Physica C 514 (2015) 279–289

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Physica C
journal homepage: www.elsevier.com/locate/physc

Organic superconductors: The Bechgaard salts and relatives

S.E. Brown ⇑
Department of Physics and Astronomy, UCLA, Los Angeles, CA 90095-1547 USA

a r t i c l e i n f o a b s t r a c t

Article history: Organic conductors were originally considered a route to achieving high temperature superconductivity.
Received 14 January 2015 While that goal could not be met, what came to be was a class of materials in which the interplay
Received in revised form 13 February 2015 between correlations and dimensionality, and sometimes geometric frustration, lead to a spectacular
Accepted 15 February 2015
diversity of phases and phenomena that are tuned by magnetic field, pressure, and temperature.
Available online 24 February 2015
Highlighted here are the physical properties of the superconducting and normal states of the first family
of organic superconductors, the quasi-one dimensional Bechgaard salts (TMTSF)2X, as well as the
Keywords:
quasi-two dimensional compounds j-(BEDT-TTF)2X. In both cases, the preponderance of experiments
Molecular conductors
Superconductivity
indicate that the superconductivity is nodal. As well, the importance of correlations is evident in the
Organic superconductors temperature/pressure phase diagrams, and the influence of low-energy magnetic fluctuations over the
normal state properties above the superconducting transition temperature is substantial.
Ó 2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
2. Some molecules and crystal structures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
2.1. The Bechgaard salts, (TMTSF)2X, and sulfur analogs (TMTTF)2X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
2.2. Salts based on the BEDT-TTF donor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
3. Superconductivity and normal state properties of the q1d materials, (TMTSF)2X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
3.1. Superconducting properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
3.2. Normal state properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
4. Superconductivity and normal state properties of the q2d superconductors j-(ET)2X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
4.1. Superconducting properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
4.2. Normal state properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
4.3. High-field phases of the q2d superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
5. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288

1. Introduction In this model, carriers propagate freely along a polymeric backbone,

Following acceptance of the BCS theory of superconductivity
came interest in exploiting that understanding toward creating
materials with higher transition temperatures T c . Commonly associ-
ated with the push for synthesizing organic superconductors was
Little’s 1964 proposal for a superconducting polymeric chain [1].
⇑ Tel.: +1 310 825 4234.
E-mail address: brown@physics.ucla.edu
which is augmented by a highly polarizable sidegroup in each unit,
Fig. 1. The ability to adjust the constituents would allow for
optimizing parameters so as to maximize T c . In the following years,
there was substantial interest in synthetic metals, not just for
high temperature superconductivity, but also for the range of appli-
cations a lightweight, flexible conductor could offer. Of course,
research into polymer conductors exploded following the 1980 dis-
covery that polyacetylene could be doped and conduct electricity.
Unfortunately, doped polymers were never found to superconduct,

http://dx.doi.org/10.1016/j.physc.2015.02.030
0921-4534/Ó 2015 Elsevier B.V. All rights reserved.
280 S.E. Brown / Physica C 514 (2015) 279–289
polarizable
sidechain
polymer
spine
Fig. 1. Model of Little’s proposal [1] for a superconducting synthetic metal. The
polarizable sidechains are intended to provide a means for screening the repulsive
interaction for delocalized carriers moving along the spine.
whereas an alternative route, based on charge transfer salts of
molecular constituents, is widely known for just that.
In the 1970s, considerable effort went into building organic
conductors from structures incorporating a molecular donor and
acceptor, charge transfer salts (CTS). Among the most significant
advances was the synthesis of the donor tetrathiafulvalene (TTF)
molecule [2], and subsequent crystallization with the electron
acceptor tetracyanoquinodimethane (TCNQ) [3]: not only was it
conducting at room temperature, it was also specifically metallic.
Single crystals of TTF itself, in fact, reveal the structural aspect
crucial to the CTS route to synthetic metals. Namely, the highly
symmetric and planar TTF molecules stack with considerable inter-
molecular p–p alignment and overlap. The oxidation potential is
small, and a wide range of salts were synthesized. Further, owing
to the high molecular symmetry the crystal quality can be quite
good. Thus, the necessary ingredients for metallic properties were
all present: delocalized electronic states from p–p overlap, high
degree of crystalline order, and partial band filling from oxidation,
setting the Fermi energy inside the bands associated with the TTF
HOMO and TCNQ LUMO [4,5]. A further consideration was that
with sufficient intermolecular orbital overlap, Coulomb energies
would not be so great so as to localize the carriers.
The structure of TTF-TCNQ with its segregated stacks, arranged
in layers, appears in Fig. 2 [6]. Two bands cross the Fermi energy EF
and correspond to the anti-bonding dispersion of predominant TTF
character, and the bonding TCNQ states. Since the intrastack p–p
overlap is strongest, the Fermi surface consists of two pairs of open
sheets, warped by interchain coupling resulting in substantial con-
ductivity anisotropy.
While TTF-TCNQ was known for its metallic properties, the high
degree of Fermi surface nesting makes it unstable to charge-
density wave formation below T P ¼ 54 K [7], which structural
studies associate with distortions primarily on the TCNQ stacks
[8]. Additional transitions occur at lower temperature (49 K,
38 K). Variants on this theme, with TSF (tetraselenafulvalene), or
HMTSF, lead to similar results [9]. The wavevector of the 54 K
transition phase is incommensurate, due to the incomplete charge
Fig. 2. Crystal structure of TTF-TCNQ, projected along the stacking (b) axis (left),
and the a-axis. Yellow corresponds to sulfur, blue to nitrogen, and black to carbon.
(For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
transfer between the stacks. Pressure broadens both bands,
shifting the wavevector toward the Brillouin zone center due to
the increased charge transfer [10].
Since constructing synthetic metals in this way leads to
relatively narrow bandwidths, the influence of Coulomb interac-
tions would ordinarily be expected, and indeed 4kF fluctuations
were detected in the case of TTF-TCNQ [11]. Nevertheless, a
striking success of this example is that the bandwidths are
sufficient to overcome the repulsions, perhaps assisted by the
polarizability of the TTF HOMO. Going forward, the results invited
a strategy by which the nesting conditions are worsened by
increasing the overlap orthogonal to the stack direction.
The Bechgaard salts, (TMTSF)2X, with X = ClO4, PF6, AsF6, etc.,
were a natural direction in following this strategy. As for TTF, the
molecules stack and the p–p overlap is the most important for
the electronic properties. There is also some interstack overlap,
since the packing arrangement for the donors is different from that
of TTF-TCNQ in a crucial way. Specifically, The TMTSF layers align
the molecules so that there is greater interstack contact, see
Fig. 4 (though there is some cancelation due to overlap con-
tributions of opposite sign). Further, the bandwidths are larger
due to greater Se–Se overlap within the stacks. Noteworthy also
is that the acceptors are singly charged, such that there is a large
potential to further ionization. Thus, the Bechgaard salts and the
vast majority of well-studied organic CTS crystallize in a 2:1 ratio,
with one electron donated for every two donors.
In 1979, Jérome et al., reported superconductivity in
(TMTSF)2PF6 under about 0.9 GPa of pressure, and with that dis-
covery came the new field of organic superconductivity [12]. In
the particular case of (TMTSF)2PF6, a metal–insulator transition
occurs at 12.1 K in the absence of applied pressure. It was rea-
lized from NMR experiments that the resulting ground state is
a linearly-polarized spin-density wave (SDW), with lineshapes
consistent with incommensurate wavevector components [13].
Analysis of 1H NMR lineshapes revealed the wavevector compo-
nents as [14], in spite of the integral hole count. In the following
decades, many dozens of organic CTS superconductors were dis-
covered [15]. A prevalent theme is the proximity of the super-
conducting phase to antiferromagnetic insulating states, which
are considered either Mott insulators, or SDW insulators. The lat-
ter are epitomized by the Bechgaard salts; in this family of con-
ductors, the Fermi surface consists of open sheets with very
good, but nevertheless imperfect nesting that drives the spin-
density wave incommensurability, and consequently often
referred to as quasi-one dimensional (q1d). Typically, the
superconductivity emerges once the SDW ground state is
suppressed. The compounds exhibiting direct transitions
Mott ? superconductor are characterized by stronger interstack
contacts and consequently q2d. In almost all cases, the donor
and counterion sublattices are arranged in layers, with strongly
reduced interlayer hopping.
Below, we discuss the materials in Section 2. This is followed by
the physical properties and understandings of the normal and
superconducting states in the Bechgaard salts and related TMTTF
salts in Section 2.1. The best known q2d superconductors are also
2:1 salts of the BEDT-TTF (ET) donor, which are discussed in
Section 2.2. By now, it is widely accepted that the superconductors
are singlet paired. Nevertheless, in a number of compounds, the
superconducting state is stable beyond the paramagnetic limiting
field, so long as orbital suppression is avoided by applying the
magnetic field precisely in the plane of the layers. By now,
experimental evidence for inhomogeneous superconductivity,
sometimes referred to as LOFF or FFLO states, is convincing. And
since the organic superconductors are so far unique in this regard,
 S.E. Brown / Physica C 514 (2015) 279–289
we include some brief remarks pertaining to the novel supercon-
ductivity observed beyond the Pauli field.
Unfortunately, brevity forces the exclusion of many subtopics
and contributions of great interest. For example, organic
conductors have served well as prototypes for exploring quantum
oscillations and angular-dependent magnetoresistance (AMRO) in
high magnetic fields, and exploiting those to extract Fermi surface
parameters in quasi-one dimensional and quasi-two dimensional
cases. These explorations led to the discovery of field-induced
spin density waves [16–18], first seen in (TMTSF)2PF6 and
(TMTSF)2ClO4, which are also accompanied by quantized Hall
plateaus in a bulk system [19]. Field-induced superconductivity,
maximally stable at 30 T in k-(BETS)2FeCl4, is overlooked [20].
Also omitted is the subject of quantum spin liquids, which became
a subject for direct experimentation only after the report for
absence of magnetic order to T=J  1 in j-(ET)2Cu2(CN)3 [21].
Expansive reviews and collections related to these subjects and
others, as well as the material presented here, can be found, for
example, in Refs. [15,22–25].
It is perhaps useful to contrast the opportunities presented by
the organic superconductors to inorganic materials such as the
cuprates. From the transport perspective, the organic materials
are relatively cleaner owing to the fixed stoichiometry (e.g., 2:1)
and good crystalline quality, and hence the utility of high-field
research. However, that constraint goes along with fixed carrier
concentration. Historically, ground state tuning has instead been
accomplished through control over the lattice constants either by
counterion substitution or mechanical pressure. A lot has been
learned from a few measurement techniques, such as transport
and optics, magnetotransport, thermodynamic measurements,
and magnetic resonance probes. Unfortunately, some of the probes
that saw tremendous developments recently have not been
successfully applied to the organic CTS. For example, the crystals
have proven too small, or result in too much diffuse scattering
for measurements of the magnetic Bragg peaks in the AF ordered
materials, let alone inelastic scattering measurements. Also, the
crystals are particularly prone to photon damage in ARPES
experiments, and to date there is a notable scarcity of scanning
tunneling microscopy/spectroscopy.
2. Some molecules and crystal structures
In Fig. 3 is shown a number of organic molecules used for crys-
tallization in conducting charge transfer complexes, and including
many known superconductors. Many of the favorable properties of
TTF are transferred from one to the other, namely relatively low
oxidation potential of the chalcogen-centered pz dominated
Fig. 3. Selected donor molecules used as building blocks in organic superconduc-
tors and conductors. While there are no known superconductors with TTF itself,
there are more than 100 using the TTF derivatives TMTSF or TMTTF, BEDT-TTF, and
BETS.
281
Fig. 4. A representative crystal structure for the Bechgaard salts. Shown here is the
structure for (TMTSF)2PF6, with views projected along the b-axis and with the
stacking (a) axis vertical (left), and along the a-axis. The hash marks correspond to
the unit cell.
HOMO, and high degree of crystallinity when forming salts by the
standard electrolysis method. The highly symmetric TMTTF/TMTSF,
and ET donors are associated with more than 10, and greater than
50 independent superconducting compounds, respectively, and
more than 50 have been identified in compounds made from
other organic molecules. In this article, we will discuss physical
phenomena associated with the superconductors made from
TMTSF and BEDT-TTF donor molecules. Here, we introduce the
materials, their crystal and electronic structures, in order to pro-
vide some context for the more detailed descriptions that follow.
2.1. The Bechgaard salts, (TMTSF)2X, and sulfur analogs (TMTTF)2X
Just as for TTF-TCNQ, the stacking arrangement of the donor
molecules is the predominant feature of the crystal structure for
the Bechgaard salts (TMTSF)2X and their isostructural TMTTF
analogs. We will refer to the broader family as (TM)2X, where the
choices for anions X = PF6, ClO4, etc., are singly charged and elec-
tronically inert. The (high-temperature) triclinic unit cell (P1) con-
sists of two donor molecules per unit cell [26]. An example is
shown in Fig. 4, which depicts two views of (TMTSF)2PF6. Within
the stacks, the separation between the molecules is roughly twice
the Van der Waals radius, which for TMTSF is 3.8 Å. The coun-
terions for the TM salts are falling into two classes, centrosymmet-
ric and non-centrosymmetric. In either case, they are confined to
the well-separated spaces between the donors. The centrosymmet-
ric anions are mostly hexafluorides, including the octahedral PF6,
As6, and SbF6, but include also Br. The non-centrosymmetric anions
include the tetrahedral ClO4, ReO4, and BF4, and the distorted,
polarized tetrahedron FSO3. In all cases, at high temperature, the
counterions are undergoing rotations and positioned at locations
of inversion symmetry, which has at least two notable
consequences. First, the inter-donor distance within the stacks is
slightly dimerized, which formally sets the formal band-filling to
1/2. Second, for the non-centrosymmetric case, an order–disorder
symmetry breaking transition is expected upon cooling.
The electronic band structures are calculated in the tight-bind-
ing approximation by assuming that Se–Se contact is the dominant
source of overlap, and that the molecular orbital approximation
applies [27–29]. Thus,
Eðk ¼ 2t a cosðka aÞ  2t b cosðkb bÞ  2tc cosðkc cÞÞ; ð1Þ
with some characteristic band parameters for the a–b plane are
summarized in Table 1, where the intrastack dimerization is
ignored. As for TTF, the HOMO for TMTSF and TMTTF are the anti-
bonding out-of-plane p-orbitals, resulting in much larger intrastack
bandwidths so that ta is negative. Due to partial cancelation of
interstack hopping integrals in the b direction, one-dimensional
282 S.E. Brown / Physica C 514 (2015) 279–289

Table 1
Characteristic band parameters for selected TM salts, in the molecular orbital
104 (TMTSF)2PF6
approximation. Energies displayed are in meV. (a) = Ref. [30], (b) = Ref. [31].

Salt ta tb Ref. 103

S–SbF6 179 3 a
S–PF6 179 24 a c*
102
Se–PF6 230 58 b

physics remains important. Since the inert anions also leave the lay-
ers well-separated, the overlap in the third direction is considerably
smaller. The resulting open Fermi surface with exaggerated overlap
is depicted in Fig. 5, for an orthorhombic unit cell comprised of two
donors and relatively weaker t c .
The experimental evidence for the proposed electronic struc-
ture comes, for example, by way of anisotropic conductivity mea-
surements and angle-dependent magnetoresistance. In the first
case, a large anisotropy, qb =qa  100 over temperatures ranging
from the SDW transition at 12–300 K [32], which suggests a ratio
for the transfer integrals of ta =tb  10 (Fig. 6). The ratio qc =qa is
even larger, albeit temperature dependent. This latter effect has
been interpreted as a dimensionality crossover [33]. The angular
dependence of the magnetoresistance of the Bechgaard salts has
been studied thoroughly as the prototypical quasi-one dimensional
conductor [34,35]. For example, Fermi surface parameters have
been inferred from prominent features in the c-axis magnetoresis-
tance qzz using a–c rotations of the field with results proportionally
consistent.
Typically, however, the correlations are more significant than
those producing the SDW state for (TMTSF)2PF6. A more complete
phase diagram for the series of salts (TMTSF)2X, (TMTTF)2X appears
in Fig. 7 [36,37]. The principal method for achieving ground-state
control is through the lattice spacing, which in turn influences
the ratio of orbital overlap integrals t b =t a , and their relationship
to the on-site and near neighbor repulsive interactions U; V. The
insulators are found on the low-pressure side of the phase diagram,
where the overlap is smaller and correlation effects are more effec-
tive in localizing carriers. More precisely, that control is exercised
by the application of chemical or mechanical pressure. In the first
case, substitution of the counterion, such as PF6 for SbF6 leads to
reduced lattice constants. Likewise, choosing the TMTSF molecule
in place of the TMTTF molecule with its larger chalcogen pz orbitals
leads to greater overlap. To illustrate, we consider the calculated
band parameters and lattice constants for (TMTTF)2SbF6,
(TMTTF)2PF6, and (TMTSF)2PF6 in Table 1. Modest mechanical
pressure produces similar effects, since molecular crystals are also
relatively soft in all directions. Even 1 GPa from a standard BeCu
ρdc (Ω cm)
101
b'
100
10-1
a
10-2
10-3
10-4
1 10 100
Temperature (K)
Fig. 6. Temperature dependent resistivity measured along the orthogonal axes
0
a; b ; c in (TMTSF)2PF6. After Ref. [32].
clamp pressure cell is sufficient to move considerably beyond the
suppression of the spin-density wave (SDW) ground state of
(TMTSF)2PF6, and well into the superconducting phase. Likewise,
the spin-Peierls (SP) ground state of the insulating (TMTTF)2PF6
is replaced by an antiferromagnetic phase with comparable
pressures. Thus, the phase diagram was pieced together from the
pressure effect on a series of salts. In fact, however, much larger
pressures have been applied to TMTTF salts with PF6 [38,39], and
later with SbF6 [40], AsF6 [41] counterions, and driven the systems
through the expected sequence of phases and finally terminating
with superconducting ground states. Thus, a broader perspective
of the physics of the Bechgaard salts and the TMTTF analogs
includes not just relatively weak correlations and resulting
spin-density waves, but also the Mott states of the TMTTF salts.
Ground states and ordering temperatures for a few salts are
included in Table 2.
In fact, an important aspect for the insulators is the prevalence
of charge-ordering (CO) instabilities [42–44]. That is, there are two
T
TM2X

CO
1

0.5 SP
AF AF/SDW
SC
k /π

0
y

P
(TMTSF) 2PF6
(TMTTF) 2PF6
(TMTTF) 2SbF6

(TMTTF) 2Br

−0.5

−1
0.5
1
0
0
Fig. 7. Generic phase diagram for the TMTSF/TMTTF salts with centrosymmetric
kx/π −0.5 −1 anions. Pressure increases the interchain overlap tb , influencing directly the ground
kz/π states. Ambient-pressure properties for selected salts are shown by their position-
ing along the pressure axis. The ground states are labeled as CO = charge ordered,
Fig. 5. Model quasi-one dimensional Fermi surface for an orthorhombic cell. The SP = spin-Peierls, AF = antiferromagnet, SC = superconductivity. The effective pres-
warping in the b; c directions is exaggerated for emphasis. sure span is of order 5.0 GPa.
 S.E. Brown / Physica C 514 (2015) 279–289 283

Table 2 which are observed when forming salts with a remarkably wide
Transition temperatures to broken-symmetry ground states for TM2X. The designa- variation of counterion species. The polytypes are each designated
tions are: AF = antiferromagnetic, SP = spin-Peierls, SDW = spin-density wave,
SC = superconducting.
with a Greek letter; an example is the j-phase arrangement,
j-ET2Cu(NCS)2, shown in Fig. 8, with its highly dimerized arrange-
Salt Gnd. state T c (K) P ment on a parquet-like pattern. Some of the other polytype
S–SbF6 AF 8 Ambient arrangements are depicted in Fig. 9. Quite generally, the ethylene
S–AsF6 SP 13 Ambient endgroups are located adjacent to the neighboring counterion
S–PF6 SP 20 Ambient
Se–PF6 SDW 12.1 Ambient
spacer layers, so the bar-like entities shown are intended to sug-
Se–PF6 SC 1.4 0.6 GPa gest a projected view orthogonal to the long molecular axis.
Se–ClO4 SC 1.4 Ambient The molecular stacks in ET salts tend to have a shifted overlap,
due to steric effects originating with the ethylene endgroups. This
weakens the p-orbital overlap and reduced conductivities along
routes to the insulating state. In the first, the CO results from an the stacking direction when compared to the TMTSF salts or TTF-
effective 1/4-filling and significant near-neighbor repulsion V. TCNQ. On the other hand, the staggered interstack S–S contacts
The starting point here is the extended Hubbard model [45]. are significant and provide sufficient overlap along with higher
Perhaps, also, it is assisted by coupling to the counterion displace- relatively higher conductivity in the ET salts perpendicular to the
ments [46–48]. A second, distinct route to an insulating state stacks, and hence are commonly grouped as quasi-two dimen-
occurs even when V is less important, because bond alternation sional organic conductors and superconductors [22, see Ch. 11].
along the stacks leads to the so-called Dimer-Mott state. When discussing the ET salts, a consideration sometimes
neglected is also a source of disorder. The molecular conformation
2.2. Salts based on the BEDT-TTF donor shown in the figure includes a notable twist at each end, resulting
from ethylene group ordering. This is common to the case of ET
The large number of conductors and superconductors based on donors, which are nonplanar, and in this way different from TTF
the BEDT-TTF donor can be linked to the considerable variety of or TMTSF. Where the twists are in the identical direction, the
intralayer molecular arrangements for the ET-based compounds conformation is said to be eclipsed, and in opposite directions they
are staggered. Considerable conformational disorder is not
uncommon, is often quenched upon cooling, and can lead to thermal
hysteresis in transport properties [49].
The interlayer overlap is extremely weak in most cases. For
some materials, such as the familiar j phase conductors, there
has been sufficient effort in determining whether coherent inter-
layer transport occurs at all, and in other cases it is very weak
[23,50]. Consequently, the band structure is usually discussed in
terms of the intralayer overlaps and Fermi surface. Then, for many
of the polytypes, there are four donors per unit cell. This would
apply to the j; a, and b00 cases, for example. With two holes dis-
tributed among the four donors, the projected FS area is precisely
one (2d) Brillouin zone. Typically, two bands cross the Fermi
energy producing a FS featuring a q2d hole pocket and a q1d sheet,
such as that shown in Fig. 10, and reproduced from Ref. [51].
Again, there is ample experimental evidence supporting this
general picture, particularly when it comes to magnetotransport
results. The quantum oscillations set in at relatively modest mag-
netic fields for the q2d pockets, with magnetic breakdown giving
the expected area of one BZ at higher fields [23,50, and references
therein].
The picture is incomplete, however, since correlations play a
significant role in many of the ET salt families, with the relative
importance again tuned with chemical or mechanical pressure.
The j-phase materials illustrate this point very simply. In that

Fig. 8. Crystallographic arrangement of donor molecules and counterions in j-

(BEDT-TTF)2Cu(NCS)2. (Top:) view along b-axis, and (bottom:) along the a-axis, Fig. 9. Intralayer BEDT-TTF arrangements for representative polymorphs of BEDT-
showing the strongly dimerized arrangement of the donors for the j phase. TTF, designated as a; b; b00 .
284 S.E. Brown / Physica C 514 (2015) 279–289
Fig. 10. Example of quasi-two dimensional band structure and Fermi surface, containing a closed pocket and an open sheet, from j-(ET)2Cu(NCS)2 (after Ref. [51]). Many of
the ET salts containing four donors in the unit cell have electronic structure with these features.
case, the minimal model frequently adopted is that where the
overlap integral associated with intradimer pair (Fig. 8) effectively
distributes the hole over both donors [52], such that the on-site
Coulomb repulsion U also pertains to the dimer. Then, the
interdimer overlaps are relevant for carrier delocalization. In this
case, the T=P phase diagram is somewhat simpler than for the q1d
materials. In Fig. 11 is a depiction of the tuning by pressure for
j-(ET)2Cu[N(CN)2]Cl (j-Cl) [53]. Effectively, pressure influences
the U=t ratio, which was also manipulated indirectly by deuterating
the ethylene groups in the ambient-pressure superconductor
j-(ET)2Cu[N(CN)2]Br (j-Br) [49]. Unlike the TM salts, the q1d insta-
bilities (SP, SDW) associated with the quasi-one dimensionality are
missing. Instead, there is a line of first-order phase transitions
separating the conducting and insulating sides, which terminates
at a critical point [53,54]. The ground state on the conducting side
is superconducting, where the low-temperature resistivities follow
the form characteristic of a Fermi Liquid, dqðTÞ  T 2 [55,56]. The
ground state on the insulating side is apparently determined by
the details of the frustration on the anisotropic triangular lattice
(on which the dimer pairs are situated): it is either AF (j-Cl), or
Quantum Spin Liquid (QSL, j-(ET)2Cu2(CN)3) [21,57,58].
In those polytypes absent a strong dimerization, CO instabilities
often prevail [59,60]. In principle, the transition separating
conducting and insulating phases can be continuous or first-order,
with the symmetry-breaking leading to horizontal or diagonal
stripes. However, generic expectations would have the transition
be first order at sufficiently low temperature that a magnetic order
parameter develops on top of the CO. Should the transition remain
T
crossover
insulating
CP
R~T2
AFI
SC
P
κ-Br
κ-Cl
κ-NCS
Fig. 11. Depiction of temperature/pressure phase diagram for j-(ET)2Cu[N(CN)2]Cl.
See Ref. [53].
only weakly first order, an interesting question to ask is, what is
the influence of the collective charge fluctuations at low tempera-
ture and nearby to the CO phase boundary? In Ref. [61], it was sug-
gested that they are associated with an effective attraction
sufficient for pairing. We return to this point at the conclusion of
the article.
3. Superconductivity and normal state properties of the q1d
materials, (TMTSF)2X
With the phase transition to a fully-gapped density wave state
occurring only at T SDW  12 K in (TMTSF)2PF6, the uniaxially-ori-
ented SDW is suppressed with only modest pressure by worsening
the nesting conditions. Superconductivity is stabilized at pressures
greater than Pc ’ 0:6 GPa. Antiferromagnetic spin fluctuations (SF)
nevertheless persist to much greater pressures, and consequently,
the Bechgaard salts are among the first known examples where
superconducting pairing is often linked to magnetic interactions.
In the same year, superconductivity was discovered in the heavy
fermion compound CeCu2Si2 [62].
The temperature/pressure phase diagram for (TMTSF)2PF6
appears in Fig. 12. NMR experiments indicate that the SDW ground
state is incommensurate, arising from imperfect nesting condi-
tions. Pressure increases overlap, in turn worsening the nesting
conditions. The Peierls temperature TSDW = 12.1 K is reduced
smoothly to T = 0 at a critical value of Pc  0:6 GPa. For P > Pc ,
superconductivity is observed at temperatures less than
14
12
(TMTSF)2PF6
10
temperature (K)
8
6
SDW SC
4
2
0
0 0.2 0.4 0.6 0.8 1 1.2
pressure (GPa)
Fig. 12. Temperature/pressure phase diagram for (TMTSF)2PF6, showing the
suppression of the spin density wave ground state with pressure, and the
emergence of a superconducting state. The ground states of (TMTSF)2AsF6 evolve
with pressure similarly [63].
 S.E. Brown / Physica C 514 (2015) 279–289 285

T c K 1:5 K, with the transition temperature slowly and monotoni- 6

cally decreasing upon increasing the pressure beyond Pc . The
superconducting transition temperature is maximum close to P c , 5 μ0H//b’
and decreases with greater pressures [64]. Replacing PF 6 for other

magnetic field μ0H (T)


counterions, such as AsF 6 or ClO4 gives similar results, with the
perchlorate salt already superconducting at ambient pressure.
3.1. Superconducting properties
At the time of discovery, the physical properties of the super-
conducting state were expected conventional, fully independent
of the spin-density wave instability and with a fully-gapped
s-wave order parameter. In the 3–4 years that followed, that pic-
ture was very much in doubt for several reasons. On the experi-
mental side, counter-evidence accumulated quickly. For instance,
a rapid suppression of the critical temperature results from the
introduction of non-magnetic impurities [65,66] was regarded as
evidence for a sign change of the order parameter over the Fermi
surface. This, and the quasi-one-dimensionality of the electronic
structure led to the suggestion that intrastack triplet (px -wave)
pairing was a possibility [67]. At about the same time, a model
for interstack pairing by antiferromagnetic spin fluctuations [68]
was introduced for the first time [69]. These two proposals lead
to distinctly different properties in the superconducting state. In
the first case, the FS is fully-gapped, and therefore the low tem-
perature thermodynamic quantities are activated. In addition, a
Hebel–Slichter (HS) enhancement of the spin-lattice relaxation
rate is expected for T 6 T c , and quasiparticle Zeeman coupling does
not suppress the superconconductivity. On the other hand, the
interstack AF spin fluctuation picture leads to a d-wave-like order
parameter with lines of gap zeroes. Thus, the thermodynamic
properties in the limit T ! 0 are power laws in temperature and
the HS peak in the relaxation rate should be suppressed.
1
H was the target nucleus in the first exploration of the relax-
ation rate in the ambient-pressure superconductor (TMTSF)2ClO4
[70]. To avoid orbital suppression of the superconductivity with
high magnetic field, Takigawa and co-workers followed the origi-
nal 27Al example of Hebel and Slichter [71], by cycling the mag-
netic field to zero for the evolution time. The magnetic field was
raised again to the resonance condition only to read the resulting
magnetization decay. The relaxation rate was found to follow
roughly a T 3 power law from T c down to  T c /2, and interpreted
as evidence for line nodes in the SC order parameter [70,72]. Not
long afterward, similar behavior was observed for cuprate super-
conductor YBa2Cu3O6.91 [73].
At that time, the idea of a nodal superconductor, for TMTSF as
well as the cuprates was still controversial. With regard to the for-
mer, the highly anisotropic field/temperature phase diagram
reported for the PF6 salt regenerated interest in the problem [74].
Later, similar results were reported for the perchlorate salt [75].
The upper critical field shown in Fig. 13 was determined using
4 (TMTSF) PF
2 6
P = 0.6GPa)
3
2 μ0H//a μ0HP
1
μ0H//c*
0
0 0.5 1 1.5
temperature T (K)
Fig. 13. l0 Hc2 for (TMTSF)2PF6, determined resistively and with the field parallel to
0
the conducting planes (a-, b -directions), and orthogonal to the planes (c ). (After
Ref. [74]).
length is shorter than the mean-free-path. That leaves other
possibilities: that the superconductor is driven unstable by the
magnetic field, but does not revert directly to the normal state.
Instead, there is an intermediate state which is superconducting
but characterized by a nonzero spin susceptibility. The inhomoge-
neous state first proposed Fulde and Ferrell [78] and independently
by Larkin and Ovchinnikov [79], follows that prescription. Such
LOFF (or 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
because orbital suppression is quenched for in-plane fields. Even
then, however, Pauli-limiting behavior would be expected, and
then the LOFF state is accessed through a line of phase transitions
at a magnetic field of the order of the paramagnetic limit. However,
0
with Hkb , there is no signature for Pauli-limiting behavior, and
therefore, (TMTSF)2PF6 was instead considered a candidate for a
spin triplet pairing state [76,80].
Knight shift measurements on (TMTSF)2ClO4 make the possibil-
ity for triplet pairing very unlikely, at least at low magnetic field
strengths. In Ref. [81] is reported 77Se NMR spectroscopy at
temperatures less than 100 mK, and magnetic fields less than 1 T.
Under these conditions, the spin polarization was found to be less
than half that expected for the normal state. The remaining
response could be attributed to triplet pairing [82], but then it is
important to note that even Zeeman shifts of the quasiparticle
states near to gap zeroes assure non-zero spin polarization in a
magnetic field [83]. Therefore, the experimental results are
40
−1 −1
0.4
(T1T) (s−K) , H//b’
−1 −1
[ T T] −1 (s−K)−1

resistivity measurements, which revealed stable superconductivity 30 6×(T1T) (s−K) , H//a 0.3
to magnetic fields significantly greater than the paramagnetic- Rzz
Rzz (Ω)

limiting field HP  2:5 T [76]. The robustness against magnetic 20 0.2

fields applies only when the field is aligned to the molecular layers,
0
that is, in the a—b plane. Tilting of the field quickly leads to orbital
1

10 0.1
suppression of the SC state. Avoiding orbital suppression is particu-
77

0
larly strong for fields aligned orthogonal to the stacks, along b . 0 0
A superconductor surviving to fields exceeding the para- 0 1 2 3 4 5
magnetic limit can occur under several circumstances. From a
magnetic field μ H (T)
thermodynamic perspective, if the superconducting state acquires 0
a spin susceptibility of the order of the normal state, there is noth-
Fig. 14. 77Se ½T T 1 vs. l0 H, in the limit T ! 0, normalized to the normal state, and
ing to be gained by reverting to the normal state. The most familiar contrasted to the interlayer resistance Rzz ðl0 HÞ. The recovery of the NMR relaxation
means for doing that is strong spin-orbit scattering [77]. For that to toward the normal state is observed to occur at much smaller fields than the
apply, the superconductor is in the dirty limit, where the coherence resistance.
286 S.E. Brown / Physica C 514 (2015) 279–289

5 Similar behavior was documented in the field-dependent speci-

fic heat. The phase diagram obtained from those results, for the
H // a
4
field applied along the stacking axis, is shown in Fig. 15. Shown
C onset are the onset temperatures in different fields for both specific heat,
R onset and transport. In the former case, the field beyond which
μ 0Hc2 (T)

3 R zero superconductivity is undetectable appears paramagnetic limited.

Whereas, the transport results include signatures for the persis-
2 tence of an SC state to much larger fields. Therefore, despite the
transport properties, evidence for a superconductivity state at high
fields, in the bulk, remains elusive for the Bechgaard salts. On the
1
other hand, we discuss briefly later that the Zeeman-driven
inhomogeneous (LOFF) phase is stabilized in some quasi-two
0 dimensional systems, such as j-(ET)2CuðNCSÞ2 ; k-(BETS)2FeCl4,
0 0.5 1 1.5
and b00 -(ET)2SF5CH2CF2SO3.
T (K)

Fig. 15. Comparison of the phase diagram obtained from specific heat and transport 3.2. Normal state properties
measurements. The magnetoresistance is measured along the c-axis. After [84].

The normal state properties of the TMTSF salts lend credibility

considered as strong evidence for a singlet pairing state with lines
of zeroes over the Fermi surface.
The argument is only strengthened by specific heat measure-
ments performed on (TMTSF)2ClO4. In Ref. [84] are reported
detailed measurements using a vector magnet to apply in-plane
fields, the results of which were used to map the gap structure,
which resembles a d-wave-like order parameter. With the excep-
tion of the loose end of the indication for a full gap from thermal
conductivity measurements [85], all of these features, as well as
the normal state properties, are consistent with superconducting
pairing mediated by interstack antiferromagnetic spin fluctuations
[86].
What remains unclear is the nature of the superconducting
state at high magnetic fields, for field strength of the order of
and exceeding the paramagnetic limiting field of 2–2.5 T. Both
the specific heat [84] and the NMR relaxation [81] rates would
appear inconsistent with interesting proposals, such as the
possibility for a field-induced transition to a triplet order parame-
ter [87–89], or the transition to the inhomogeneous LOFF state
[90,91]. In the case of the relaxation rates, significant field-depen-
dence of the SC state relaxation rate were reported. At lower fields,
½T 1 T1 is a field-dependent constant in the limit T ! 0. However,
as shown in Fig. 14, ½T 1 T1 approaches the normal state result very
rapidly at fields in the range 1.5–2 T, while the interlayer
resistance Rzz , measured in situ, remains negligible.
150
P(GPa)
100
T −1 (s−1)
to the scenario for pairing mediated by AF spin fluctuations. For
instance, signatures are evident in the 77Se nuclear spin lattice
relaxation rate (SLRR), and furthermore, what is interpreted as
non-Fermi Liquid (NFL) behavior is detected in the resistivities.
With respect to the SLRR, the manifestation of the fluctuations is
in an enhancement over what could be expected from the
Korringa relaxation of an ordinary metal. In Fig. 16 is T 1 vs. T
1
for (TMTSF)2PF6 over a range of pressures covering both sides of
the critical pressure at Pc ¼ 0:6 GPa. At lower pressures, T 1 1
increases and tends to diverge as the temperature is lowered
toward T SDW . Such behavior is expected for critical slowing of the
dynamics. For P > Pc , the divergence is suppressed. Nevertheless,
an enhanced rate, largely temperature independent and therefore
very different from Korringa, remains. Clearly, however, in the
limit that T ! 0, ½T 1 T1 ! constant, which we take to be the
hallmark of a Fermi Liquid ground state.
A Curie–Weiss (CW) relation T 1 eT þ H, with H increasing
monotonically with pressure [81,92] describes the SLRR extremely
well for pressure P > P c (Fig. 17). The behavior matches what is
expected for 2d overdamped spin fluctuations, provided that the
temperature is not low when compared to the spin fluctuation
damping scale [93,94]. Following that phenomenology,
½T 1 T1  vðQ Þ; ð2Þ
and vðQ Þ  T þ H. Notably, similar observations have been made
for the cuprates, e.g., Ref. [95], and the pnictides e.g., Ref. [96]. In
0.45
0.53
0.60
0.68 45
0.78
0.95 40 (TMTSF)2PF6
1.15 P=0.9GPa μ H=4.91T//b’

35 0
Se T −1 (s−1)

30

25
0.8 T1T (s−K)
1

50
20
0.6
Θ∼11K
77

15 0.4

10 0.2
T (K)
0 0
0 5 10 15 20 25 30 5 0 10 20 30

temperature T (K) 0
0 5 10 15 20 25 30
77
Fig. 16. Se NMR spin lattice relaxation rate vs. temperature for (TMTSF)2PF6, for temperature T (K)
applied pressures P <> P c . T 1
1 tends to diverge on approaching T SDW ðPÞ. For higher
pressures the ground state is superconducting, coincident with large enhancements Fig. 17. Normal state 77Se T 1
1 vs. T in the regime at P = 0.9 GPa. The red line follows
1
of T 1 from spin fluctuations. a Curie–Weiss form, T 1 T  ðT þ HÞ. The data is replotted as T 1 T vs. T in the inset.
 S.E. Brown / Physica C 514 (2015) 279–289
the case of the Bechgaard salts, however, there is no indication for
pseudogap behavior, and significantly, the Curie–Weiss behavior
is uninterrupted to temperatures significantly less than T c [81],
whereas the expectation would be a crossover to constant T 1 T. To
our knowledge, the temperature regime T  T c has not been exam-
ined in other systems such as the pnictides.
Coincident with the Curie–Weiss relaxation rate is a low-tem-
perature resistivity of the form qðTÞ ¼ q0 þ aT. In a magnetotrans-
port of several families of correlated superconductors including
Bechgaard salts, cuprates, and pnictides, the magnitude of the
intrinsic linear-T contribution was correlated to the superconduct-
ing transition temperature [97,98]. As for the relaxation rate, the
linear-T resistivity persists to T  T c .
These observations are provided some context by the results of
renormalization group calculations [86,99]. Scattering amplitudes
from particle-hole and particle–particle channels are included;
the effect of the pairing interaction on the SF is to suppress the
low-temperature saturation of the correlation length. T-linear
resistivity implied for temperatures greater than the SF energy
scale. However, the behavior is linked directly to the highly-nested
Fermi surface, proximity to a quantum critical point at Pc , and the
interference between electron–electron and electron–hole scatter-
ing. The suggestion is that the interference modifies the physical
properties within some range of the SDW critical point, leading
to the unexpected observations.
4. Superconductivity and normal state properties of the q2d
superconductors j-(ET)2X
4.1. Superconducting properties
The first ET superconductor identified was b-(ET)2ReO4, with
T c  2 K [100]. The highest transition temperatures for any of the
ET-based compounds are in the j-phase materials [22] [and refer-
ences therein], with T c = 13.4 K, 11.5 K, and 10.5 K, with coun-
terions X = Cu[N(CN)2]Cl [101], Cu[N(CN)2]Br [102], and Cu(NCS)2
[103]. With regard to the pairing, 13C Knight shift measurements
in the superconducting state of j-Br show that the spin part of
the wave function is a singlet [104], and this carries over to j-
(BEDT-TTF)2Cu(NCS)2 (j-NCS) as well [105]. Measurements of
the 13C spin lattice relaxation are consistent with the presence of
nodal quasiparticles, in that ½T 1 T1 scales as T 3 in low fields and
T  T c , and moreover, there is no evidence for a Hebel–Slichter
enhancement of the relaxation rate for T ! T  c [104,106,107].
Both aspects are similar to what is observed for the cuprates. The
conclusion has carried with it considerable controversy. For exam-
ple, different methods for determining the superfluid density, lþ SR
and microwave conductivity experiments, produced evidence for
both line nodes [108,109] and a full gap [110], respectively.
Specific heat experiments were interpreted differently as well;
these experiments are described in Ref. [111] (gap zeroes) and in
Ref. [112] full gap. Recent measurements and interpretation of
superfluid density from microwave conductivity measurements
on j-NCS were found consistent with line nodes [113].
Regrettably, we have overlooked other important work dedicated
to this issue, and for that we apologize. Nevertheless, it would
appear that most of the evidence appears to support a nodal super-
conducting state, though notably missing from the discussion are
phase-sensitive experiments as were performed on the cuprates
[114,115]. We make a final note regarding an investigation of the
effects of defects on T c . With the Bechgaard salts [65,66] and with
Sr2RuO4 [116], T c is sharply suppressed by introducing defects or
impurities. In a similar investigation of j-NCS, the transition tem-
perature was found to decrease only marginally [117], and to our
knowledge the apparent discrepancy has not yet been resolved.
287
4.2. Normal state properties
Following the discussion on the Bechgaard salts, it is natural to
question whether overdamped AF spin fluctuations are providing
the pairing for the j-phase materials, as well as others. On that
basis, we wish to recount the evidence for spin fluctuations in
the normal state. First, we note that in Ref. [118] is a model cal-
culation based on the fluctuation–exchange approximation which
supports a superconducting state with T c  10 K, with 4 gap nodes
over the FS, two each for the closed pocket and the q1d sheets. The
gap symmetry is dx2 y2 . Incorporating the Mott physics requires a
strong-coupling approach; there, as well, d-wave superconductiv-
ity is found to emerge [119]. Specific heat experiments in an in-
plane magnetic field were carried out to probe the gap symmetry
in j-NCS Xand j-Br, with results consistent with the gap nodes
identified by the spin fluctuation model [120].
In Fig. 18 appears the temperature dependence of the 13C relax-
ation rate for j-NCS and j-Br [121]. For both, ½T 1 T1 increases upon
cooling to about 50 K, in a manner consistent with the development
of AF spin correlations. For T < 50 K, ½T 1 T1 sharply but continu-
ously decreases. The change in behavior coincides with the metal–
insulator crossover line, with Fermi Liquid behavior on the conduct-
ing side, depicted in Fig. 11. An important question then is how to
evaluate the role of spin fluctuations at temperatures of the order
of the superconducting transition temperature T c . The decrease in
½T 1 T1 has been discussed as possibly one of a pseudogap phe-
nomenon, associated with the onset of short-range spin fluctuations
and coherence of the intralayer transport [122,123]. Of course, the
notion of a pseudogap is attractive in that it is suggestive of related
phenomena in systems such as the cuprates. However, there are
many reasons to question whether such a relationship exists.
Perhaps most clear is this: contrary to underdoped cuprates, there
is no evidence for a broken symmetry and subsequent folding of
the Brillouin zone, with the exception of those effects associated
with a pressure-dependent lattice superstructure that is reported
to develop at quite high temperatures in j-Br [124]. Specifically,
the quantum oscillations observed in magnetotransport experi-
ments in j-NCS are attributed to expected sections of the Fermi sur-
face. The Korringa ratio K 2s T 1 T is shown to increase some marginally
below 50 K [106,122]. Nevertheless, the enhancement relative to
high temperatures is still present, so spin fluctuations remain
important in the normal state properties at T  T c .
4.3. High-field phases of the q2d superconductors
We divert the discussion here to comment briefly on the unu-
sual results obtained in some organic superconductors in high
0.2
κ−NCS
κ−Br
0.15
T T] −1 (s−K) −1
0.1
1
13
0.05
[
0
0 50 100 150 200 250 300
temperature (K)
Fig. 18. ½T 1 T1 vs. T for j-NCS and j-Br, after Ref. [121].
288 S.E. Brown / Physica C 514 (2015) 279–289
magnetic fields. A consequence of the very weak interplane
coupling, to the degree that the interlayer Ginzburg–Landau
correlation length n? is considerably less than the separation of
the conducting planes for T  T c [125,126]. Therefore, for in-plane
fields, the flux penetrates in the form of Josephson vortices. An
important consequence is that in larger fields, where the inter-
Josephson vortex separation falls below the Josephson penetration
depth, intralayer orbital currents vary as the inverse field. That is,
orbital energy shifts become inconsequential relative to Zeeman
shifts, making selected organic superconductors ideal cases for a
high-field transition to a high-field phase as discussed by Larkin
and Ovchinnikov [79] and Fulde and Ferrell [78]. Such LOFF (or
FFLO) states could be considered intermediate phases, between
uniform superconducting and normal states, in which the Cooper
pairs acquire momentum and associated spin response. In the
Larkin/Ovchinnikov manifestation, the order parameter changes
sign in real space. The best known system for LOFF physics is j-
NCS, and by now the evidence is convincing. It has been long
appreciated that the system remains in the SC state well beyond
the paramagnetic limiting field [112,127]. A transition to a high
field superconducting phase (normal ? LOFF) has been seen
independently in the electrodynamic response [128] and torque
measurements [129]. NMR gives clear evidence for a continuous
transition connected to an inhomogeneous spin polarization in a
bulk superconductor [105] as well as evidence in the relaxation
rate for spin-polarized bound states at the gap zeroes [130]. This
example is not unique: observations consistent with LOFF physics
have been reported in k-(BETS)2FeCl4 [131], as well as the
all-organic superconductor b00 -(ET)2SF5CH2CF2SO3 [132].
5. Concluding remarks
In the j-phase superconductors, as for TMTSF, the preponder-
ance of evidence would support AF spin fluctuations as responsible
for superconducting pairing and which leads to sign changes and
nodal structures in the gap function. This seems most clear for
the case of TMTSF, where the nuclear spin lattice relaxation rate
is seen greatly enhanced prior to the transformation to the SC state,
and close to the critical pressure the resistivity varies linearly in
temperature. Thus, the 1979 discovery of superconductivity in
the TMTSF salts, coinciding with the first observations of heavy fer-
mion superconductivity, marked the beginning of an era in which
electronic correlations were recognized as an indispensable ingre-
dient in many superconducting compounds. In q2d organics such
as the j phases, magnetic fluctuations are important for T > T c ,
though the anamolous drop in the Korringa constant below about
50 K remains an open question. In all, the case for the sign change
of the gap is strong but perhaps not bullet-proof. Unfortunately,
the deeper understanding that would come to both the
Bechgaards and the j systems from inelastic neutron scattering
measurements, let alone elastic scattering, is still missing. With
that backdrop, we emphasize that our goal here was not to be all
inclusive, even regarding the ET salts. Instead, we focused on those
two systems studied most thoroughly, and moving away from
them may change the story. For example, there remains another
proposed route to superconductivity, which nevertheless depends
on correlations. In Ref. [61], it is proposed that collective charge
fluctuations related to nearby CO instabilities can induce pairing,
and several candidate systems are suggested among the b00 or h
polytypes. (Note that this would ordinarily not apply to the j
materials where CO instabilities are less likely.) Optics measure-
ments, both Raman and infrared, have resulted in some unusual
observations in the superconductor b00 -(ET)2SF5CH2CF2SO3, includ-
ing the temperature-dependent oscillator strength at low energies,
which are attributed to CO fluctuations [133].
Acknowledgements
The author is grateful for many discussions and insights learned
from colleagues and collaborators on the subject of organic
superconductors. Here, special recognition is given to our friend,
the late Professor James Brooks. Support from NSF under Grant
No. DMR-1410343 is also acknowledged.
References
[1] W. Little, Phys. Rev. 134 (1964) A1416–A1424.
[2] F. Wudl, G.M. Smith, E.J. Hufnagel, Chem. Commun. 1 (1970) 1435.
[3] J. Ferraris, D.O. Cowan, V. Walatka, J.H. Perstein, J. Am. Chem. Soc. 95 (1973)
948–949.
[4] A.J. Berlinsky, J.F. Carolan, L. Weiler, Solid State Commun. 15 (5) (1974) 795–
801.
[5] S. Shitzkovsky, M. Weger, H. Gutfreund, J. Phys. 39 (1978) 711–717.
[6] T.J. Kistenmacher, T.E. Phillips, D.O. Cowan, Acta Cryst. B 30 (3) (1974) 763–
768.
[7] R. Comès, G. Shirane, S.M. Shapiro, A.F. Garito, A.J. Heeger, Phys. Rev. B 14
(1976) 2376–2383.
[8] R.H. Friend, M. Miljak, D. Jérome, Phys. Rev. Lett. 40 (1978) 1048–1051.
[9] D. Jerome, H.J. Shulz, Adv. Phys. 31 (1982) 299–490.
[10] S. Megtert, R. Coms, C. Vettier, R. Pynn, A. Garito, Solid State Commun. 31 (12)
(1979) 977–980.
[11] S. Khanna, J. Pouget, R. Comes, A. Garito, A. Heeger, Phys. Rev. B 16 (1977)
1468–1479.
[12] D. Jérome, A. Mazaud, M. Ribault, K. Bechgaard, J. Phys. Lett. 41 (1980) L95–
L98.
[13] A. Andrieux, D. Jerome, K. Bechgaard, J. Phys. Lett. 42 (4) (1981) L87–L90.
[14] T. Takahashi, Y. Maniwa, H. Kawamura, G. Saito, J. Phys. Soc. Jpn. 55 (4) (1986)
1364–1373.
[15] A.G. Lebed (Ed.), The Physics of Organic Superconductors and Conductors,
Springer Series in Materials Science, vol. 110, Springer, Heidelberg, 2008.
[16] J.F. Kwak, J.E. Schirber, R.L. Greene, E.M. Engler, Phys. Rev. Lett. 46 (19) (1981)
1296–1299.
[17] P.M. Chaikin, M.Y. Choi, R.L. Greene, J. Mag. Mag. Mat. 31–34 (1983) 1268–
1272.
[18] L.P. Gor’kov, A.G. Lebed, J. Phys. Lett. 45 (1984) L433–L440.
[19] W. Kang, S.T. Hannahs, P.M. Chaikin, Phys. Rev. Lett. 70 (20) (1993) 3091–
3094.
[20] S. Uji, H. Shinagawa, T. Terashima, T. Yakabe, Y. Terai, M. Tokumoto, A.
Kobayashi, H. Tanaka, H. Kobayashi, Nature 410 (2001) 908–910.
[21] Y. Shimizu, K. Miyagawa, K. Kanoda, M. Maesato, G. Saito, Phys. Rev. Lett. 91
(2003) 107001.
[22] T. Ishiguro, K. Yamaji, G. Saito, in: Organic Superconductors, Springer Series in
Solid State Sciences, Springer Verlag, Berlin, Heidelberg, 1998.
[23] J. Singleton, C. Mielke, Contemp. Phys. 43 (2002) 63–96.
[24] P. Batail (Ed.), Molecular Conductors, Chemical Reviews, vol. 104, 2004
(special issue).
[25] R. Kato (Ed.), Molecular Conductors, Crystals, vol. 2, 2012 (special issue).
[26] N. Thorup, G. Rindorf, H. Soling, K. Bechgaard, Acta Cryst. B 37 (1981) 1236–
1240.
[27] P.M. Grant, Phys. Rev. B 26 (12) (1982) 6888–6895.
[28] P.M. Grant, Phys. Rev. Lett. 50 (13) (1983) 1005–1008.
[29] A. Jacko, H. Feldner, E. Rose, F. Lissner, M. Dressel, R. Valentí, H. Jeschke, Phys.
Rev. B 87 (2013) 155139.
[30] K. Yoshimi, H. Seo, S. Ishibashi, S. Brown, Phys. Rev. Lett. 108 (2012) 096402.
[31] L. Ducasse, M. Abderrabba, J. Hoarau, M. Pesquer, B. Gallois, J. Gaultier, J. Phys.
C 19 (20) (1986) 3805.
[32] M. Dressel, K. Petukhov, B. Salameh, P. Zornoza, T. Giamarchi, Phys. Rev. B 71
(7) (2005) 075104.
[33] H. Wilhelm, D. Jaccard, R. Duprat, C. Bourbonnais, D. Jérome, J. Moser, C.
Carcel, J.M. Fabre, Eur. Phys. J. B 21 (2) (2001) 175–183.
[34] G.M. Danner, W. Kang, P.M. Chaikin, Phys. Rev. Lett. 72 (23) (1994) 3714–
3717.
[35] S.E. Brown, M.J. Naughton, P.M. Chaikin, in: The Physics of Organic
superconductors and Conductors, Springer Series in Materials Science, 110,
Springer, Heidelberg, 2008. Ch. La tour des sels Bechgaard, pp. 49–87.
[36] W. Yu, F. Zhang, F. Zamborszky, B. Alavi, A. Baur, C.A. Merlic, S.E. Brown, Phys.
Rev. B 70 (12) (2004) 121101.
[37] F. Iwase, K. Sugiura, K. Furukawa, T. Nakamura, Phys. Rev. B 84 (2011)
115140.
[38] T. Adachi, E. Ojima, K. Kato, H. Kobayashi, T. Miyazaki, M. Tokumoto, A.
Kobayashi, J. Am. Chem. Soc. 122 (13) (2000) 3238–3239.
[39] D. Jaccard, H. Wilhelm, D. Jérome, J. Moser, C. Carcel, J.M. Fabre, J. Phys.:
Condens. Matter 13 (4) (2001) L89.
[40] M. Itoi, C. Araki, M. Hedo, Y. Uwatoko, T. Nakamura, J. Phys. Soc. Jpn. 77 (2)
(2008) 023701.
[41] M. Itoi, M. Kano, N. Kurita, M. Hedo, Y. Uwatoko, T. Nakamura, J. Phys. Soc.
Jpn. 76 (5) (2007) 053703.
[42] D.S. Chow, F. Zamborszky, B. Alavi, D.J. Tantillo, A. Baur, C.A. Merlic, S.E.
Brown, Phys. Rev. Lett. 85 (8) (2000) 1698–1701.
 S.E. Brown / Physica C 514 (2015) 279–289
[43] P. Monceau, F.Y. Nad, S. Brazovskii, Phys. Rev. Lett. 86 (18) (2001) 4080–4083.
[44] F. Zamborszky, W. Yu, W. Raas, S.E. Brown, B. Alavi, C.A. Merlic, A. Baur, Phys.
Rev. B 66 (8) (2002) 081103.
[45] H. Seo, H. Fukuyama, J. Phys. Soc. Jpn. 66 (1997) 1249–1252.
[46] J. Riera, D. Poilblanc, Phys. Rev. B 63 (2001) 241102.
[47] P. Auban-Senzier, C.R. Pasquier, D. Jérome, S. Suh, S.E. Brown, C. Mézière, P.
Batail, Phys. Rev. Lett. 102 (2009) 257001.
[48] L. Zorina, S. Simonov, C. Méziére, E. Canadell, S. Suh, S.E. Brown, P. Foury-
Leylekian, P. Fertey, J.P. Pouget, P. Batail, J. Mater. Chem. 19 (2009) 6980–
6994.
[49] Y. Nakazawa, H. Taniguchi, A. Kawamoto, K. Kanoda, Phys. Rev. B 61 (2000)
R16295–R16298.
[50] J. Wosnitza, J. Low Temp. Phys. 146 (2007) 641–667.
[51] K. Oshima, T. Mori, H. Inokuchi, H. Urayama, H. Yamochi, G. Saito, Phys. Rev. B
38 (1988) 938–941.
[52] H. Kino, H. Fukuyama, J. Phys. Soc. Jpn. 64 (8) (1995) 2726–2729.
[53] S. Lefebvre, P. Wzietek, S. Brown, C. Bourbonnais, D. Jérome, C. Mézière, M.
Fourmigué, P. Batail, Phys. Rev. Lett. 85 (25) (2000) 5420–5423.
[54] F. Kagawa, K. Miyagawa, K. Kanoda, Nature 436 (2005) 534–537.
[55] K. Kanoda, Physica C 282–287 (Part 1) (1997) 299–302.
[56] B.J. Powell, R.H. McKenzie, J. Phys.: Condens. Matter 18 (45) (2006) R827.
[57] Y. Kurosaki, Y. Shimizu, K. Miyagawa, K. Kanoda, G. Saito, Phys. Rev. Lett. 95
(2005) 177001.
[58] B.J. Powell, R.H. McKenzie, Rep. Prog. Phys. 74 (5) (2011) 056501.
[59] T. Takahashi, Y. Nogami, K. Yakushi, J. Phys. Soc. Jpn. 75 (5) (2006) 051008.
[60] H. Seo, C. Hotta, H. Fukuyama, Chem. Rev. 104 (11) (2004) 5005–5036.
[61] J. Merino, R.H. McKenzie, Phys. Rev. Lett. 87 (2001) 237002.
[62] F. Steglich, J. Aarts, C.D. Bredl, W. Lieke, D. Meschede, W. Franz, H. Schäfer,
Phys. Rev. Lett. 43 (25) (1979) 1892–1896.
[63] R. Brusetti, M. Ribault, D. Jérome, K. Bechgaard, Journal de Physique 43 (Paris)
(1982) 801.
[64] R.L. Greene, E.M. Engler, Phys. Rev. Lett. 45 (19) (1980) 1587–1590.
[65] M.Y. Choi, P.M. Chaikin, S.Z. Huang, P. Haen, E.M. Engler, R.L. Greene, Phys.
Rev. B 25 (10) (1982) 6208–6217.
[66] N. Joo, P. Auban-Senzier, C.R. Pasquier, D. Jérome, K. Bechgaard, Europhys.
Lett. 72 (2005) 645–651.
[67] A.A. Abrikosov, J. Low Temp. Phys. 53 (1983) 359–374.
[68] C. Bourbonnais, D. Jérome, in: The Physics of Organic superconductors and
Conductors, Springer Series in Materials Science, 110, Springer, Heidelberg,
2008. Ch. Interacting Electrons in Quasi-One-Dimensional Organic
Superconductors, pp. 357–412.
[69] V.J. Emery, J. Phys. 44 (NC-3) (1983) 977–982.
[70] M. Takigawa, H. Yasuoka, G. Saito, J. Phys. Soc. Jpn. 56 (1) (1987) 873–876.
[71] L. Hebel, C. Slichter, Phys. Rev. 107 (1957) 901–902.
[72] Y. Hasegawa, H. Fukuyama, J. Phys. Soc. Jpn. 56 (1987) 877–880.
[73] T. Imai, T. Shimizu, H. Yasuoka, Y. Ueda, K. Kosuge, J. Phys. Soc. Jpn. 57 (1988)
2280–2283.
[74] I.J. Lee, M.J. Naughton, G.M. Danner, P.M. Chaikin, Phys. Rev. Lett. 78 (18)
(1997) 3555–3558.
[75] J.I. Oh, M.J. Naughton, Phys. Rev. Lett. 92 (6) (2004) 67001.
[76] A.G. Lebed, K. Yamaji, Phys. Rev. Lett. 80 (12) (1998) 2697–2700.
[77] J. Vicent, S. Hillenius, R. Coleman, Phys. Rev. Lett. 44 (1980) 892–895.
[78] P. Fulde, R.A. Ferrell, Phys. Rev. 135 (3A) (1964) A550–A563.
[79] A.I. Larkin, Y.N. Ovchinnikov, JETP 20 (3) (1965) 762–768.
[80] A.G. Lebed, Phys. Rev. B 59 (2) (1999) R721–R724.
[81] J. Shinagawa, Y. Kurosaki, F. Zhang, C. Parker, S.E. Brown, D. Jérome, J.B.
Christensen, K. Bechgaard, Phys. Rev. Lett. 98 (14) (2007) 147002.
[82] B.J. Powell, J. Phys.: Condens. Matter 20 (34) (2008) 345234.
[83] K. Yang, S.L. Sondhi, Phys. Rev. B 57 (14) (1998) 8566–8570.
[84] S. Yonezawa, Y. Maeno, K. Bechgaard, D. Jérome, Phys. Rev. B 85 (2012)
140502.
[85] S. Belin, K. Behnia, Phys. Rev. Lett. 79 (11) (1997) 2125–2128.
[86] C. Bourbonnais, A. Sedeki, Phys. Rev. B 80 (8) (2009) 085105.
[87] H. Shimahara, J. Phys. Soc. Jpn. 69 (7) (2000) 1966–1969.
[88] N. Belmechri, G. Abramovici, M. Héritier, Europhys. Lett. 82 (4) (2008) 47009.
[89] K. Kajiwara, M. Tsuchiizu, Y. Suzumura, C. Bourbonnais, J. Phys. Soc. Jpn. 78
(10) (2009) 104702.
[90] S. Yonezawa, S. Kusaba, Y. Maeno, P. Auban-Senzier, C. Pasquier, K. Bechgaard,
D. Jérome, Phys. Rev. Lett. 100 (11) (2008) 117002.
[91] Y. Fuseya, C. Bourbonnais, K. Miyake, Europhys. Lett. 100 (5) (2012) 57008.
[92] W. Wu, P.M. Chaikin, W. Kang, J. Shinagawa, W. Yu, S.E. Brown, Phys. Rev.
Lett. 94 (9) (2005) 097004.
[93] A.J. Millis, H. Monien, D. Pines, Phys. Rev. B 42 (1) (1990) 167–178.
[94] T. Moriya, Adv. Phys. 49 (2000) 555–606.
[95] Y. Kitaoka, K. Ishida, G.Q. Zheng, S. Ohsugi, K. Asayama, J. Phys. Chem. Solids
54 (10) (1993) 1385–1392. special Issue Spectroscopies in Novel
Superconductors.
[96] F. Ning, K. Ahilan, T. Imai, A. Sefat, M. McGuire, B. Sales, D. Mandrus, P. Cheng,
B. Shen, H.-H. Wen, Phys. Rev. Lett. 104 (2010) 037001.
289
[97] N. Doiron-Leyraud, P. Auban-Senzier, S. René de Cotret, C. Bourbonnais, D.
Jérome, K. Bechgaard, L. Taillefer, Phys. Rev. B 80 (21) (2009) 214531.
[98] N. Doiron-Leyraud, S. René de Cotret, A. Sedeki, C. Bourbonnais, L. Taillefer, P.
Auban-Senzier, D. Jérome, K. Bechgaard, Europhys. J. B 78 (2010) 23–36.
[99] A. Sedeki, D. Bergeron, C. Bourbonnais, Physica B 405 (11, Supplement 1)
(2010) S89–S91;
A. Sedeki, D. Bergeron, C. Bourbonnais, in: Proceeding of the 8th International
Symposium on Crystalline Organic Metals, Superconductors and
Ferromagnets; Yamada Conference LXIV – ISCOM, 2009.
[100] S.S.P. Parkin, E.M. Engler, R.R. Schumaker, R. Lagier, V.Y. Lee, J.C. Scott, R.L.
Greene, Phys. Rev. Lett. 50 (1983) 270–273.
[101] J.M. Williams, A.M. Kini, H.H. Wang, K.D. Carlson, U. Geiser, L.K. Montgomery,
G.J. Pyrka, D.M. Watkins, J.M. Kommers, S.J. Boryschuk, A.V.S. Crouch, W.K.
Kwok, J.E. Schirber, D.L. Overmyer, D. Jung, M.-H. Whangbo, Inorg. Chem. 29
(18) (1990) 3272–3274.
[102] A.M. Kini, U. Geiser, H.H. Wang, K.D. Carlson, J.M. Williams, W.K. Kwok, K.G.
Vandervoort, J.E. Thompson, D.L.A. Stupka, Inorg. Chem. 29 (14) (1990) 2555–
2557.
[103] H. Urayama, H. Yamochi, G. Saito, K. Nozawa, T. Sugano, M. Kinoshita, S. Sato,
K. Oshima, A. Kawamoto, J. Tanaka, Chem. Lett. 17 (1) (1988) 55–58.
[104] H. Mayaffre, P. Wzietek, D. Jérome, C. Lenoir, P. Batail, Phys. Rev. Lett. 75 (22)
(1995) 4122–4125.
[105] J.A. Wright, E. Green, P. Kuhns, A. Reyes, J. Brooks, J. Schlueter, R. Kato, H.
Yamamoto, M. Kobayashi, S.E. Brown, Phys. Rev. Lett. 107 (2011) 087002.
[106] S.M. De Soto, C.P. Slichter, A.M. Kini, H.H. Wang, U. Geiser, J.M. Williams,
Phys. Rev. B 52 (14) (1995) 10364–10368.
[107] K. Kanoda, K. Miyagawa, A. Kawamoto, Y. Nakazawa, Phys. Rev. B 54 (1)
(1996) 76–79.
[108] L.P. Le, G.M. Luke, B.J. Sternlieb, W.D. Wu, Y.J. Uemura, J.H. Brewer, T.M.
Riseman, C.E. Stronach, G. Saito, H. Yamochi, H.H. Wang, A.M. Kini, K.D.
Carlson, J.M. Williams, Phys. Rev. Lett. 68 (1992) 1923–1926.
[109] D. Achkir, M. Poirier, C. Bourbonnais, G. Quirion, C. Lenoir, P. Batail, D. Jérome,
Phys. Rev. B 47 (1993) 11595–11598.
[110] M. Dressel, O. Klein, G. Grüner, K.D. Carlson, H.H. Wang, J.M. Williams, Phys.
Rev. B 50 (1994) 13603–13615.
[111] O.J. Taylor, A. Carrington, J.A. Schlueter, Phys. Rev. Lett. 99 (2007) 057001,
http://dx.doi.org/10.1103/PhysRevLett. 99.057001.
[112] R. Lortz, Y. Wang, A. Demuer, P.H.M. Böttger, B. Bergk, G. Zwicknagl, Y.
Nakazawa, J. Wosnitza, Phys. Rev. Lett. 99 (2007) 187002.
[113] S. Milbradt, A.A. Bardin, C.J.S. Truncik, W.A. Huttema, A.C. Jacko, P.L. Burn, S.-
C. Lo, B.J. Powell, D.M. Broun, Phys. Rev. B 88 (2013) 064501.
[114] D.A. Wollman, D.J. Van Harlingen, W.C. Lee, D.M. Ginsberg, A.J. Leggett, Phys. Rev.
Lett. 71 (1993) 2134–2137, http://dx.doi.org/10.1103/PhysRevLett.71.2134.
[115] C.C. Tsuei, J.R. Kirtley, C.C. Chi, L.S. Yu-Jahnes, A. Gupta, T. Shaw, J.Z. Sun, M.B.
Ketchen, Phys. Rev. Lett. 73 (4) (1994) 593–596.
[116] A.P. Mackenzie, R.K.W. Haselwimmer, A.W. Tyler, G.G. Lonzarich, Y. Mori, S.
Nishizaki, Y. Maeno, Phys. Rev. Lett. 80 (1998) 161–164.
[117] J.G. Analytis, A. Ardavan, S.J. Blundell, R.L. Owen, E.F. Garman, C. Jeynes, B.J.
Powell, Phys. Rev. Lett. 96 (2006) 177002.
[118] J. Schmalian, Phys. Rev. Lett. 81 (1998) 4232–4235.
[119] G. Sordi, P. Sémon, K. Haule, A.-M.S. Tremblay, Phys. Rev. Lett. 108 (2012)
216401.
[120] L. Malone, O.J. Taylor, J.A. Schlueter, A. Carrington, Phys. Rev. B 82 (2010)
014522.
[121] A. Kawamoto, K. Miyagawa, Y. Nakazawa, K. Kanoda, Phys. Rev. Lett. 74
(1995) 3455–3458.
[122] E. Yusuf, B.J. Powell, R.H. McKenzie, Phys. Rev. B 75 (2007) 214515.
[123] B.J. Powell, E. Yusuf, R.H. McKenzie, Phys. Rev. B 80 (2009) 054505.
[124] H. Weiss, M.V. Kartsovnik, W. Biberacher, E. Steep, E. Balthes, A.G.M. Jansen,
K. Andres, N.D. Kushch, Phys. Rev. B 59 (1999) 12370–12378.
[125] P.A. Mansky, G. Danner, P.M. Chaikin, Phys. Rev. B 52 (10) (1995) 7554–7563.
[126] J.R. Kirtley, K.A. Moler, J.A. Schlueter, J.M. Williams, J. Phys.: Condens. Matter
11 (8) (1999) 2007.
[127] J. Singleton, J.A. Symington, M.-S. Nam, A. Ardavan, M. Kurmoo, P. Day, J.
Phys.: Condens. Matter 12 (40) (2000) L641–L648.
[128] C.C. Agosta, J. Jin, W.A. Coniglio, B.E. Smith, K. Cho, I. Stroe, C. Martin, S.W.
Tozer, T.P. Murphy, E.C. Palm, J.A. Schlueter, M. Kurmoo, Phys. Rev. B 85
(2012) 214514.
[129] B. Bergk, A. Demuer, I. Sheikin, Y. Wang, J. Wosnitza, Y. Nakazawa, R. Lortz,
Phys. Rev. B 83 (2011) 064506.
[130] H. Mayaffre, S. Krämer, M. Horvatić, C. Berthier, K. Miyagawa, K. Kanoda, V.F.
Mitrović, Nat. Phys. 10 (2014) 928–932.
[131] 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, J.S. Brooks, Phys. Rev. Lett. 97 (2006) 157001.
[132] R. Beyer, B. Bergk, S. Yasin, J.A. Schlueter, J. Wosnitza, Phys. Rev. Lett. 109
(2012) 027003.
[133] A. Girlando, M. Masino, J.A. Schlueter, N. Drichko, S. Kaiser, M. Dressel, Phys.
Rev. B 89 (2014) 174503.