in x4.4. Therefore, electron correlation and spin is the width of the conduction band.114,115) The X ¼
frustration come into key roles in the nature of electronic Cu½NðCNÞ2 Cl salt116) is an antiferromagnetic Mott insula-
phases.111–113) This section is devoted to the magnetic and tor117) with a commensurate antiferromagnetic order,118)
transport characterization of charge and spin excitations near whereas the X ¼ Cu½NðCNÞ2 Br116) and Cu(NCS)2 20) salts
the Mott transition with varied frustration, the observation of are marginal and stable superconductors with Tc higher than
superconducting precursory behavior in the Nernst effect, 10 K, respectively. Their t0 =t values evaluated by first-
and the discussion of the pairing mechanism and symmetry principles calculations119,120) (molecular orbital-based tight-
in the superconducting condensate. binding calculations121)) are 0.44 (0.75), 0.42 (0.68), and
011004-11 #2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

0.58–0.66 (0.84), respectively, which are all well below

unity. In this series of less frustrated salts, superconductivity
competes with antiferromagnetic order.111,114,115) Actually,
the fully deuterated Cu[N(CN)2 ]Br salt (denoted as d[4,4]-
Cu[N(CN)2 ]Br in Fig. 14), which is pulled back to the
critical region of Mott transition by the ‘‘negative’’ chemical
pressure, shows phase separation of superconducting and
antiferromagnetic phases residing across the first-order d[4,4]−
Mott transition.122,123) Another member, X ¼ Cu2 ðCNÞ3 ,
not shown in the phase diagram is distinctive in that the
spins exhibit no ordering in spite of being in the Mott-
(a)
insulating state but is in a quantum spin-liquid state,124)
which is of current interest.125,126) The t0 =t value, 0.80–0.83
(1.06), indicates the highly frustrated nature,119,120) which
enhances spin fluctuations against antiferromagnetic order-
ing. This spin-liquid phase, when pressurized, shows a Mott
transition into a metallic phase, which undergoes a super-
conducting transition around 3–4 K, which is considerably
lower than Tc in the less-frustrated systems.121,127,128) The (b)
spin frustration seems harmful to superconductivity near the
Mott transition. Actually, Tc of the Cu2 (CN)3 salt is raised
up to 7 K under uniaxial strain, which deforms the triangular
lattice.32) In connection to this, it is interesting that another
spin liquid material, EtMe3 Sb[Pd(dmit)2 ],113) does not show
superconductivity in the metallic state under pressure down −
d[4,4]−
to the lowest temperature studied to date.
In addition, there are several contrasting features between 13 C NMR
Mott transitions from an antiferromagnet and spin liquid.
First, it is found in the profile of the Mott-transition
boundary in the temperature–pressure (T –P) plane. Accord-
ing to the Clausius–Clapeyron relation, the slope of the
phase boundary of the first-order transition dT =dP is Fig. 15. (Color online) Temperature dependence of (a) spin susceptibility
determined by the entropy balance between the two phases, and (b) 13 C NMR 1=T1 T for -(d[4,4], BEDT-TTF)2 Cu[N(CN)2 ]Br at
S, through dT =dP ¼ V =S, with V the volume ambient pressure and -(BEDT-TTF)2 Cu2 (CN)3 at 0.4 GPa and ambient
pressure.
difference between the two phases. At high temperatures
larger than the magnetic interaction energy, every kind of
Mott insulator shows higher spin entropy in the paramag-
netic state than the degenerate Fermi liquid has; namely S 4.2 Pseudo-gapped behavior and symmetry of electron
is positive. When they are cooled, the antiferromagnetic pairing
Mott insulator exhibits a drastic decrease in spin entropy due An influence of frustration is also seen in the magnetism
to the spin ordering to make S negative, whereas the of the metallic phase. Figure 15 displays the static suscepti-
entropy of the spin liquid without ordering is moderately bility and NMR relaxation rate divided by temperature,
temperature-dependent, remaining S positive down to low 1=T1 T , for the two marginally metallic phases, d[4,4]-
temperatures. This explains why the temperature-induced re- Cu[N(CN)2 ]Br at ambient pressure and Cu2 (CN)3 at 0.4 GPa
entrant Mott transition is clear in the anitiferromgnetic Mott (the data at ambient pressure are also shown). While the
insulator, Cu[N(CN)2 ]Cl salt129–132) but not in the spin- former, which is just on the border of the Mott transition,
liquid, Cu2 (CN)3 salt.128) It is noted that spins are not shows a macroscopic phase separation below 30 K into an
ordered all the way up to the Mott critical pressure128) and AF insulating phase and a metallic phase even in a single
application of magnetic field induces staggered moments as crystal, NMR can probe the two phases selectively by
detected with NMR124) and SR133) experiments. dealing with the well separated lines (only the metallic phase
Another contrasting feature appears in the charge excita- data shown).139) d[4,4]-Cu[N(CN)2 ]Br at ambient pressure
tion gap in the insulating side on the verge of Mott and Cu2 (CN)3 at 0.4 GPa (the value of hydrostatic pressure
transition. The optical conductivity shows a charge gap of applied at room temperature) show sharp Mott transitions/
0.11 eV in the Cu[N(CN)2 ]Cl salt,134) while the gap is not so crossovers at 30 and 15 K in resistivity, respectively. As seen
clear in the Cu2 (CN)3 salt.135) This evidences that the spin in the figure, the spin susceptibility continuously decreases
degrees of freedom are responsible for the nature of the without any anomaly around the Mott transition.140)
charge excitations in Mott insulators. Theoretically, exotic In contrast, 1=T1 T , which measures the wave-vector
charge excitations are proposed for several models of the summation of the dynamical spin susceptibility, is sensitive
spin-liquid state136,137) and the possible quantum nature of to the Mott transition. 1=T1 T shows a sudden drop indicative
the Mott transition emerging from the spin liquid is of the depression of AF spin fluctuations at 30 K in d[4,4]-
discussed.138) Cu[N(CN)2 ]Br and at 15 K in Cu2 (CN)3 .140) The sharp
011004-12 #2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
turnabout of the 1=T1 T variation coincides with the
inflection point of the metal–nonmetal resistivity crossover.
In the metallic phase, the two systems behave different. The
d[4,4]-Cu[N(CN)2 ]Br salt exhibits an anomalous decrease in
1=T1 T below 20 K, which is much higher than Tc of 11 K.139)
The decrease becomes too steep on approaching Tc to
observe a clear kink associated with the superconducting
transition at Tc . This feature is similar to the so-called
pseudo-gapped behavior observed for the underdoped high-
Tc cuprates141) and can be addressed as a common feature
near Mott transitions. In the Cu2 (CN)3 salt, however, 1=T1 T
is constant down to Tc once the system gets into the metallic
state.140) This is the Korringa relation as expected in
conventional metals. Thus, it is likely that the pseudo-gap
is inherent in less-frustrated systems with short-range spin
ordering, which leads to long-range order in the insulating
side. It has recently been found that the suppression of
superconductivity by magnetic field accompanies the closing
of the pseudo-gap. This fact suggests that the pseudogap has
something to do with the superconducting precursor as well
as the spin correlation mentioned above. Its connection to
the observation of an enhanced Nernst effect well above Tc
as described in x4.3 is of keen interest.142) It is remarkable
that a relatively high-Tc superconductivity is emergent from
this pseudo-gapped phase.
The symmetry of electron pairing in the superconducting
state is not fully agreed on but evidences for unconventional
pairing has been accumulated.143) Figure 16 shows the low-
temperature behavior of 1=T1 for the Cu[N(CN)2 ]Br salt
neighboring antiferromagnet and the Cu2 (CN)3 salt neigh-
boring spin-liquid states.140,144) They behave similar in the
superconducting state. The Hebel–Slichter coherence peak,
which is a hallmark of s-wave pairing, is absent and 1=T1
follows a T 3 law at lower temperatures. This behavior
common to the two systems points to a non-s-wave
anisotropic superconducting gap with line nodes, which is
consistent with an electronic mechanism for electron pairing
as discussed in x4.4. There is a slight difference between
the two behaviors; 1=T1 follows T 3 immediately below Tc in
the Cu2 (CN)3 salt but has a steep decrease before following
the T 3 dependence in the Cu[N(CN)2 ]Br salt. The former
type of behavior is observed as well in CeIrIn5 145) and
(TMTSF)2 ClO4 ,54) whereas the latter one is seen in
YBa2 Cu3 O7 in a more enhanced manner. The difference is
attributable to the superconducting coupling strength;146)
assuming d-wave pairing, the superconductivity in the
Cu[N(CN)2 ]Br salt turns out to be more strongly coupled
than in the Cu2 (CN)3 salt. The 13 C NMR Knight shift in the
Cu[N(CN)2 ]Br salt shows a clear decrease below Tc and
approach a vanishingly small value at lower temperatures,
pointing to singlet pairing,143,144,147) while the shift in the
Cu2 (CN)3 salt exhibits only a small decrease,140) which
should be further explored experimentally since the triplet
pairing is among the possible scenarios consistent with this
features.
4.3 Superconducting fluctuations and the Nernst effect
Traditionally, the superconducting transition in bulk
systems is considered in a mean-field picture within BCS
theory;148) the superconducting properties are associated
with the formation of an energy gap and of a phase-coherent
011004-13
A. ARDAVAN et al.
superfluid. Alternatively, it might be expected that thermal
fluctuations of the phase of condensate could destroy
superconductivity for materials with sufficiently low super-
fluid density (i.e., low phase stiffness). The fundamental
thermal excitations of the phase of a two-dimensional
superconductor are bound vortex–antivortex pairs.149) These
localized phase distortions exist at all finite temperatures,
and while they are bound, they do not affect the long-range
phase coherence of the superfluid. However, above some
temperature (corresponding to a Kosterlitz–Thouless transi-
tion temperature for the purely two-dimensional case) the
energy cost of separating the pairs is balanced by the
increase in entropy associated with the increase in available
configurations, and the pairs dissociate, destroying the
long-range phase coherence. An analogous phase-fluctuation
mechanism has been identified for bulk superconductors;150)
it is found that for a range of low-superfluid-density layered
superconductors including some high-Tc cuprates and
-(BEDT-TTF)2 X, the temperature scale at which phase
fluctuations are expected to become important is comparable
with Tc . In this scenario there is a temperature range over
which a condensate, and therefore an energy gap, exists, but
the mobile vortex-like excitations disrupt the long-range
phase coherence of the condensate. This offers an appealing
explanation for some of the pseudogap phenomena observed
in -(BEDT-TTF)2 X (see x4.2) and other materials.151)
The thermoelectric properties of the superconductor are
sensitive to the existence of such a state. Under the influence
of a temperature gradient rx T applied parallel to the
superconducting layers, mobile vortices, which can carry
heat more effectively than the surrounding superfluid, flow
down the temperature gradient. When the density of vortices
and antivortices is equal, this has no net effect other than to
transport heat. However, if a static magnetic field 0 Hz is
applied perpendicular to the layers there are more vortices in
the system than antivortices, and the net flow of flux down
the temperature gradient winds a phase across the superfluid
in the transverse direction perpendicular to both the
temperature gradient and the applied magnetic field. This
results in a transverse electric field Ey , known as the Nernst
effect, which is proportional to the applied magnetic field,
the magnitude of the temperature gradient and the mobility
of the vortices.
In principle, normal metals can exhibit a Nernst effect
too, but it is expected to be small152,153) (athough narrow
bandwidths and multiple bands crossing the chemical
potential can enhance it significantly154)). A Nernst effect
may also be expected in the regime of Gaussian fluctuations
of the order parameter close to the mean-field super-
conducting transition.155,156) The Nernst effect has been
studied extensively in high-Tc cuprates to investigate the
role of superconducting fluctuations in contributing to the
pseudogap properties.151,157,158)
-(BEDT-TTF)2 X offers several advantages for studying
superconducting fluctuations close to the Mott transition
over other systems such as high-Tc cuprates.142) The
magnetic field and temperature scales are smaller, so the
normal state is accessible and well-characterized; and the
key parameter tuning the superconducting properties, the
ratio of the on-site Coulomb repulsion to the band-
width U=W, is not associated with chemical or structural
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

10
X= Cu[N(CN)2]Br X=Cu2(CN)3
13C-NMR
1 13C NMR

(b)
1/T 1 (1/s)

(a)
0.1 μ 0 H =2.3 T

0.01

0.001
1 10 100
Temperature (K)

Fig. 16. (Color online) 13 C NMR 1=T1 in the superconducting states of (a) -(BEDT-TTF)2 Cu[N(CN)2 ]Br at ambient pressure and (b) -(BEDT-
TTF)2 Cu2 (CN)3 at 0.4 GPa. Magnetic fields of 2.3 T for X ¼ Cu½NðCNÞ2 Br and 2.0 T (closed circle)/3.5 T (open circles) for X ¼ Cu2 ðCNÞ3 are applied
parallel to the conducting layers. Broken and dotted lines in (b) are calculations for =kB Tc ¼ 2:2 and 4.0 in case of d-wave pairing. Lower inset: a linear
plot of 1=T1 .

(a) (b)

Fig. 17. (Color online) Nernst coefficient as a function of temperature for a range of magnetic fields in (a) -(BEDT-TTF)2 Cu(NCS)2 and (b) -(BEDT-
TTF)2 Cu[N(CN)2 ]Br. In each case, the zero magnetic field resistivity is also plotted (dashed line), showing the superconducting transition.

disorder. Figure 17 shows the Nernst coefficient N ¼ Ey =
ð0 Hz rx T Þ as a function of temperature for a range of
magnetic fields for the superconductors (a) X ¼ CuðNCSÞ2
(which lies far from the Mott transition) and (b) X ¼
Cu½NðCNÞ2 Br (which is closer to the Mott state, see
Fig. 14). Also shown in each case is the resistive transition
in zero applied magnetic field (dashed lines).
In X ¼ CuðNCSÞ2 lying away from the Mott transition, at
temperatures above Tc ¼ 10 K the Nernst coefficient is, as
expected for a normal metal, small and linear (i.e., the
Nernst voltage is proportional to the applied magnetic field;
note that the effect is so small that the signal exceeds the
noise only for applied fields above about 1 T). As the
temperature falls through the superconducting transition
temperature, a vortex-liquid state is established. The Nernst
signal becomes positive and increases dramatically in
magnitude, peaking at about 7.5 K and then falling again
at lower temperatures as the irreversibility line is approached
011004-14
and vortex motion freezes. The drop in the Nernst signal
occurs at the same temperature as the resistive transition in a
magnetic field159) because mobile vortices contribute to a
finite resistivity in the vortex-liquid state. In contrast to the
normal state, the Nernst coefficient arising from vortices is
strongly magnetic-field dependent, indicating that the vortex
mobility is dependent on the vortex density. In this material
the penetration depth is about 1 m, which is much larger
than the average vortex separation even at the lowest
magnetic fields studied. Thus the vortices are mutually
repulsive and this modifies their mobility as their density
increases. These observations are consistent with a simple
normal-superconducting transition, with a small and linear
Nernst coefficient above Tc and a large, positive and field-
dependent Nernst coefficient in the vortex-liquid state.
The situation is quite different for X ¼ Cu½NðCNÞ2 Br
lying closer to the Mott transition [Fig. 17(b)]. As for
X ¼ CuðNCSÞ2 , at temperatures well above Tc ¼ 11:8 K, the
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

Nernst coefficient is small, linear and negative, and well (a) (b)
below Tc , a large magnetic-field-dependent peak arising
from vortex motion appears. However, at intermediate
temperatures between Tc and about 1:5Tc ¼ 18 K, there is
a positive and magnetic-field-dependent contribution to the
Nernst coefficient that evolves smoothly into the peak below
Tc associated with vortices, and there is no sharp change in
behavior at Tc . Although it appears at temperatures above
the zero-magnetic-field resistive transition (which signals the
onset of long-range phase coherence), this contribution is
completely inconsistent with the small, linear and negative
Nernst coefficient associated with the normal state. It is
much more characteristic of the signal associated with
vortices, and is, therefore, strongly suggestive of a range of (c)
temperatures over which vortex-like excitations exist but
long-range phase coherence does not.
The fact that a fluctuating regime is found in X ¼
Cu½NðCNÞ2 Br but not in X ¼ CuðNCSÞ2 suggests several
things. Firstly, the behavior is not consistent with the theory
of the Nernst effect for Gaussian fluctuations, because
although the two compounds have comparable normal-state Fig. 18. The tight-binding hopping integrals of (a) the original four-band
conductivities and coherence lengths, they exhibit very model, (b) the two-band dimer model, and (c) the single-band dimer model.
different fluctuation behavior. Secondly, proximity to the
Mott state seems to be important. The number-phase
uncertainty in the superconducting state incurs an energy
penalty via the Coulomb interaction as the importance of
Coulomb repulsions increases150,160) and this should enhance
the susceptibility of the system to phase fluctuations as the
Mott state is approached.142)

4.4 Pairing mechanisms and symmetries

4.4.1 Effective models
A number of experiments suggest the occurrence of an
unconventional superconducting state in -(BEDT-TTF)2 X,
so there is a strong possibility that the Cooper pairing occurs
due to an unconventional mechanism where electron
correlations play an important role. An important step
towards theoretically understanding the mechanism of
superconductivity as well as the pairing symmetry is to
construct an effective Hamiltonian. Assuming that the origin
of superconductivity is purely electronic, namely, pairing
occurs due to electron correlation (not by electron–phonon
interaction), a many-body electronic Hamiltonian that takes
into account the band structure of the material is necessary to
construct a theory on the pairing mechanism.
For organic materials, the kinetic energy part of the
Hamiltonian can be described by a tight-binding model,
where each site corresponds to a molecule. Namely, the
electronic energy bands lying close to the Fermi level
usually originate from a single molecular orbital per
molecule, so that a molecule can be considered as a site in
the tight-binding model. The tight-binding hopping integrals
of -(BEDT-TTF)2 X were first estimated using the extended
Hückel method.121,161) As shown in Fig. 18(a), the hopping
integrals in the b direction alternate as tb1 ; tb2 ; tb1 . . . , where
jtb1 j > jtb2 j because of the dimerization of the molecules. In
the limit of large tb1 , namely, when the dimerization is
strong, each dimer can be considered as a single site, so the
system reduces to a two band model with n ¼ 1 (half-filling)
as shown in Fig. 18(b), where the band filling n here is
defined as n = the number of electrons/the number of
011004-15
Fig. 19. (Color online) The values of t and t0 in the dimer model
evaluated by the extended Hückel method in ref. 121, or by first-
principles band calculations in refs. 119 or 120. The (CN), (SCN), and
(Cl,Br) stand for X ¼ Cu2 ðCNÞ3 , Cu(NCS)2 , and Cu[N(CN)2 ](Cl,Br),
respectively.
sites.111,162) This corresponds to neglecting the lower two
bands which are separated by the bonding–antibonding gap
in the originally four band system. In the strong dimerization
limit, the effective hopping integrals tb and tc are given as
tb ¼ tb2 =2, tc ¼ ðtp þ tq Þ=2, and tc0 ¼ ðtp0 þ tq0 Þ=2 in
terms of the original hopping integrals.162) The system
further reduces to a half-filled single-band model (single site
per unit cell) when tc ¼ tc0 as in Fig. 18(c), and the Brillouin
zone can be unfolded. In this case, tc and tb are often denoted
as t and t0 , respectively.
More recently, the values of the hopping integrals have
been evaluated using first-principles band-structure calcula-
tions.119,120) The values of t and t0 are summarized in Fig. 19.
There is a tendency that the value of t does not differ much
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
(a) (b)
Fig. 20. (Color online) (a) The dx2 y2 -wave and (b) dxy superconducting
;
Þ, and also
gap in the unfolded Brillouin zone of the single-band model (upper panels)
or in the folded Brillouin zone of the two- or four-band models (lower). The
solid (dashed) curves represent the portions of the Fermi surface where the
gap has a positive (negative) sign. Q represents the wave vector of the spin
fluctuation mode that favors each pairing symmetry, and the long dashed
arrows represent the pair-scattering processes mediated by those spin
;
Þ
fluctuations. The short arrows denote the positions of the gap nodes.
from those evaluated by the extended Hückel method, while
t0 is reduced in the first-principles evaluation. Consequently,
the system deviates more substantially from the ‘‘regular
triangle’’ line of t ¼ t0 .
Another important part of the Hamiltonian is the electron–
electron interaction. In ref. 120, the electron–electron
interactions have been evaluated from first-principles
calculations using the constrained random phase approxima-
tion method. According to this study, the on-site interaction
U of the dimer model is U=t ¼ 12{15, which is substantially
larger than the previously adopted values. Also, the nearest-
neighbor repulsion is estimated to be about 40 percent of the
on-site interaction, which may not be neglected as has been
done in most of the theoretical studies of the dimer model of
-(BEDT-TTF)2 X.
4.4.2 Spin correlations and d-wave superconductivity
It was theoretically shown in ref. 111 that the insulating
state of -(BEDT-TTF)2 X can be understood as a Mott
insulator of the half-filled dimer model. Following this
study, there have been a number of theoretical studies on
superconductivity in the dimer model at half filling.163–174) In
these studies, the dx2 y2 -wave state, as shown in Fig. 20(a),
has been found to be the most dominant pairing symmetry.
This can be understood as follows. In a half-filled system on
a square lattice with on-site interaction, the spin correlation
develops at Q ¼ ð
;
Þ in the unfolded Brillouin zone if occurrence of an excitonic state of pairs of fermions with
t0 ¼ 0. In fact, this ð
;
Þ spin correlation is rather robust different charges as well as the superconducting state arising
against the introduction of t0 , and remains unless the system
is very close to the ‘‘regular triangle’’ line of t ¼ t0 (tb ¼ tc ).
The Q ¼ ð
;
Þ spin correlation induces a repulsive pairing is the degeneracy between dx2 y2 and dxy pairings. When
interaction, which scatters the electron pairs from ðk; kÞ to
ðk þ Q; k  QÞ as shown in Fig. 20(a), and forces the
011004-16
A. ARDAVAN et al.
Fig. 21. (Color online) The phase diagram of the single-band dimer
model in t0 –U space obtained by variational Monte Carlo method.172)
superconducting gap (order parameter)  to change its sign
between k and k þ Q, namely, ðkÞðk þ QÞ < 0. In order
to have opposite signs of the gap across Q ¼ ð
to satisfy the even parity condition for spin-singlet pairing
ðkÞ ¼ ðkÞ, the dx2 y2 gap is most favored.
Figure 21 shows the phase diagram of the dimer model
obtained by variational Monte Carlo method.172) When t0 =t
is small, antiferromagnetism with the wave vector ð
dominates as expected, but upon increasing t0 , dx2 y2 -wave
superconductivity sets in for not too large U. Similar phase
diagrams, especially regarding the dx2 y2 -wave supercon-
ductivity, have been obtained using cellular dynamical
mean-field theory173) and a Gutzwiller approximation
approach.174) It is interesting to note that the values of t
and t0 estimated from first-principles band calculation lie in
the regime where superconductivity takes place in this
theoretical approach. On the other hand, if the on-site U is as
large as those evaluated from first-principles calculation,
namely, U=t ¼ 12{15,120) then the system should be
insulating according to these studies. Since the off-site
interactions are also estimated to be large in ref. 120, its
effect on the boundary between superconductivity and other
phases is also of interest and remain as a future study.
4.4.3 Degree of frustration and dimerization
In the dimer model, the effect of geometrical frustration
becomes maximum at t ¼ t0 , namely, for the regular
triangular lattice. -(BEDT-TTF)2 Cu2 (CN)3 and also
Pd(dmit)2 -based salts have often been considered to be
close to this situation. The superconductivity in the vicinity
of the Mott transition on the triangular lattice has often been
discussed in connection with the spin-liquid state.137,175,176)
The coupling of spinons to the U(1) gauge field has been
considered as an origin of the pairing in the spin-singlet
channel175) or in the triplet channel.176) Reference 137 on the
other hand considers two types (e and e charge) of
fermionic excitations of the Z2 spin liquid, and proposes the
from the pairing of the same fermions.
One of the prominent features of the triangular lattice
d-wave pairing is realized, the two pairing symmetries have
the same Tc , and a fully gapped state with the form d þ id
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

takes place below Tc , where the two d-wave states are mixed
with a phase shift of
=2 and thus the time reversal
symmetry is broken.177) As the system deviates from t ¼ t0 ,
the degeneracy between dx2 y2 and dxy is lifted, so that the
system should undergo a double superconducting transition,
first to a pure d-wave, and then to the d þ id-wave.177) The
extended Hückel estimation of the hopping integrals of
-(BEDT-TTF)2 Cu2 (CN)3 gave nearly t ¼ t0 , so the possi-
bility of the d þ id state has often been discussed for this
material. On the other hand, as stated in x4.4.1, the first
principles estimations show that the frustration is not so
strong, which implies that the realization of d þ id pairing in
-(BEDT-TTF)2 Cu2 (CN)3 may be less likely provided that
the dimer model is valid. The possibility of d þ id pairing in
another candidate of a nearly ideal triangular lattice system,
Pd(dmit)2 salts, has also been proposed theoretically.178)
Another point of interest is the strength of the dimeriza-
tion. Since the dimer model is an effective model in the limit
of strong dimerization, it is interesting to look into the
relation between the dimer model and the original model
with four sites in a unit cell. Surprisingly, fluctuation
exchange approximation studies on the four-band model
have found that (i) Tc as high as those obtained in the dimer
model, which explains the experiments, cannot be reached
unless the dimerization is taken to be unrealistically strong
(jtb1 =tb2 j > 5),179) and (ii) the pairing symmetry is indeed
dx2 y2 for materials with relatively strong dimerization such
as X ¼ Cu½NðCNÞ2 Br (tb1 =tb2 ¼ 2:7121)), but the symmetry
changes to dxy in the more weakly dimerized X ¼ CuðNCSÞ2
(tb1 =tb2 ¼ 2:0121)).180,181) This is because the spin-fluctuation
wave vector Q moves to the one shown in Fig. 20(b) when
the dimerization becomes moderate, namely, when the
character of the quarter-filled system becomes stronger. In
this sense, the two pairing symmetries can be closely
competing (and thus a possibility of d þ id pairing arises)
even if the frustration in the sense of the dimer model is
not so strong. Experimentally, thermal conductivity182) and
STM experiments183) have suggested dxy -like gap for X ¼
CuðNCSÞ2 , consistent with the four-band theory, but a recent
specific-heat measurement shows that the pairing symmetry
is dx2 y2 regardless of the anion,184) so that the situation is
controversial. Clearly more study is necessary to clarify the
relationship among the dimer model, the original four-band
model, and the experimental observations of the super-
conducting gap and Tc in the actual materials.
5. Superconductivity near Charge Ordering
Among highly correlated organic superconductors,185) the
superconducting (SC) state neighboring to the Mott insulat-
ing state112,181) has been intensively investigated and
reviewed in x4. On the other hand, the research of the SC
state next to the charge-ordered state186–188) is on the way
to develop new materials and clarify the mechanism of
superconductivity. The structures, the characterization, and
the phase diagram of molecular conductors whose SC states
are next to charge-ordered states are described in x5.1 and
the theoretical aspect is reviewed in x5.2.
5.1 Structure, characterization, and phase diagram of
conductors
The donor arrangement of molecular conductors have
011004-17
Table I. Molecular conductors whose SC states are next to CO states.
Tco Tc Pc
Materials Ref.
(K) (K) (GPa)
0.2
-(BEDT-TTF)2 I3 135 7.2 192
(uniaxial pressure)
-(BEDT-TTF)2 I3 — 3.6 — 193
00 -(BEDT-TTF)3 Cl2 (H2 O)2 — 2 1.6 194
00 -(BEDT-TTF)4 Pt(CN)4 H2 O 2 0.65 195
00 -(BEDT-TTF)4 Pd(CN)4 H2 O 1.2 0.7 196
00 -(BEDT-TTF)4 (H3 O)Fe(C2 O4 )3 PhCN 8 0 197
00 -(BEDT-TTF)2 SF5 CH2 SF2 SO3 5.2 0 198
00 -(DODHT)2 PF6 255 3.1 1.65 199
-(meso-DMBEDT-TTF)2 PF6 70 4.3 0.4 200
Tco : CO transition temperature, Tc : SC transition temperature, Pc : critical
pressure.
been symbolized by Greek letters such as , , 0 , 00 , , , ,
etc.189–191) Among them, the molecular conductors whose
superconducting states are neighboring to charge-ordered
states belong to the , , 00 , and  types, which form the
3/4-filled band structure with small donor dimerization as
shown in Table I.192–200) The relation between the super-
conductivity and the charge ordering (CO) is described by
the view point of materials and their phase diagrams for
three kinds of donor arrangements, namely -(BEDT-
TTF)2 I3 and -(BEDT-TTF)2 I3 in x5.1.1, -(meso-
DMBEDT-TTF)2 PF6 in x5.1.2, and 00 -type charge-ordered
complexes in x5.1.3.
5.1.1 -(BEDT-TTF)2 I3 and -(BEDT-TTF)2 I3
The molecular conductor -(BEDT-TTF)2 I3 demonstrates
a peculiar solid state: electronic ferroelectricity below
135 K201) at ambient pressure due to the appearance of
stripe-type CO,186,187,202–207) superconductivity at Tc ¼ 7 K
under uniaxial strain of 0.2 GPa,192) and a zero-gap state
above 1.8 GPa.208,209)
This complex has a layered structure, consisting of
conducting BEDT-TTF donor sheets and insulating I3
layers. Since two molecules are situated in the inversion
center and one molecule is in a general position, two donor
molecules are crystallographically independent. The esti-
mated donor charges based upon the bond lengths are
+0.47(3) (A and A0 ), +0.57(4) (B), +0.41(3) (C) at room
temperature.207) The calculated band structure gives a
semimetallic state.202)
A metal–insulator transition occurs at 135 K under
ambient pressure. Calculations based on the extended
Hubbard model suggests a stripe-type CO.186) Crystal-
structure analyses by synchrotron radiation show that the
space group changes to the non-centrosymmetirc P1. The
charges of the crystallographically independent molecules
are estimated to be A [+0.82(9)], A0 [+0.29(9)], B
[+0.73(9)], and D [+0.26(9)], which constructs the stripe-
type CO.207) The CO has been observed by NMR203,204) and
Raman spectroscopy.205,206) The magnetic susceptibility
reveals a spin-singlet state below 135 K.210)
By applying uniaxial strain along the a axis, a resistance
drop has been observed under 0.15–5 GPa at Tc 7 K.192)
The pressure dependence is anisotropic and the uniaxial
strain along the b axis leads to a metallic state without
superconductivity. The phase diagram demonstrates that the
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

(a) (b)

(c) (e)

(d)

Fig. 22. (Color online) (a) Crystal structure, (b) donor arrangement, (c) band structure, (d) temperature dependence of the resistivity of -(BEDT-TTF)2 I3 ,
and (e) phase diagram of -type BEDT-TTF (abbreviated as ET) complexes. The red and blue regions correspond to the superconducting state of -(BEDT-
TTF)2 I3 and the non-magnetic insulating state for -(BEDT-TTF)2 RbM 0 (SCN)4 [M 0 ¼ Zn and Co] in the slow cooling condition, respectively.

SC state is neighboring to charge-ordered and non-gapped
singlet state.202) Analytical calculations by use of the random
phase approximation have been carried out based upon the
reconstructed Fermi surface under the horizontal stripe-type
CO in the metallic phase, where small hole and electron
pockets exist. This calculation has indicated s-wave-type
full-gap superconductivity mediated by the strong spin
fluctuations.33)
On the other hand, the -type donor arrangement has
a similar herringbone structure to that of the -type
[Figs. 22(a) and 22(b)]. Since the donor stacks regularly in
the -type complex, the calculated Fermi surface is a two-
dimensional closed one [Fig. 22(c)].211,212) It is reported
that about 1/3 of the measured crystals -(BEDT-TTF)2 I3
became superconducting below 3.6 K [Fig. 22(d)], whereas
the others stayed metallic. All annealed T -(BEDT-TTF)2 I3
crystals heat treated for 2 h at 70  C, however, show
superconducting properties at a slightly higher temperature,
5 K. This has been discussed as being due to an order–
disorder phenomenon of the terminal ethylene groups.213)
011004-18
The metallic state in -(BEDT-TTF)2 I3 shows no sign of CO
by NMR and Raman spectroscopy.206)
All -type BEDT-TTF complexes are characterized by
the inter-column transfer integral (t) proportional to the
bandwidth (8t) and the dihedral angle between columns ()
in Fig. 22(e).27) By increasing the transfer integral and
narrowing the dihedral angle, the electronic state changes
from insulating, SC, to the metallic state. Among them,
the superconducting state of -(BEDT-TTF)2 I3 is next to
the charge-ordered state of -(BEDT-TTF)2 MM0 (SCN)4
[M ¼ Tl, Rb, Cs, M0 ¼ Zn, Co].214) Especially, the compet-
itive CO patterns of q1 ð2=3; k; 1=3Þ and q2 ð0; k; 1=2Þ215)
due to the triangular charge frustration for -(BEDT-
TTF)2 CsCo(SCN)4 coexist below 50 K and cause a peculiar
nonlinear conduction at 4 K, namely an organic thyristor
effect: the thyristor-type voltage–current characteristics
function as the dc voltage–ac current conversion.216)
5.1.2 -(meso-DMBEDT-TTF)2 PF6
Recently, a novel pressure-induced superconductor with
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

(a) (c)
S S S S
(d)
S S
0.8
S S
V kc
meso-DMBEDT-TTF B Z
V
EF
(b) X

-0.5
BV Z X V

Charge Rich (R)

a
Charge Poor (P)
o c
3.6°

(e) (f)
100
8
ρ (ohm cm)

6
Resistivity (ohm cm)

4
Metal
LR- (or SR-CO)
Temperature (K)
2
CCO
LR-CCO
T (K) 10
8 +SR-CO
6

2 SC
1
0 1 2 3 4 5
Temperature (K) Pressure (kbar)

Fig. 23. (Color online) (a) Molecular structure of meso-DMBEDT-TTF, (b) crystal structure, (c) checkerboard-type donor arrangement composed of
charge rich (R) and charge poor (P) donors, (d) band structure, (e) temperature dependence of resistivity, and (f ) phase diagram of -(meso-DMBEDT-
TTF)2 PF6 . LR-CCO; long-range checkerboard-type charge-ordered state. SR-CO: short-range charge-ordered state. SC; superconducting state.

Tc ¼ 4:3 K under 0.4 GPa, -(meso-DMBEDT-TTF)2 PF6 200)
[DMBEDT-TTF = dimethyl-BEDT-TTF, Fig. 23(a)] has
been found.
This salt has a layered structure, with conducting donor
layers and insulating PF6  sheets. At ambient pressure, the
salt shows a metal–insulator transition at 90 K, and below
70 K a long-range checkerboard-type CO starts to grow.
In Figs. 23(b) and 23(c), the crystal structure and the
donor DODHT [1,4-dioxane-2,3-diyl-
checkerboard CO pattern determined by use of the
synchrotron radiation at 11.5 K are shown.217) If the CO
pattern is caused only by the inter-site Coulomb interaction
(V ), this salt should have a stripe-type order such as
-(BEDT-TTF)2 I3 rather than the checkerboard-type pattern.
The relation between the characteristic checkerboard-type
CO state and the peculiar electric-field induced metastable
state218) will be clarified by the X-ray and Raman spec-
troscopy measurements under the electric field. The
calculated band structure based upon the crystal structure
at 11.5 K is shown in Fig. 23(d). As shown in Fig. 23(e), the
checkerboard-type charge-ordered insulating state is sup-
pressed by pressure and a resistance drop signifying
superconductivity appears. The results of pressure-depen-
dent resistivity and Raman spectroscopy are summarized
in Fig. 23(f ).219) The SC state is neighboring to long-range
checkerboard-type and short-range charge-ordered states. A
011004-19
theoretical analysis of the extended Hubbard model based
upon the random phase approximation and Eliashberg
equations has proposed a competition of triplet SC due to
the charge fluctuations and the singlet SC owing to the
enhancement of spin fluctuations.220)
5.1.3 00 -type charge-transfer ordered complexes
The reduced
dithiodihydrotetrathiafulvalene, Fig. 24(a)], compared with
conventional TTF (tetrathiafulvalene), builds the super-
conductor 00 -(DODHT)2 PF6 with Tc ¼ 3:1 K under 1.65
GPa [Fig. 24(e)].199) Crystal-structure analysis reveals a
two-dimensional layered structure with conducting donor
sheets and insulating anion PF6  layers [Fig. 24(b)]. The
donor arrangement is 00 type, where the donors stack at 0
(side-by-side direction),189) 30 , and 60 [Fig. 24(c)]. The
band structure is calculated to be pseudo-one-dimensional
with additional hole pockets [Fig. 24(d)]. At ambient
pressure, a semiconductor-semiconductor transition occurs
at TCO ¼ 255 K with a doubling of the a axis due to CO.
Since the magnetic susceptibility is fitted by the alternating
Heisenberg model with J ¼ 159 K,  ¼ 0:38, and g ¼
2:0067, the pattern of the CO might be the stripe-type
[Fig. 24(c)]. By applying pressure, the transition tempera-
ture is lowered and a resistance drop is observed at Tc ¼ 3 K
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS A. ARDAVAN et al.

(a) (c)

(b)

(d)

(e) (f)

Fig. 24. (Color online) (a) Molecular structure of DODHT, (b) crystal structure, (c) donor arrangement, magnetic susceptibility, (d) band structure,
(e) temperature dependence of the resistivity, and (f ) phase diagram of 00 -DODHT2 PF6 . The TI in (c) and (e) denotes the temperature of the semiconductor-
semiconductor transition. The red line in (c) indicates the fitted susceptibility based upon the one-dimensional S ¼ 1=2 alternating Heisenberg chain model
along the molecular side-by-side direction. The gray circles and the arrows represent the charge rich sites and the magnetic moments, respectively.

under 1.37 GPa. The results of the resistivity study under
various pressures are summarized in the phase diagram as
shown in Fig. 24(f ).221)
As for other 00 -type BEDT-TTF complexes listed in
Table I, time-averaged charges of the molecular donors have
been observed by using vibrational spectroscopy and the
energy levels of the site-charge distributions were estimated.
The observations indicate that the instability due to the
closeness in the energy of several charge-ordered distribu-
tions correlates with the insulator–superconductor transition
in non-dimerized or weakly dimerized molecular conduc-
tors. Around the phase boundary, the site charges are neither
a well-defined charge-ordered state nor homogeneously
degenerated, but nearly degenerated in the charge-frustrated
state.222)
5.2 Superconductivity induced by charge fluctuations
As discussed in x4.4, each molecule can be regarded as a
single ‘‘site’’ in the extended Hubbard model, which enables
us to investigate physical properties very easily.223–225)
In this extended Hubbard model, nearest-neighbor and
011004-20
next-nearest-neighbor Coulomb repulsive interactions are
important for understanding various patterns of charge
ordering.187,226) There are several reasons why such an
extended Hubbard model is relevant in organic compounds.
First of all, the on-site Coulomb repulsion, U, is relatively
small because of the large size of the molecules. In contrast,
the long-range repulsion, V , is not negligible because of the
relatively weak screening effect. These facts were pointed
out by Hubbard in early days. Actual values of V =U are
around 0.2–0.6 depending on materials,227) and thus its value
is often used as a parameter in theoretical calculations.
Also it is to be noted that the electron density in organic
compounds is often commensurate, i.e., 1/4, which will
maximize the effects of nearest-neighbor repulsive interac-
tions. In fact, in the Mott insulator where the electron density
is half-filling, or 1/2, the long-range Coulomb repulsion has
negligible effects.228)
Naively thinking, the long-range nature of the Coulomb
repulsion disfavors the charge ordering or inhomogeneous
distribution of charge. However, in organic compounds,
insulating states due to charge ordering are often realized.
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
Therefore, the organic materials will be the best test-material
for studying superconductivity induced by charge fluctua-
tions.
Charge-fluctuation-induced superconductivity was first
discussed in the extended Hubbard model on a simple cubic
lattice.229) Later, Merino and McKenzie230,231) pointed out
that this mechanism is relevant in the organic compounds.
On the two-dimensional square lattice, it was shown that the
superconductivity with dxy -wave symmetry is stabilized due
to the nearest-neighbor repulsive interaction, V .229,232,233)
Actually, when V is very large, a charge order with
checkerboard pattern appears. As V decreases, the critical
temperature, Tc , of the phase transition into the charge order
also decreases. The parameter, V ¼ Vc , at which Tc becomes
zero is the quantum critical point. The superconductivity
appears when V is less than Vc , but the parameter region of
superconductivity is rather narrow, which is a usual situation
obtained in the random-phase approximation. This indicates
that, although the superconductivity is actually induced
by charge fluctuations, it is not so strongly stabilized. Its
physical reason will be that the charge ordering in this case
is very strong because of the commensurability of the
charge-order pattern (checkerboard) and the square lattice.
In this sense, if the charge-order pattern has frustration, one
can expect that the charge-order is not so strongly stabilized
and instead the superconductivity is stabilized. This will be
discussed below.
In the square lattice, the dxy -wave symmetry of super-
conductivity is understood rather easily in the real-space
picture. When the gap function of dxy -wave symmetry is
Fourier transformed into the real space, one can see that the
Cooper pairing occurs mainly on the next-nearest-neighbor
sites, i.e., positive amplitude in the y ¼ x direction and
negative amplitude in the y ¼ x direction. This Cooper
pairing is equivalent with the checkerboard pattern of the
charge order. Basically, the instability towards the checker-
board pattern enhances the probability that the two electrons
are located in the next-nearest-neighbor sites. This favors the
pairing on these two sites, leading to the dxy -wave super-
conductivity. Later it is shown that a similar picture is
effective even in the frustrated lattices.
Here it is worthwhile noting that a reentrant behavior is
found in RPA and dynamical mean-field theory; i.e., as the
temperature is lowered, the system undergoes a charge-order
phase transition, and then at a lower temperature it goes into
sign shown in Fig. 25(b). This Cooper
a superconducting state. This is rather surprising that the
(charge-)ordered phase exists at higher temperatures than the
metallic or superconducting state. However, it is believed
that this kind of reentrant behavior can be understood in the
following mechanism. At low temperatures, the Fermi
surface is sharp and then the violation of the nesting
condition is apparent. In this case, the charge ordering does
not occur. However, as the temperature increases, the
smearing of the Fermi surface helps to recover the nesting
condition partly. This leads to the instability of charge
ordering at high temperatures.
As discussed in the previous subsection, -type BEDT-
TTF complexes have a deformed triangular lattice rather
than a simple square lattice. Therefore it is an interesting
problem to study the superconductivity in the deformed
triangular lattice. As discussed before, it seems that the two
011004-21
A. ARDAVAN et al.
(a) (b)
Fig. 25. (Color online) (a) 3-fold charge-order pattern realized in the
extended Hubbard model on a frustrated triangular lattice and (b)
corresponding Cooper pairing in the real space.
kinds of charge-order patterns compete with each other due
to frustration in the triangle geometry. In such a case, the
tendency toward charge ordering is weakened and there
appears a large parameter region in which a metallic state is
realized. This was called as a ‘‘quantum melting’’ of charge
order.234,235) Simultaneously, the possibility of superconduc-
tivity becomes large. Based on these ideas, several
researches for superconductivity have been carried out, for
example, by RPA,236) FLEX,233) and variational Monte Carlo
simulations.237)
Interesting result is that a spin-triplet superconductivity is
realized with f-wave-like gap symmetry.235,237) This triplet
pairing is not surprising because the charge fluctuation (spin-
independent) equally contributes to the singlet and triplet
pairing channels. As in the case of the square lattice, the
physical reason of this f-wave symmetry can be understood
in the real-space picture. Due to the frustration in the
deformed triangular lattice, the 3-fold pattern shown in
Fig. 25(a) is stabilized. Basically the nearest-neighbor
repulsive interaction repels electrons from the nearest-
neighbor sites, and as a result, there is a tendency that the
electrons are located in the next-nearest neighbor sites which
leads to the 3-fold pattern in Fig. 25(a). (Note, however, that
if one electron occupies every next-nearest-neighbor site, the
electron density is not equal to 1/4 but becomes 1/3. Since
-type BEDT-TTF has an electron density of 1/4, this 3-fold
charge order is not strong, and it will be rather a CDW-type
order.) When the gap function of f-wave symmetry is
Fourier transformed into the real space, one can see that
the Cooper pairing can occur mainly on the next-nearest-
neighbor sites with
pairing is equivalent with the above 3-fold pattern. In this f-
wave case, the pair amplitude on the nearest-neighbor sites
vanishes because of the presence of the nodes in this
direction. Another candidate of the symmetry is an extended
s-wave, in which all the phases on the 6 next-nearest-
neighbor sites are equal. However, in this case, there is no
reason why the pair amplitude on the 6 nearest-neighbor
sites vanishes. This disfavors the extended s-wave pairing.
As discussed in this section, there are several interesting
possibilities of new types of superconductivity in the vicinity
of charge ordering. However, the nature of superconductiv-
ity, in particular for -(BEDT-TTF)2 I3 shown in Fig. 22(d),
has not been clarified yet because of the difficulty of
preparing good-quality samples. It remains an interesting
problem to search for superconductivity in the vicinity of
quantum critical point of the charge ordering.
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
6. Summary and Perspectives
The discovery of the conductive perylene-Br2 in 1954 was
the starting point of research into organic conductors.1) The
extremely high conductivity observed in the charge transfer
salt, TTF-TCNQ, and the doped polyacetylene films in the
1970’s further promoted the quest for organic metals and
superconductors. Then, the discovery of superconductivity
in a quasi-one-dimensional TMTSF salt in 1979, coinciding
with the first observations of heavy-fermion superconduc-
tivity, marked the beginning of a new era in basic
superconductivity research, in which electron correlations
are inseparable from the superconducting phenomenon. The
Bechgaard salts share with other more highly correlated
materials the layered structure, and most likely magneti-
cally-mediated pairing, but with no pseudo-gap phenomena.
The behavior near to the critical pressure cannot be
accounted for by the self-consistent renormalized theory of
spin fluctuations, and it appears this is a consequence of the
interference between the pairing interaction and the spin
fluctuations. Experimental observations are consistent with a
singlet ground state and an energy gap with lines of zeros
over the Fermi surface. Persistence of superconductivity to
fields significantly exceeding the Pauli-limiting field, leaves
open the possibility for triplet pairing, or other novel states
at high magnetic fields.
The layered materials exhibit experimental indications of
an exotic Cooper pairing under high magnetic field parallel
to the layers, where the orbital pair-breaking effect is
quenched. In this condition, a possible Cooper paring with
spatially varying order parameter called FFLO state result-
ing from the compromise between the singlet paring and the
Pauli paramagnetism has long been argued. The specific-
heat measurements of a BEDT-TTF salt provided thermo-
dynamic evidence for a phase transition within the mixed
state and the transport experiments of a BETS salt point to
some sort of periodic modulation which is effective to pin
the Josephson-vortex lattice. Both can be indications of
the FFLO state. Direct observation of a modulated order
parameter is anticipated.
In dimerized BEDT-TTF salts with half-filled band
nature, superconductivity is emergent nearby the Mott
insulating phase when the electron correlation is varied by
physical or chemical pressure. Both of Mott insulating and
metallic phases are affected by the frustration of the dimer
lattice, which is modeled to the anisotropic triangular lattice.
In the Mott insulating side, the spins exhibit antiferromag-
netic ordering in the less-frustrated lattices but are in a
quantum-liquid state without ordering in frustrated lattices.
In the metallic side, superconductivity with Tc over 10 K
appears with pseudo-gapped behavior in NMR relaxation
above Tc in less frustrated lattices where short-range
magnetic correlations are expected to be enhanced, whereas
superconductivity has lower Tc and accompanies no pseudo-
gapped behavior nearby the spin-liquid phase in a frustrated
lattice. As far as the half-filled band is concerned, the
frustration seems to work against superconductivity. Many
of the experimental results suggest nodal superconductivity
of spin-singlet pairing, which is among the theoretical
consequences of spin-fluctuation-mediated superconductiv-
ity, although the spin state of the superconductivity
011004-22
A. ARDAVAN et al.
neighboring the spin liquid remains open. It is remarkable
that the Nernst effect is clearly visible even well above Tc on
the verge of the Mott transition, signifying the enhancement
of phase fluctuations in the correlated electrons that are
about to be localized. The interrelationship between the
pseudo-gap and the enhanced Nernst effect which are
manifestations in spin and orbital channels, respectively, is
an intriguing issue for further investigations.
In some of non-dimerized or weakly dimerized salts with
quarter-filled bands, superconductivity appears in competi-
tion or coexistence with charge ordering.238) Theoretical
studies suggest the possible involvement of charge fluctua-
tions in the emergence of superconductivity and predict a
new type of f-wave paring on a triangular lattice where
charges are strongly correlated but fail to be ordered due to
the frustration. Experimental characterization of the pairing
symmetry of the superconductivity as described in x5.1 is a
forthcoming issue.
As demonstrated in the study of the high-Tc cuprates, to
dope Mott insulators is a promising route to produce
superconductivity. However, organics have difficulty in
accommodating differently valent anions or cations as
dopants. Nevertheless, there are a few trials, which
succeeded in metalizing the insulators:239–241) superconduc-
tivity is reported only in ref. 239. One possible reason for
difficulty in doping organic conductors is the disorder due to
the randomly distributed dopants, which should be more
significant in organics with narrower bandwidth than
transition-metal oxides; in particular, the random Coulomb
potential produced by the dopants should not be negligible.
The non-stoichiometric compounds, -(BEDT-TTF)4 X (X ¼
Hg2:78 Cl8 and Hg2:89 Br8 )242) can be doped Mott insulators
with the randomness minimized, because the deficiency
from three in the Hg composition, which contributes to
hole doping to the half-filled band, is produced by the
incommensurate anion lattice against the BEDT-TTF
lattice, not by the random congigulation of the ions. The
non-Fermi liquid properties243,244) and inhomogeneity245,246)
around the superconducting dome against pressure point
to a similarity to the cuprates and are expected to stimu-
late further research. The electric-field-induced charge
injection into a Mott insulator with FET structure is another
way of doping. A drastic change in conductivity under
gating voltage points to the filling-controlled Mott transi-
tion,247) while superconductivity has not been seen at
present. The liquid-gated electric-double-layer FET has
been attracting attention as a method to induce high density
of carriers.248)
The synthesis of new materials is in the center of the
superconductivity research. The discovery of superconduc-
tivity at 18 K or higher in alkali-metal-picene compounds
with a 3 : 1 composition is the latest news, which has
renewed the highest Tc among organic superconductors.23)
This finding has been followed by the recent observation of
superconductivity in an analogous potassium-phenanthrene
compound,249) which implies the birth of a new family of
organic superconductors. The structural identification of the
18-K superconducting phase is keenly anticipated. Most of
the organic superconductors have 2 : 1 composition with one
carrier per two conducting molecules, where the short-range
Coulomb interactions are less significant due to the quarter-
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
filling nature even in the dimeric cases. In order to
strengthen the electron correlations, 1 : 1 salts with one
carrier per molecule are more attractive systems, where the
short-range Coulomb interaction is enhanced in a half-filled
band and can be made competitive with the electron kinetic
energy (bandwidth) in a higher energy scale for getting
higher Tc . From the viewpoint of molecular orbitals, the
conduction band in most of the organic superconductors is
composed of a single orbital, HOMO or LUMO. Systems
having different orbitals responsible for the conduction band
as in the single-component molecular conductors250) can be
another frontier for novel superconductors. Besides phonon
excitations, spin fluctuations and charge fluctuations, the
excitonic or dielectric degrees of freedom were argued
as possible mechanisms for novel superconductivity long
before. In several materials the charge order accompanies
ferroelectric or antiferroelectric order. Whether the fluctua-
tions of electric polarization can be a glue of electron pairing
is an interesting issue. In this sense, highly polarizable
and potentially conductive materials such as neutral-ionic
transition systems are interesting. As another category of
materials, organic polymers, which has been studied parallel
to the charge-transfer salts, have afforded attractive
conducting properties particularly for applications and also
provided distinctive flavors of physics such as mobile
solitons. If this class of materials, in particular non-
crystalline-polymers, comes into the field of superconduc-
tivity, it would be a breakthrough for basic and applied
sciences. The one-dimensionality and disorder inherent in
conventional polymers, which are harmful to superconduc-
tivity, are main problems to be conquered. To produce novel
superconductivity, pressure is effective means especially for
highly compressible molecular materials, which was demon-
strated in the 14.2 K-superconductivity found under a high
pressure of 8.2 GPa.251)
The organic systems are known to be so clean that the
disorder effect, which often obscures intrinsic phenomena, is
minimized. This is an advantageous point for the experi-
mental study. In contrast, organic materials are not
experimentally friendly for the k-dependent probes such as
angle-resolved photo-emission and neutron spectroscopy
because of surface degradation against light irradiation for
the former probe and small crystal sizes for the latter. When
these two probes become accessible to organic materials,
one can imagine a breakthrough in the superconductivity
research.
Acknowledgments
The authors would like to thank B. Bergk, R. Lortz, Y.
Nakazawa, G. Zwicknagl, J. S. Brooks, H. Shimahara,
R. Ikeda, K. Miyagawa, Y. Shimizu, F. Kagawa, M.
Matsumoto, M.-S. Nam, K. Takahashi, K. Yamamoto, K.
Yakushi, H. Sawa, and C. Bourbonnais for collaboration and
discussion. This material is based on work supported by
MEXT/JSPS Grants-in Aid for Scientific Research [Cate-
gory ‘‘A’’ (No. 20244055), Category ‘‘B’’ (No. 20340087)
and Category ‘‘Innovative Areas’’ (Nos. 20110002,
20110004, and 20110007)], the National Science Foundation
under Grant Nos. DMR-0804625 and DMR-1105531, and
EuroMagNET under contract No. 228043. A.A. is supported
by the Royal Society.
011004-23
A. ARDAVAN et al.
1) H. Akamatu, H. Inokuchi, and Y. Matsunaga: Nature 173 (1954) 168.
2) W. A. Little: Phys. Rev. 134 (1964) A1416.
3) J. Ferraris, D. O. Cowan, V. Walatka, Jr., and J. H. Perlstein: J. Am.
Chem. Soc. 95 (1973) 948.
4) L. B. Coleman, M. J. Cohen, D. J. Sandman, F. G. Yamagishi, A. F.
Garito, and A. J. Heeger: Solid State Commun. 12 (1973) 1125.
5) D. E. Schafer, F. Wudl, G. A. Thomas, J. P. Ferraris, and D. O.
Cowan: Solid State Commun. 14 (1974) 347.
6) As a review see for example, G. Grüner: Density Waves in Solids
(Addison-Wesley, 1994).
7) H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, and
A. J. Heeger: J. Chem. Soc., Chem. Commun. (1977) 578.
8) R. L. Greene, G. B. Street, and L. J. Suter: Phys. Rev. Lett. 34 (1975)
577.
9) D. Jérome, A. Mazaud, M. Ribault, and K. Bechgaard: J. Phys. Lett.
41 (1980) L95.
10) K. Bechgaard, K. Carneiro, M. Olsen, F. B. Rasmussen, and C. S.
Jacobsen: Phys. Rev. Lett. 46 (1981) 852.
11) D. Jaccard, H. Wilhelm, D. Jérome, J. Moser, C. Carcel, and J. M.
Fabre: J. Phys.: Condens. Matter 13 (2001) L89.
12) T. Adachi, E. Ojima, K. Kato, H. Kobayashi, T. Miyazaki, M.
Tokumoto, and A. Kobayashi: J. Am. Chem. Soc. 122 (2000) 3238.
13) S. S. P. Parkin, E. M. Engler, R. R. Schumaker, R. Lagier, V. Y. Lee,
J. C. Scott, and R. L. Greene: Phys. Rev. Lett. 50 (1983) 270.
14) E. B. Yagubskii, I. F. Shchegolev, V. N. Laukhin, P. A. Kononovich,
M. V. Kartsovnik, A. V. Zvarykina, and L. I. Buravov: JETP Lett. 39
(1984) 12.
15) K. Murata, M. Tokumoto, H. Anzai, H. Bando, G. Saito, K.
Kajimura, and T. Ishiguro: J. Phys. Soc. Jpn. 54 (1985) 2084.
16) V. N. Laukhin, E. E. Kostyuchenko, Yu. V. Sushko, I. F. Shchegolev,
and E. B. Yagubskii: JETP Lett. 41 (1985) 81.
17) P. C. W. Leung, T. J. Emge, M. A. Beno, H. H. Wang, and J. M.
Williams: J. Am. Chem. Soc. 106 (1984) 7644.
18) Y. Nogami, S. Kagoshima, T. Sugano, and G. Saito: Synth. Met. 16
(1986) 367.
19) S. Ravy, R. Moret, J. P. Pouget, and R. Comes: Synth. Met. 19 (1987)
237.
20) H. Urayama, H. Yamochi, G. Saito, K. Nozawa, T. Sugano, M.
Kinoshita, S. Sato, K. Oshima, A. Kawamoto, and J. Tanaka: Chem.
Lett. 17 (1988) 55.
21) A comprehensive list of organic superconductors, with references and
figures of molecular structure, is provided by H. Mori at http://
hmori.issp.u-tokyo.ac.jp/other/List-of-orgsuper.pdf
22) A comprehensive list of organic superconductors, with references and
figures of molecular structure, is available in H. Mori: J. Phys. Soc.
Jpn. 75 (2006) 051003.
23) A comprehensive list of organic superconductors, with references and
figures of molecular structure, is available in H. Mori: Introduction to
Organic Electronic and Optoelectronic Materials and Devices (CRC
Press, Taylor & Francis Group, NY, 2008) Chap. 9, pp. 263–285.
24) As a review see for example, T. Ishiguro, K. Yamaji, and G. Saito:
Organic Superconductors (Springer, Berlin, Heidelberg, 1998)
Springer Series in Solid State Sciences.
25) As a review see for example, A. G. Lebed, ed.: The Physics of
Organic Superconductors and Conductors (Springer, Heidelberg,
2008) Springer Series in Materials Science, Vol. 110.
26) R. Mitsuhashi, Y. Suzuki, Y. Yamanari, H. Mitamura, T. Kambe, N.
Ikeda, H. Okamoto, A. Fujiwara, M. Yamaji, N. Kawasaki, Y.
Maniwa, and Y. Kubozono: Nature 464 (2010) 76.
27) H. Mori, S. Tanaka, and T. Mori: Phys. Rev. B 57 (1998) 12023.
28) H. Elsinger, J. Wosnitza, S. Wanka, J. Hagel, D. Schweitzer, and W.
Strunz: Phys. Rev. Lett. 84 (2000) 6098.
29) P. Fulde and R. A. Ferrell: Phys. Rev. 135 (1964) A550.
30) A. I. Larkin and Y. N. Ovchinnikov: Sov. Phys. JETP 20 (1965) 762.
31) M. Maesato, Y. Kaga, R. Kondo, and S. Kagoshima: Rev. Sci.
Instrum. 71 (2000) 176.
32) Y. Shimizu, M. Maesato, G. Saito, O. Drozdova, and L. Ouahab:
Synth. Met. 133–134 (2003) 225; Y. Shimizu, M. Maesato, and G.
Saito: J. Phys. Soc. Jpn. 80 (2011) 074702; Y. Shimizu, M. Maesato,
and G. Saito: J. Phys. Soc. Jpn. 80 (2011) 074702.
33) A. Kobayashi, S. Katayama, and Y. Suzumura: J. Phys. Soc. Jpn. 74
(2005) 2897.
34) F. Steglich, J. Aarts, C. D. Bredl, W. Lieke, D. Meschede, W. Franz,
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
and H. Schäfer: Phys. Rev. Lett. 43 (1979) 1892.
35) N. Thorup, G. Rindorf, H. Soling, and K. Bechgaard: Acta
Crystallogr., Sect. B 37 (1981) 1236.
36) P. M. Grant: Phys. Rev. B 26 (1982) 6888.
37) J. Moser, J. R. Cooper, D. Jérome, B. Alavi, S. E. Brown, K.
Bechgaard, P. Auban-Senzier, D. Jerome, K. Bechgaard, and J.
Fabre: Phys. Rev. Lett. 84 (2000) 2674.
38) G. Mihaly, I. Kezsmarki, F. Zamborszky, and L. Forro: Phys. Rev.
Lett. 84 (2000) 2670.
39) M. Dressel, K. Petukhov, B. Salameh, P. Zornoza, and T. Giamarchi:
Phys. Rev. B 71 (2005) 075104.
40) G. M. Danner, W. Kang, and P. M. Chaikin: Phys. Rev. Lett. 72
(1994) 3714.
41) R. Brusetti, M. Ribault, D. Jérome, and K. Bechgaard: J. Phys. 43
(1982) 801.
42) T. Vuletić, P. Auban-Senzier, C. Pasquier, S. Tomić, D. Jérome, M.
Héritier, and K. Bechgaard: Eur. Phys. J. B 25 (2002) 319.
43) I. J. Lee, S. E. Brown, W. Yu, M. J. Naughton, and P. M. Chaikin:
Phys. Rev. Lett. 94 (2005) 197001.
44) L. P. Gor’kov and P. D. Grigoriev: Phys. Rev. B 75 (2007) 020507.
45) N. Kang, B. Salameh, P. Auban-Senzier, D. Jérome, C. R. Pasquier,
and S. Brazovskii: Phys. Rev. B 81 (2010) 100509.
46) S. E. Brown, M. J. Naughton, and P. M. Chaikin: The Physics of
Organic Superconductors and Conductors (Springer, Heidelberg,
2008) Springer Series in Materials Science, Vol. 110.
47) D. S. Chow, F. Zamborszky, B. Alavi, D. J. Tantillo, A. Baur, C. A.
Merlic, and S. E. Brown: Phys. Rev. Lett. 85 (2000) 1698.
48) P. Monceau, F. Y. Nad, and S. Brazovskii: Phys. Rev. Lett. 86 (2001)
4080.
49) H. Seo and H. Fukuyama: J. Phys. Soc. Jpn. 66 (1997) 1249.
50) M. Itoi, C. Araki, M. Hedo, Y. Uwatoko, and T. Nakamura: J. Phys.
Soc. Jpn. 77 (2008) 023701.
51) M. Y. Choi, P. M. Chaikin, S. Z. Huang, P. Haen, E. M. Engler, and
R. L. Greene: Phys. Rev. B 25 (1982) 6208.
52) N. Joo, P. Auban-Senzier, C. R. Pasquier, D. Jérome, and K.
Bechgaard: Europhys. Lett. 72 (2005) 645.
53) A. A. Abrikosov: J. Low Temp. Phys. 53 (1983) 359.
54) M. Takigawa, H. Yasuoka, and G. Saito: J. Phys. Soc. Jpn. 56 (1987)
873.
55) Y. Hasegawa and H. Fukuyama: J. Phys. Soc. Jpn. 56 (1987) 877.
56) S. Belin and K. Behnia: Phys. Rev. Lett. 79 (1997) 2125.
57) I. J. Lee, M. J. Naughton, G. M. Danner, and P. M. Chaikin: Phys.
Rev. Lett. 78 (1997) 3555.
58) J. I. Oh and M. J. Naughton: Phys. Rev. Lett. 92 (2004) 67001.
59) A. G. Lebed and K. Yamaji: Phys. Rev. Lett. 80 (1998) 2697.
60) A. G. Lebed: Phys. Rev. B 59 (1999) R721.
61) J. Shinagawa, Y. Kurosaki, F. Zhang, C. Parker, S. E. Brown, D.
Jérome, J. B. Christensen, and K. Bechgaard: Phys. Rev. Lett. 98
(2007) 147002.
62) B. J. Powell: J. Phys.: Condens. Matter 20 (2008) 345234.
63) K. Yang and S. L. Sondhi: Phys. Rev. B 57 (1998) 8566.
64) C. Bourbonnais and A. Sedeki: Phys. Rev. B 80 (2009) 085105.
65) H. Shimahara: J. Phys. Soc. Jpn. 69 (2000) 1966.
66) N. Belmechri, G. Abramovici, and M. Heritier: Europhys. Lett. 82
(2008) 47009.
67) K. Kajiwara, M. Tsuchiizu, Y. Suzumura, and C. Bourbonnais:
J. Phys. Soc. Jpn. 78 (2009) 104702.
68) S. Yonezawa, S. Kusaba, Y. Maeno, P. Auban-Senzier, C. Pasquier,
K. Bechgaard, and D. Jérome: Phys. Rev. Lett. 100 (2008) 117002.
69) S. Yonezawa: private communication.
70) W. Wu, P. M. Chaikin, W. Kang, J. Shinagawa, W. Yu, and S. E.
Brown: Phys. Rev. Lett. 94 (2005) 097004.
71) A. J. Millis, H. Monien, and D. Pines: Phys. Rev. B 42 (1990) 167.
72) T. Moriya: Adv. Phys. 49 (2000) 555.
73) Y. Kitaoka, K. Ishida, G.-q. Zheng, S. Ohsugi, and K. Asayama:
J. Phys. Chem. Solids 54 (1993) 1385.
74) N. Doiron-Leyraud, P. Auban-Senzier, S. Rene de Cotret, C.
Bourbonnais, D. Jérome, K. Bechgaard, and L. Taillefer: Phys.
Rev. B 80 (2009) 214531.
75) N. Doiron-Leyraud, S. René de Cotret, A. Sedeki, C. Bourbonnais, L.
Taillefer, P. Auban-Senzier, D. Jérome, and K. Bechgaard: Eur. Phys.
J. B 78 (2010) 23.
76) L. Taillefer: Annu. Rev. Condens. Matter Phys. 1 (2010) 51.
011004-24
A. ARDAVAN et al.
77) A. Sedeki, D. Bergeron, and C. Bourbonnais: Physica B 405 (2010)
S89.
78) K. Kanoda: Physica C 282–287 (1997) 299.
79) S. Uji, H. Shinagawa, T. Terashima, T. Yakabe, Y. Terai, M.
Tokumoto, A. Kobayashi, H. Tanaka, and H. Kobayashi: Nature 410
(2001) 908.
80) G. Zwicknagl and J. Wosnitza: Int. J. Mod. Phys. B 24 (2010) 3915.
81) R. Lortz, Y. Wang, A. Demuer, P. H. M. Böttger, B. Bergk, G.
Zwicknagl, Y. Nakazawa, and J. Wosnitza: Phys. Rev. Lett. 99
(2007) 187002.
82) J. M. Caulfield, W. Lubczynskii, F. L. Pratt, J. Singleton, D. Y. K.
Ko, W. Hayes, M. Kurmoo, and P. Day: J. Phys.: Condens. Matter 6
(1994) 2911.
83) J. Singleton, P. A. Goddard, A. Ardavan, N. Harrison, S. J. Blundell,
J. A. Schlueter, and A. M. Kini: Phys. Rev. Lett. 88 (2002) 037001.
84) J. Müller, M. Lang, R. Helfrich, F. Steglich, and T. Sakai: Phys. Rev.
B 65 (2002) 140509.
85) J. Wosnitza, S. Wanka, J. Hagel, M. Reibelt, D. Schweitzer, and
J. Schlueter: Synth. Met. 133–134 (2003) 201.
86) H. Elsinger, J. Wosnitza, S. Wanka, J. Hagel, D. Schweitzer, and W.
Strunz: Phys. Rev. Lett. 84 (2000) 6098.
87) B. Bergk, A. Demuer, I. Sheikin, Y. Wang, J. Wosnitza, Y.
Nakazawa, and R. Lortz: Physica C 470 (2010) 586.
88) B. Bergk, A. Demuer, I. Sheikin, Y. Wang, J. Wosnitza, Y.
Nakazawa, and R. Lortz: Phys. Rev. B 83 (2011) 064506.
89) K. Maki and H. Won: Czech. J. Phys. 46 (1996) 1035.
90) H. Kobayashi, H. Tomita, T. Naito, A. Kobayashi, F. Sakai, T.
Watanabe, and P. Cassoux: J. Am. Chem. Soc. 118 (1996) 368.
91) H. Seo and H. Fukuyama: Synth. Met. 103 (1999) 1951.
92) S. Uji, H. Shinagawa, C. Terakura, T. Terashima, T. Yakabe, Y.
Terai, M. Tokumoto, A. Kobayashi, H. Tanaka, and H. Kobayashi:
Phys. Rev. B 64 (2001) 024531.
93) H. Akiba, S. Nakano, Y. Nishio, K. Kajita, B. Zhou, A. Kobayashi,
and H. Kobayashi: J. Phys. Soc. Jpn. 78 (2009) 033601.
94) L. Brossard, R. Clerac, C. Coulon, M. Tokumoto, T. Ziman, D. K.
Petrov, V. N. Laukhin, M. J. Naughton, A. Audouard, F. Goze, A.
Kobayashi, H. Kobayashi, and P. Cassoux: Eur. Phys. J. B 1 (1998)
439.
95) L. Balicas, J. S. Brooks, K. Storr, S. Uji, M. Tokumoto, H.
Kobayashi, A. Kobayashi, V. Barzykin, and L. P. Gor’kov: Phys.
Rev. Lett. 87 (2001) 067002.
96) S. Uji, T. Terashima, C. Terakura, T. Yakabe, Y. Terai, S. Yasuzuka,
Y. Imanaka, M. Tokumoto, A. Kobayashi, F. Sakai, H. Tanaka, H.
Kobayashi, L. Balicas, and J. S. Brooks: J. Phys. Soc. Jpn. 72 (2003)
369.
97) S. Uji and J. S. Brooks: J. Phys. Soc. Jpn. 75 (2006) 051014.
98) O. Fischer: Helv. Phys. Acta 45 (1972) 331.
99) V. Jaccarino and M. Peter: Phys. Rev. Lett. 9 (1962) 290.
100) S. Uji, C. Terakura, T. Terashima, T. Yakabe, Y. Terai, M.
Tokumoto, A. Kobayashi, F. Sakai, H. Tanaka, and H. Kobayashi:
Phys. Rev. B 65 (2002) 113101.
101) K. Hiraki, M. Kitahara, T. Takahashi, H. Mayaffre, M. Horvatić,
C. Berthier, S. Uji, H. Tanaka, B. Zhou, A. Kobayashi, and H.
Kobayashi: J. Phys. Soc. Jpn. 76 (2007) 124708.
102) M. Houzet, A. Buzdin, L. Bulaevskii, and M. Maley: Phys. Rev. Lett.
88 (2002) 227001.
103) H. Shimahara: J. Phys. Soc. Jpn. 71 (2002) 1644.
104) S. Uji, T. Terashima, M. Nishimura, Y. Takahide, T. Konoike, K.
Enomoto, H. Cui, H. Kobayashi, A. Kobayashi, H. Tanaka, M.
Tokumoto, E. S. Choi, T. Tokumoto, D. Graf, and J. S. Brooks: Phys.
Rev. Lett. 97 (2006) 157001.
105) L. Bulaevskii, A. Buzdin, and M. Maley: Phys. Rev. Lett. 90 (2003)
067003.
106) M. Tachiki: Z. Phys. B 100 (1996) 369.
107) H. A. Radovan, N. A. Fortune, T. P. Murphy, S. T. Hannahs, E. C.
Palm, S. W. Tozer, and D. Hall: Nature 425 (2003) 51.
108) A. Bianchi, R. Movshovich, C. Capan, P. G. Pagliuso, and J. L.
Sarrao: Phys. Rev. Lett. 91 (2003) 187004.
109) H. Shimahara: J. Phys. Soc. Jpn. 67 (1998) 736.
110) C. Mora and R. Combescot: Europhys. Lett. 66 (2004) 833.
111) H. Kino and H. Fukuyama: J. Phys. Soc. Jpn. 64 (1995) 2726; H.
Kino and H. Fukuyama: J. Phys. Soc. Jpn. 65 (1996) 2158.
112) K. Kanoda: J. Phys. Soc. Jpn. 75 (2006) 051007.
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
113) K. Kanoda and R. Kato: Annu. Rev. Condens. Matter Phys. 2 (2011)
167.
114) K. Kanoda: Hyperfine Interactions 104 (1997) 235.
115) R. McKenzie: Science 278 (1997) 820.
116) J. M. Williams, A. J. Schultz, U. Geiser, K. D. Carlson, A. M. Kini,
H. H. Wang, W.-K. Kwok, M.-H. Whangbo, and J. E. Schirber:
Science 252 (1991) 1501.
117) U. Welp, S. Fleshler, W. K. Kwok, G. W. Crabtree, K. D. Carlson,
H. H. Wang, U. Geiser, J. M. Williams, and V. M. Hitsman: Phys.
Rev. Lett. 69 (1992) 840.
118) K. Miyagawa, A. Kawamoto, Y. Nakazawa, and K. Kanoda: Phys.
Rev. Lett. 75 (1995) 1174.
119) H. C. Kandpal, I. Opahle, Y.-Z. Zhang, H. O. Jeschke, and R.
Valenti: Phys. Rev. Lett. 103 (2009) 067004.
120) K. Nakamura, Y. Yoshimoto, T. Kosugi, R. Arita, and M. Imada:
J. Phys. Soc. Jpn. 78 (2009) 083710.
121) T. Komatsu, N. Matsukawa, T. Inoue, and G. Saito: J. Phys. Soc. Jpn.
65 (1996) 1340.
122) A. Kawamoto, K. Miyagawa, and K. Kanoda: Phys. Rev. B 55 (1997)
14140; A. Kawamoto, H. Taniguchi, and K. Kanoda: J. Am. Chem.
Soc. 120 (1998) 10984.
123) H. Taniguchi, A. Kawamoto, and K. Kanoda: Phys. Rev. B 67 (2003)
014510; H. Taniguchi, A. Kawamoto, and K. Kanoda: Phys. Rev. B
59 (1999) 8424.
124) Y. Shimizu, K. Miyagawa, K. Kanoda, M. Maesato, and G. Saito:
Phys. Rev. Lett. 91 (2003) 107001; Y. Shimizu, K. Miyagawa, K.
Kanoda, M. Maesato, and G. Saito: Phys. Rev. B 73 (2006) 140407.
125) P. A. Lee: Science 321 (2008) 1306.
126) See ref. 113 and references therein.
127) U. Geiser, H. H. Wang, K. D. Carlson, J. M. Williams, H. A.
Charlier, Jr., J. E. Heindl, G. A. Yaconi, B. H. Love, M. W. Lathrop,
J. E. Schirber, D. L. Overmyer, J. Ren, and M.-H. Whangbo: Inorg.
Chem. 30 (1991) 2586.
128) Y. Kurosaki, Y. Shimizu, K. Miyagawa, K. Kanoda, and G. Saito:
Phys. Rev. Lett. 95 (2005) 177001.
129) H. Ito, M. Kubota, T. Ishiguro, and G. Saito: J. Phys. Soc. Jpn. 65
(1996) 2987.
130) S. Lefebvre, P. Wzietek, S. Brown, C. Bourbonnais, D. Jérome, C.
Mézière, M. Fourmigué, and P. Batail: Phys. Rev. Lett. 85 (2000)
5420; P. Limelette, P. Wzietek, S. Florens, A. Georges, T. A. Costi,
C. Pasquier, D. Jérome, C. Mézière, and P. Batail: Phys. Rev. Lett. 91
(2003) 016401.
131) D. Founier, M. Poirier, M. Castonguay, and K. D. Truong: Phys. Rev.
Lett. 90 (2003) 127002.
132) F. Kagawa, K. Miyagawa, and K. Kanoda: Nature 436 (2005) 534; F.
Kagawa, T. Itou, K. Miyagawa, and K. Kanoda: Phys. Rev. B 69
(2004) 064511; F. Kagawa, T. Itou, K. Miyagawa, and K. Kanoda:
Phys. Rev. Lett. 93 (2004) 127001.
133) F. L. Pratt, P. J. Baker, S. J. Blundell, T. Lancaster, S. Ohira-
Kawamura, C. Baines, Y. Shimizu, K. Kanoda, I. Watanabe, and G.
Saito: Nature 471 (2011) 612.
134) K. Kornelsen, J. E. Eldridge, H. H. Wang, H. A. Charlier, and J. M.
Williams: Solid State Commun. 81 (1992) 343.
135) I. Kezsmarki, Y. Shimizu, G. Mihaly, Y. Tokura, K. Kanoda, and G.
Saito: Phys. Rev. B 74 (2006) 201101.
136) T.-K. Ng and P. A. Lee: Phys. Rev. Lett. 99 (2007) 156402.
137) Y. Qi and S. Sachdev: Phys. Rev. B 77 (2008) 165112.
138) T. Senthil: Phys. Rev. B 78 (2008) 045109.
139) K. Miyagawa, A. Kawamoto, and K. Kanoda: Phys. Rev. Lett. 89
(2002) 017003.
140) Y. Shimizu, H. Kasahara, T. Furuta, K. Miyagawa, K. Kanoda, M.
Maesato, and G. Saito: Phys. Rev. B 81 (2010) 224508.
141) For example, T. Timusk and B. Statt: Rep. Prog. Phys. 62 (1999) 61.
142) M.-S. Nam, A. Ardavan, S. J. Blundell, and L. A. Schlueter: Nature
449 (2007) 584.
143) K. Miyagawa, K. Kanoda, and A. Kawamoto: Chem. Rev. 104 (2004)
5635; and references therein.
144) K. Kanoda, K. Miyagawa, A. Kawamoto, and Y. Nakazawa: Phys.
Rev. B 54 (1996) 76.
145) G.-q. Zheng, K. Tanabe, T. Mito, S. Kawasaki, Y. Kitaoka, D. Aoki,
Y. Haga, and Y. Onuki: Phys. Rev. Lett. 86 (2001) 4664.
146) M. Sigrist and K. Ueda: Rev. Mod. Phys. 63 (1991) 239.
147) H. Mayaffre, P. Wzietek, D. Jérome, C. Lenoir, and P. Batail: Phys.
011004-25
A. ARDAVAN et al.
Rev. Lett. 75 (1995) 4122.
148) M. Tinkham: Introduction to Superconductivity (Dover, Mineola,
New York, 2004) 2nd ed.
149) M. R. Beasley, J. E. Mooij, and T. P. Orlando: Phys. Rev. Lett. 42
(1979) 1165.
150) V. J. Emery and S. A. Kivelson: Nature 374 (1995) 434.
151) Y. Wang, L. Li, and N. P. Ong: Phys. Rev. B 73 (2006) 024510.
152) E. H. Sondheimer: Proc. R. Soc. London, Ser. A 193 (1948) 484.
153) W. Wu, N. P. Ong, and P. M. Chaikin: Phys. Rev. B 72 (2005)
235116.
154) K. Behnia: J. Phys.: Condens. Matter 21 (2009) 113101.
155) I. Ussishkin, S. L. Sondhi, and D. A. Huse: Phys. Rev. Lett. 89 (2002)
287001.
156) M. N. Serbyn, M. A. Skvortsov, A. A. Varlamov, and V. Galitski:
Phys. Rev. Lett. 102 (2009) 067001.
157) Z. A. Xu, N. P. Ong, Y. Wang, T. Kakeshita, and S. Uchida: Nature
406 (2000) 486.
158) Y. Wang, N. P. Ong, Z. A. Xu, T. Kakeshita, S. Uchida, D. A. Bonn,
R. Liang, and W. N. Hardy: Phys. Rev. Lett. 88 (2002) 257003.
159) M.-S. Nam, J. A. Symington, J. Singleton, S. J. Blundell, A. Ardavan,
J. A. A. J. Perenboom, M. Kurmoo, and P. Day: J. Phys.: Condens.
Matter 11 (1999) L477.
160) S. Doniach: Phys. Rev. B 24 (1981) 5063.
161) K. Oshima, T. Mori, H. Inokuchi, H. Urayama, H. Yamochi, and G.
Saito: Phys. Rev. B 38 (1988) 938.
162) M. Tamura, H. Tajima, K. Yakushi, H. Kuroda, A. Kobayashi, R.
Kato, and H. Kobayashi: J. Phys. Soc. Jpn. 60 (1991) 3861.
163) J. Schmalian: Phys. Rev. Lett. 81 (1998) 4232.
164) H. Kino and H. Kontani: J. Phys. Soc. Jpn. 67 (1998) 3691.
165) H. Kondo and T. Moriya: J. Phys. Soc. Jpn. 67 (1998) 3695.
166) K. Kuroki and H. Aoki: Phys. Rev. B 60 (1999) 3060.
167) M. Vojta and E. Dagotto: Phys. Rev. B 59 (1999) 713.
168) R. Louati, S. Charfi-Kaddour, A. Ben Ali, R. Bennaceur, and M.
Heritier: Synth. Met. 103 (1999) 1857.
169) T. Jujo, S. Koikegami, and K. Yamada: J. Phys. Soc. Jpn. 68 (1999)
1331.
170) B. J. Powell and R. H. McKenzie: Phys. Rev. Lett. 94 (2005) 047004.
171) J. Y. Gan, Y. Chen, Z. B. Su, and F. C. Zhang: Phys. Rev. Lett. 94
(2005) 067005.
172) T. Watanabe, H. Yokoyama, Y. Tanaka, and J. Inoue: J. Phys. Soc.
Jpn. 75 (2006) 074707.
173) J. Y. Gan, Y. Chen, and F. C. Zhang: Phys. Rev. B 74 (2006) 094515.
174) B. Kyung and A.-M. S. Tremblay: Phys. Rev. Lett. 97 (2006)
046402.
175) S.-S. Lee, P. A. Lee, and T. Senthil: Phys. Rev. Lett. 98 (2007)
067006.
176) V. Galitski and Y. B. Kim: Phys. Rev. Lett. 99 (2007) 266403.
177) B. J. Powell: J. Phys.: Condens. Matter 18 (2006) L575.
178) J. G. Rau and H.-Y. Kee: Phys. Rev. Lett. 106 (2011) 056405.
179) H. Kondo and T. Moriya: J. Phys. Soc. Jpn. 70 (2001) 2800.
180) K. Kuroki, T. Kimura, R. Arita, Y. Tanaka, and Y. Matsuda: Phys.
Rev. B 65 (2002) 100516; Note that the definition of dx2 y2 and dxy
pairings in the present review is opposite to that in refs. 170 and 171
because we define the pairing states in the unfolded Brillouin zone of
the single band model as shown in Fig. 20.
181) A more detailed review on this issue is given in K. Kuroki: J. Phys.
Soc. Jpn. 75 (2006) 051013.
182) K. Izawa, H. Yamaguchi, T. Sasaki, and Y. Matsuda: Phys. Rev. Lett.
88 (2002) 027002.
183) T. Arai, K. Ichimura, K. Nomura, S. Takasaki, J. Yamada, S.
Nakatsuji, and H. Anzai: Phys. Rev. B 63 (2001) 104518.
184) L. Malone, O. J. Taylor, J. A. Schlueter, and A. Carrington: Phys.
Rev. B 82 (2010) 014522.
185) H. Mori: J. Phys. Soc. Jpn. 75 (2006) 51003.
186) H. Seo: J. Phys. Soc. Jpn. 69 (2000) 805.
187) H. Seo, C. Hotta, and H. Fukuyama: Chem. Rev. 104 (2004) 5005.
188) K. Hiraki and K. Kanoda: Phys. Rev. Lett. 80 (1998) 2737.
189) T. Mori: Bull. Chem. Soc. Jpn. 71 (1998) 2509.
190) T. Mori, H. Mori, and S. Tanaka: Bull. Chem. Soc. Jpn. 72 (1999)
179.
191) T. Mori: Bull. Chem. Soc. Jpn. 72 (1999) 2011.
192) N. Tajima, A. Ebina-Tajima, M. Tamura, Y. Nishio, and K. Kajita:
J. Phys. Soc. Jpn. 71 (2002) 1832.
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
193) H. Kobayashi, R. Kato, A. Kobayashi, Y. Nishio, K. Kajita, and W.
Sasaki: Chem. Lett. 15 (1986) 789.
194) T. Mori and H. Inokuchi: Solid State Commun. 64 (1987) 335.
195) H. Mori, I. Hirabayashi, S. Tanaka, T. Mori, Y. Maruyama, and H.
Inokuchi: Solid State Commun. 80 (1991) 411.
196) T. Mori, K. Kato, Y. Maruyama, H. Inokuchi, H. Mori, I.
Hirabayashi, and S. Tanaka: Solid State Commun. 82 (1992) 177.
197) M. Kurmoo, A. W. Graham, P. Day, S. J. Coles, M. B. Hursthouse,
J. L. Caulfield, J. Singleton, F. L. Pratt, W. Hayes, L. Ducasse, and P.
Guionneau: J. Am. Chem. Soc. 117 (1995) 12209.
198) U. Geiser, J. A. Schlueter, H. H. Wang, A. M. Kini, J. M. Williams,
P. P. Sche, H. I. Zakowicz, M. L. VanZile, and J. D. Dudek: J. Am.
Chem. Soc. 118 (1996) 9996.
199) H. Nishikawa, T. Mormoto, T. Kodama, I. Ikemoto, K. Kikuchi, J.
Yamada, H. Yoshino, and K. Murata: J. Am. Chem. Soc. 124 (2002)
730.
200) S. Kimura, T. Maejima, H. Suzuki, R. Chiba, H. Mori, T. Kawamoto,
T. Mori, H. Moriyama, Y. Nishio, and K. Kajita: Chem. Commun.
(2004) 2454.
201) K. Yamamoto, S. Iwai, S. Boyko, A. Kashiwazaki, F. Hiramatsu, C.
Okabe, N. Nishi, and K. Yakushi: J. Phys. Soc. Jpn. 77 (2008)
074709.
202) N. Tajima, S. Sugawara, M. Tamura, Y. Nishio, and K. Kajita:
J. Phys. Soc. Jpn. 75 (2006) 051010.
203) Y. Takano, K. Hiraki, H. M. Yamamoto, T. Nakamura, and T.
Takahashi: J. Phys. Chem. Solids 62 (2001) 393.
204) Y. Takano, K. Hiraki, H. M. Yamamoto, T. Nakamura, and T.
Takahashi: Synth. Met. 120 (2001) 1081.
205) R. Wojciechowski, K. Yamamoto, K. Yakushi, and A. Kawamoto:
Synth. Met. 135 (2003) 587.
206) R. Wojciechowski, K. Yamamoto, and K. Yakushi: Phys. Rev. B 67
(2003) 224105.
207) T. Kakiuchi, Y. Wakabaashi, H. Sawa, T. Takahashi, and T.
Nakamura: J. Phys. Soc. Jpn. 76 (2007) 113702.
208) S. Katayama, A. Kobayashi, and Y. Suzumura: J. Phys. Soc. Jpn. 75
(2006) 054705.
209) N. Tajima, S. Sugawara, R. Kato, Y. Nishio, and K. Kajita: Phys.
Rev. Lett. 102 (2009) 176403.
210) B. Rothaemel, L. Forro, J. R. Cooper, J. S. Schilling, M. Weger, P.
Bele, H. Brunner, D. Schweitzer, and H. J. Keller: Phys. Rev. B 34
(1986) 704.
211) H. Kobayashi, R. Kato, A. Kobayashi, Y. Nishio, K. Kajita, and W.
Sasaki: Chem. Lett. 15 (1986) 833.
212) R. Kato, H. Kobayashi, A. Kobayashi, Y. Nishio, K. Kajita, and W.
Sasaki: Chem. Lett. 15 (1986) 957.
213) B. Salameh, A. Nothardt, E. Balthes, W. Schmidt, D. Schweitzer,
J. Strempfer, B. Hinrichsen, M. Jansen, and K. Maude: Phys. Rev. B
75 (2007) 054509.
214) H. Mori, S. Tanaka, and T. Mori: Bull. Chem. Soc. Jpn. 71 (1998)
797.
215) M. Watanabe, Y. Nogami, K. Oshima, H. Mori, and S. Tanaka:
J. Phys. Soc. Jpn. 68 (1999) 2654.
216) F. Sawano, I. Terasaki, H. Mori, T. Mori, M. Watanabe, N. Ikeda, Y.
Nogami, and Y. Noda: Nature 437 (2005) 522.
217) S. Kimura, H. Suzuki, T. Maejima, H. Mori, J. Yamaura, T.
Kakiuchi, H. Saw, and H. Moriyama: J. Am. Chem. Soc. 128 (2006)
1456.
218) S. Niizeki, F. Yoshikane, K. Kohno, K. Takahashi, H. Mori, Y.
Bando, T. Kawamoto, and T. Mori: J. Phys. Soc. Jpn. 77 (2008)
073710.
219) N. Morinaka, K. Takahashi, R. Chiba, F. Yoshikane, S. Niizeki, M.
Tanaka, K. Yakushi, M. Koeda, M. Hedo, T. Fujiwara, Y. Uwatoko,
Y. Nishio, K. Kajita, and H. Mori: Phys. Rev. B 80 (2009) 092508.
220) K. Yoshimi, M. Nakamura, and H. Mori: J. Phys. Soc. Jpn. 76 (2007)
24706.
011004-26
A. ARDAVAN et al.
221) H. Nishikawa, Y. Sato, K. Kikuchi, T. Kodama, I. Ikemoto, J.
Yamada, H. Oshio, R. Kondo, and S. Kagoshima: Phys. Rev. B 72
(2005) 052510.
222) T. Yamamoto, H. M. Yamamoto, R. Kato, H. Akutsu, A. Sato-
Akutsu, A. Kawamoto, S. S. Turner, and P. Day: Phys. Rev. B 77
(2008) 205120.
223) H. Kino and H. Fukuyama: J. Phys. Soc. Jpn. 64 (1995) 4523.
224) H. Seo, J. Merino, H. Yoshioka, and M. Ogata: J. Phys. Soc. Jpn. 75
(2006) 51009.
225) C. Hotta and H. Fukuyama: J. Phys. Soc. Jpn. 70 (2001) 321; C.
Hotta: J. Phys. Soc. Jpn. 72 (2003) 840.
226) F. Mila and X. Zotos: Europhys. Lett. 24 (1993) 133.
227) T. Mori: Bull. Chem. Soc. Jpn. 73 (2000) 2243.
228) For a recent review, see M. Ogata and H. Fukuyama: Rep. Prog.
Phys. 71 (2008) 036501.
229) D. J. Scalapino, E. Loh, Jr., and J. E. Hirsch: Phys. Rev. B 35 (1987)
6694.
230) J. Merino and R. H. McKenzie: Phys. Rev. Lett. 87 (2001) 237002.
231) R. H. McKenzie, J. Merino, J. B. Marston, and O. P. Sushkov: Phys.
Rev. B 64 (2001) 085109.
232) A. Kobayashi, Y. Tanaka, M. Ogata, and Y. Suzumura: J. Phys. Soc.
Jpn. 73 (2004) 1115.
233) S. Onari, R. Arita, K. Kuroki, and H. Aoki: Phys. Rev. B 70 (2004)
094523.
234) H. Seo and M. Ogata: Phys. Rev. B 64 (2001) 113103.
235) J. Merino, H. Seo, and M. Ogata: Phys. Rev. B 71 (2005) 125111.
236) Y. Tanaka, Y. Yanase, and M. Ogata: J. Phys. Soc. Jpn. 73 (2004)
319; Y. Tanaka, Y. Yanase, and M. Ogata: J. Phys. Soc. Jpn. 73
(2004) 2053.
237) H. Watanabe and M. Ogata: J. Phys. Soc. Jpn. 74 (2005) 2901.
238) M. Dressel: J. Phys.: Condens. Matter 23 (2011) 293201; S. Kaiser,
M. Dressel, Y. Sun, A. Greco, J. A. Schlueter, G. L. Gard, and N.
Drichko: Phys. Rev. Lett. 105 (2010) 206402.
239) T. Komatsu, N. Matsukawa, T. Inoue, and G. Saito: J. Phys. Soc. Jpn.
65 (1996) 1340.
240) R. Kumai, A. Asamitsu, and Y. Tokura: J. Am. Chem. Soc. 120
(1998) 8263.
241) H. Mori, M. Suto, H. Suzuki, Y. Nishio, and K. Kajita: J. Phys. IV
114 (2004) 467.
242) R. N. Lyubovskaya, R. B. Lyubovskii, R. P. Shibaeva, M. Z.
Aldoshina, L. M. Gol’denberg, L. P. Rozenberg, M. L. Khidekel’,
and Yu. F. Shul’pyakov: JETP Lett. 42 (1985) 468; R. N.
Lyubovskaya, E. I. Zhilyaeva, S. I. Pesotskii, R. B. Lyubovskii,
L. O. Atovmyan, O. A. D’yachenko, and T. G. Takhirov: JETP Lett.
46 (1985) 188.
243) H. Taniguchi, T. Okuhata, T. Nagai, K. Satoh, N. Môri, Y. Shimizu,
M. Hedo, and Y. Uwatoko: J. Phys. Soc. Jpn. 76 (2007) 113709.
244) H. Oike, K. Miyagawa, K. Kanoda, H. Taniguchi, and K. Murata:
Physica B 404 (2009) 376.
245) Y. Kurosaki, A. Furuta, H. Taniguchi, K. Miyagawa, and K. Kanoda:
Physica B 404 (2009) 3138.
246) Y. Eto, M. Itaya, and A. Kawamoto: Phys. Rev. B 81 (2010) 212503.
247) Y. Kawasugi, H. M. Yamamoto, N. Tajima, T. Fukunaga, K.
Tsukagoshi, and R. Kato: Phys. Rev. Lett. 103 (2009) 116801.
248) K. Ueno, S. Nakamura, H. Shimotani, A. Ohtomo, N. Kimura, T.
Nojima, H. Aoki, Y. Iwasa, and M. Kawasaki: Nat. Mater. 7 (2008)
855.
249) X. F. Wang, R. H. Liu, Z. Gui, Y. L. Xie, Y. J. Yan, J. J. Ying, X. G.
Luo, and X. H. Chen: Nat. Commun. 2 (2011) 507.
250) A. Kobayashi, Y. Okano, and H. Kobayashi: J. Phys. Soc. Jpn. 75
(2006) 051002.
251) H. Taniguchi, M. Miyashita, K. Uchiyama, K. Satoh, N. Mori, H.
Okamoto, K. Miyagawa, K. Kanoda, M. Hedo, and Y. Uwatoko:
J. Phys. Soc. Jpn. 72 (2003) 468.
#2012 The Physical Society of Japan
J. Phys. Soc. Jpn. 81 (2012) 011004 S PECIAL TOPICS
Arzhang Ardavan was born in 1973. As a student
at Corpus Christi College, University of Oxford, he
obtained his B.A (1994) and D.Phil (1998) degrees
in Physics. After a Junior Research Fellowship at
Wolfson College, Oxford (1998–2001) he became a
University Lecturer and Tutorial Fellow in Physics
at Magdalen College, Oxford. Since 2003 he has
held a Royal Society University Research Fellow-
ship, and since 2006, the title of Reader in Physics.
His research interests include strongly correlated
electron systems, unconventional superconductivity, molecular magnetism
and quantum spin dynamics.
Stuart Brown was born in New Jersey, U.S.A. in
1958. He obtained his bachelor’s degree in physics
from the University of Colorado in 1981, and his
Ph. D. from UCLA in 1988. He did postdoctoral
research at Los Alamos National Laboratory (1986–
1989). From 1989–1992 he was appointed assistant
professor at the University of Florida. He has been a
member of the faculty in the Department of Physics
and Astronomy at UCLA since 1992. He has worked
on various problems in correlated electron physics,
with extensive experience in molecular conductors. Much of the research has
been done utilizing NMR and transport methods, sometimes under extreme
conditions such as high magnetic fields and under high pressures.
Seiichi Kagoshima was born in Osaka, Japan in
1945. He obtained his B.S. (1968), M.S. (1970), and
D.S. (1973) degrees from the University of Tokyo.
He was a research staff at Electrotechnical Labora-
tory (1973–1979), and an Associate Professor
(1979–1988) and a Professor (1998–2009) at Grad-
uate School of Arts and Sciences, the University of
Tokyo. He is now a Guest Professor of Department
of Physics, Meiji University. He has been working
on electronic and structural properties of low-
dimensional organic conductors using x-ray diffraction under uniaxial strain,
whose method was first developed by his group, and hydrostatic pressures.
Kazushi Kanoda was born in Miyagi Prefecture,
Japan in 1958. He obtained his B.E. degree (1981)
from Tohoku University and his M.E. (1983) and
Ph. D. (1987) degrees from Kyoto University. He
was a research associate (1987–1991) at Faculty of
Science, Gakushuin University, an associate profes-
sor (1991–1997) at Institute for Molecular Science,
and an associate professor (1997–1999) at Faculty of
Engineering, University of Tokyo. Since 1999 he has
been a professor at Faculty of Engineering, Uni-
versity of Tokyo. He has worked on the electronic properties of molecular
materials, where a variety of electronic phases appear due to the interplay
between low-dimensionality, electron correlation, electron lattice coupling.
His particular interests are in searching novel electronic phases related to the
metal–insulator transition or superconductivity.
Kazuhiko Kuroki was born in Tokyo, Japan in
1965. He obtained his B. Sc. (1988), M. Sc. (1990),
and D. Sc. (1994) degrees from the University of
Tokyo. He was a research associate (1992–2000) at
the Graduate School of Science, University of
Tokyo, an associate professor (2000–2007) and a
professor (2007–2010) at the Department of Applied
Physics and Chemistry, the University of Electro-
Communications. Since 2010, he is a professor at
the Department of Engineering Science, the Uni-
versity of Electro-Communications. He has mainly worked on the theory of
unconventional superconductivity in correlated electronic systems, such as
oxides, organic conductors, and pnictide superconductors. He has also
worked on the theory of thermoelectric effect in oxides and organic
conductors. He is particularly interested in the interplay between peculiar
band structures and electron correlation effects.
011004-27
A. ARDAVAN et al.
Hatsumi Mori was born in Tokyo, Japan in 1961.
She obtained her B. Sc. (1984), M. Sc. (1986)
degrees from Ochanomizu University, and D. Sc.
(1992) degree from the University of Tokyo. She
was a technical associate in Institute for Solid State
Physics (ISSP) in the University of Tokyo (1986–
1989), a researcher in International Superconductiv-
ity Technology Center (1989–2001), and an associ-
ate professor at ISSP in the University of Tokyo
(2001–2010). Since 2010, she has been a professor
at ISSP in the University of Tokyo. She has worked on the development and
the characterization of organic functional materials. Her researches are now
focused on the producing curious organic superconductors, novel organic
electron–proton related conductors, and organic–inorganic hybrid magnetic
conductors and investigating the nonlinear conductions of charge ordered
materials.
Masao Ogata was born in Tokyo, Japan in 1960.
He obtained his B. Sc. (1982), M. Sc. (1984), and
Ph. D. (1987) degrees from the University of
Tokyo. He was a research associate (1986–1993)
in Institute for Solid State Physics, University of
Tokyo and an associate professor (1993–2000) in
Institute of Physics, Faculty of Arts and Sciences,
University of Tokyo. During these periods, he
stayed in ETH Zürich (1989–1991) and Princeton
University (1991–1993) as a postdoc. He is now a
professor in Department of Physics, University of Tokyo. He has worked on
theory of condensed matter physics such as high-Tc superconductivity,
strongly correlated electron systems, one-dimensional systems, Dirac
fermions in condensed matter, and unconventional superconductivity,
magnetism and charge-order, etc. in various materials including cobaltates,
iron-pnictides and organic conductors.
Shinya UJI was born in Tokyo, Japan, 1960.
He obtained his B. Sc (1983), M. Sc. (1985), and
D. Sc. (1988) degrees from the University of
Tsukuba. He was a researcher at National Research
Institute for Metals (1988–2001), a group leader
(2001–2011) at National Institute for Materials
Science (NIMS). Since 2011, he is a unit leader of
Superconducting Properties Unit, NIMS. He is also
a Professor at Graduate School of Pure and Applied
Sciences, University of Tsukuba since 2006. He has
worked on physical properties of strongly correlated electron systems under
high magnetic field.
Jochen Wosnitza was born in Grevenbroich,
Germany, in 1959. He obtained his Diploma in
Physics (1985) from RWTH Aachen (University of
Technology), his Dr. rer. nat. (1988) and Habilita-
tion (1995) from Karlsruhe University (now KIT,
Karlsruhe Institute of Technology). He was scien-
tific assistant (1993–1999) and lecturer (1999–2001)
in Karlsruhe University before he became professor
(since 2001) at Dresden University of Technology.
Since 2004 he became in addition director of the
Dresden High Magnetic Field Laboratory at the Helmholtz–Zentrum
Dresden–Rossendorf. He has worked on thermodynamic properties of
magnetic and superconducting materials. A strong focus was laid on the
electronic properties of organic metals and superconductors. He is now
especially involved in the investigation of strongly correlated electron
systems at high magnetic fields.
#2012 The Physical Society of Japan