doi: 10.

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1. Preparation of picene

A solution of 1,2-di(1-naphthyl)ethane (2.82 g, 10 mmol) and 9-fluorenone

(5.41 g, 30 mmol) in 450 ml of chloroform was purged with nitrogen and irradiated with
a high-pressure mercury arc for 40 h at room temperature. The solution was
concentrated under reduced pressure. The precipitate formed was collected, washed
with chloroform, and then dried under reduced pressure to yield picene (0.46 g, 16%);
the melting point was > 300 °C. The synthetic route is shown in Figure S1a. 1H NMR
spectra (Figure S1b) are identical with spectra reported previously1 and that of the
commercially available sample purchased from Fluka (Figure S1c).

Figure S1 (a) Synthetic route for picene. 1H NMR spectra (500 MHz,
CDCl3) of (b) sample prepared by our synthetic method and (c) material
purchased from Fluka.

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2. Chemical stability of superconducting picene

Superconducting picene is formed by intercalating K atoms in picene crystals.

The colour of the superconducting material is black, as shown in Figure 1 of the main
text. When the superconducting material is exposed to air, its colour changes to gray
and the superconductivity rapidly disappears. Thus the picene superconductor is very
sensitive to air (moisture and O2), which is consistent with the behaviour of alkali-metal
intercalated C60 (AxC60) and metal-intercalated graphite (MxC) superconductors.
Furthermore, it was found from the effect of O2 / H2O on the O2 and H2O-sensing
ability of a picene field-effect transistor that these molecules effectively penetrate into
picene crystals.1-3 The penetration of O2 or H2O into alkali-metal intercalated picene
crystals destroys their superconductivity. Therefore, it is important to remove any O2 or
H2O molecules incorporated in pristine picene crystals before preparation of a
superconducting sample.

3. Comments on the existence of two superconducting phases at x ~ 3 and

small shielding fractions

As described in the main text, the nominal value of K in both superconducting

materials, K2.9picene and K3.3picene, is close to 3. We cannot clearly determine whether
the difference in Tc of these materials represents different crystal phases in K3picene or
different numbers of K atoms intercalated in the picene crystals. Actually, as is seen in
Table 1 in the main text, materials with a nominal value of 3.0 and above show both Tc
of 7 and of 18 K, while below nominal value of 3.0 only the Tc of 7 K is observed. No
conversion was observed between the 7 K phase and the 18 K phase. At the present
stage, we can exclusively conclude that at least two superconducting phases exist at
around the nominal value of 3, because the superconducting phase of either 7 K or 18 K
is formed by 2.6 - 3.3 of K intercalation in picene.

The shielding fraction is quite small in powder samples of picene

superconductors. This may be due to a penetration of magnetic field into
superconducting phase because of smaller size of crystallites (~200 Å from X-ray
diffraction peaks (Figure S7b)) than the London penetration depth λL; the λL is expected
to be > 2000 Å by analogy with AxC60.4 Actually, the shielding fraction of low-Tc
superconducting powder sample of K3.3picene (Tc = 7 K) was as low as about 0.002 %,
and no clear Meissner effect was observed in the powder sample. The values of
shielding and the Meissner fractions were significantly improved to be 15 % and 0.02 %,
respectively, in the pellet samples which was fabricated by pressing the K3.3picene
powder sample; the Tc was 6.9 K (Inset of Figure 2a). Because the electric contact
between the gains in the pellet samples is expected to be much stronger than that in the
powder samples, it is quite reasonable to observe the increase in the shielding fraction.
Here, it should be noted that the Meissner fraction increases as well as the shielding

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fraction in the pellet samples. The Meissner fraction reflects the exact diamagnetic
volume of the superconducting phase, and the enhancement of the Meissner fraction in
the pellet samples suggests that the superconductivity originates from the bulk phase,
and small shielding and Meissner fractions observed in the powder samples may be
attributed to the small grain size in comparison with λL. Namely, we do not require a
possibility of surface phase so as to explain the small shielding fraction because of the
small size of crystallites and large λL.

Finally, we have ruled out the possibility that a decomposition product produces
superconducting behaviour, because the picene molecule is known to be very stable at
high temperature up to 570 K and it shows no chemical reaction with alkali metals
under high vacuum. Actually, the 1H NMR spectrum of CDCl3 solution of
superconducting Rb3.1picene showed only peaks of picene. This shows strongly that
picene molecule is not decomposed in the Rb3.1picene sample, suggesting that the
superconductor is a picene based material.

4. Physics of picene superconductors

Alkali-metal intercalated picene (Axpicene) is a material similar to AxC60 and MxC
in that they are π-conduction network materials, or π-orbital in nature. In considering

Figure S2 Electronic structure of the picene molecule. The calculation was

carried out by density functional theory (DFT) with the basis set B3LYP/6-
31G.

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Figure S3 M/H vs. T curves for (a) K2.9picene (7 K superconductor), (b)

K3.3picene (18 K superconductor) and (c) Rb3.1picene (7 K superconductor)．

the physical properties of Axpicene, the properties of AxC60 are particularly relevant
because both materials are molecular superconductors having π-orbitals associated
closely with their Fermi levels. The pairing symmetry of Kxpicene superconductors is
not yet clear, but normal BCS-type superconductor, i.e., s-wave symmetry, is expected
by analogy with AxC60 superconductors and the fact that exotic behaviour is not still
observed in picene superconductor.4 The electronic structure of a pristine picene
molecule is shown in Figure S2. The LUMO and LUMO+1 are not degenerate, but the
levels are very close to each other, suggesting a high density of states, N(εF), in the
Fermi level as in AxC60.4 If three electrons are transferred from three K atoms to picene
in K3picene, the LUMO+1 level is half occupied. The phonon mode responsible for
electron-phonon coupling is probably the molecular vibration of picene, judging from
the phonon mode in the electron-phonon coupling of C60 superconductors.4

The Tc values for K2.9picene, K3.3picene and Rb3.1picene were estimated from
the onset temperature (Tconset), and the temperature of the inflection point (Tcinf) and the
minimum value (Tcend) of M/H – T plots, as is shown in Figure S3. These values are also
described in the main text. Furthermore, we estimated the Tc values (Tcth) from the
extrapolation of the M/H – T plot along the steepest slope, as shown in Figure S3; the
Tcth values are 7.03 and 18.1 K, respectively, for K2.9picene and K3.3picene. Even if the
Tcth of 18.1 K is the exact Tc without thermal fluctuation, the picene superconductor
remains a very high Tc organic superconductor. The M/H – T curves at each magnetic
field for K2.9picene are shown in Figure S4. This graph can be compared with that for
K3.3picene shown in Figure 2c of the main text.

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Figure S4 Magnetic field dependence of M/H vs. T for K2.9picene. For the
measurement of M, the K2.9picene sample was placed in a quartz tube
(ESR tube) in a glove box (O2 < 0.1 ppm and H2O < 0.1 ppm). M was
measured by SQUID magnetometer (Quantum Design MPMS2) in the
temperature region of > 5 K.

This superconductivity seems to appear with a lowering of two-dimensionality,

or an increase to three-dimensionality, owing to a decrease of interlayer distance (or
contraction of lattice constant c caused by K intercalation). The variation of lattice
constants with K intercalation is described in the main text and in the final section of
Supplementary information. As a consequence, we do not stress two-dimensionality as
nature in superconductivity of K3picene.

The magnetic susceptibilities of normal states of K2.9picene (Tc = 7 K) and

K3.3picene (Tc = 18 K) are approximately 1.5 x 10-5 emu g-1 = 5.8 x 10-3 emu mol-1 at 20
K and 4.2 x 10-5 emu g-1 = 1.6 x 10-2 emu mol-1 at 30 K, respectively. These values are
considerably larger than 9.3 x 10-4 emu mol-1 of K3C60. If all of magnetization originate
from Pauli spin, the density of states, N(εF), is quite large in Kxpicene. However, such a
large N(εF) is not expected for Kxpicene. Since the remanent field is confirmed to be
nearly 5 Oe, the actual magnetic field is at most 25 Oe even if a remanent field exists.
This magnetic field cannot explain the high magnetic susceptibilities. The temperature
dependence of magnetic susceptibilities above Tc shown in Figs. 2a and b suggests a
contribution of localized impurity spins in addition to the Pauli paramagnetism,
although no origin of any impurity spin has been identified. Consequently, the large
magnetic susceptibility above Tc may be due to an additional localized spin other than

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K3picene. Actually, even if the concentration of impurities which provides the

additional localized spins is very small, the magnetic susceptibility should become large
due to the Curie-type behavior. As a consequence, the magnetic susceptibility more by 6
- 18 times than that of K3C60 may be explained by the small amounts of additional
impurities in Kxpicene.
As described in the main text, we estimated the magnetic susceptibility to be 7.5
x 10 emu mol-1 from the conduction electron ESR spectrum for K3.3picene (Tc = 18 K) ,
-5

and this gives the N(εF) of 1.2 states eV-1 picene-1 spin-1. This N(εF) value should be
close to the exact value for K3.3picene, because the conduction electron ESR gives
selectively only the Pauli paramagnetism. Therefore, we cannot recognize the magnetic
susceptibility from SQUID as exact one of conduction electrons and it should be noted
that the magnetic susceptibility from ESR corresponds to the spin of conduction
electrons. On the other hand, the conduction electron ESR in K2.9picene (Tc = 7 K) was
too small to estimate the spin susceptibility, suggesting a smaller N(εF) for K2.9picene
(Tc = 7 K) than for K3.3picene （Tc = 18 K）. This result is reasonable judging from the
lower Tc in K2.9picene.

5. Physics of non-superconducting Kxpicene phases

Kxpicene (x < 2) shows temperature-independent magnetization (M/H) as shown

in Figure S5, while Kxpicene (x > 4) shows Curie-type behavior (Figure S6). These
magnetizations cannot be attributed to the sample container because the container is a
quartz cell (ESR tube), which shows only temperature-independent diamagnetic

Figure S5. M/H vs. T plot of K1.0picene. For the measurement of M, the
K1.0picene sample was placed in a quartz tube in a glove box (O2 < 0.1 ppm
and H2O < 0.1 ppm). M was measured by SQUID magnetometer (Quantum
Design MPMS2) in the temperature region of > 2 K.

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response. The M /H of the ESR tube was –5 x 10-7 emu g-1, and that of the core
magnetization of K3picene can be estimated to be -6.0 x 10-7 emu g-1. These values
imply very small diamagnetic contributions to the observed M /H from the ESR tube
and the core part of K3picene. Therefore, the Pauli- or Curie-like magnetization shown
in Figures S5 and S6 reflects the nature of non-superconducting picene materials.
Finally, we determined the Curie constant to be 5.1 x 10-7 emu g-1 K from M/H vs. T plot
(Figure S6), and the spin concentration was estimated to be ~14% of picene molecules,
although the origin of the spin is unknown. Details of magnetization of A1picene and
A4picene should be further investigated inclusive of normal states of 7 K and 18 K
A3picene superconductors.

Figure S6 M/H vs. T plot of K4.0picene. For the measurement of M, the

K4.0picene sample was placed in a quartz tube in a glove box (O2 < 0.1 ppm
and H2O < 0.1 ppm). M was measured by SQUID magnetometer (Quantum
Design MPMS2) in the temperature region of > 5 K.

6. Structure of Kxpicene.

The X-ray diffraction pattern of pristine picene is shown in Figure S7a. The X-
ray diffraction pattern can be reproduced well with the structure reported previously;5
space group of P21 with lattice constants a = 8.472(2), b = 6.170(2), c = 13.538(7) Å
and β = 90.81(4) º. From the Le Bail fitting for X-ray diffraction pattern (Figure S7b),
the lattice constants of a = 8. 707(7), b = 5.912(4), c = 12.97 (1) Å, and β = 92.77(5) º
were determined for K2.9picene (Tc = 7 K). Actually, the X-ray diffraction pattern of
K2.9picene shows a good correspondence with that of pristine picene (Figures S7a and

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b), and the unit cell parameters estimated by simple index analyses for picene and
K2.9picene show a good consistency with those determined by Rietveld and Le Bail fit,
respectively.

The a is expanded from 8.472 to 8.707 Å by the intercalation of K atoms into

picene crystals, but the b and c contract, suggesting the intercalation of K atoms into the
two-dimensional picene layer, i.e., the ab plane (intralayer) shown in Figure 1. Very
recently, Kosugi et al. showed that the energy of intralayer intercalation was 0.2 eV
lower in energy per molecule than those of interlayer intercalation in K3picene.6 This
theoretical calculation supports our conclusion that K atoms are inserted into the ab
plane.

Here it should be noted that the unit cell volume of pristine picene and
K2.9picene are 715.6 and 667.1 Å3, respectively, showing that the K intercalation
contracts the unit cell. This result strongly suggests a deformation of the herringbone
structure of picene. Actually, the density functional theory (DFT) calculation shows that
the crystal structure of highly K-doped pentacene, K2(pentacene)2, is different from
those of pristine pentacene and lightly doped pentacene, K1(pentacene)2.7 In highly
doped pentacene, the pentacene molecules translate relative to each other to break the
layered structure and distort the herringbone structure. Kosugi’s calculation also
predicted the deformation from Herringbone structure in K2.9picene.6 Furthermore, the
X-ray diffraction pattern of K2.9picene could not also be analyzed by use of the
herringbone structure model but by Le Bail fitting and simple index assignment without
a precise model structure, which supports the departure from the herringbone structure
in highly doped picene, or K2.9picene. Furthermore, the X-ray diffraction pattern of
K0.9picene (not shown) is quite similar to that of pristine picene, which is consistent
with the result that the crystal structure of lightly doped pentacene is similar to that of
pristine pentacene.6

As a consequence, the deformation away from a herringbone structure is

strongly suggested for K2.9picene, as is predicted in the DFT calculation of K-doped
pentacene and picene.6.7 This type of structural deformation is probably the definitive
origin of the slight expansion along the a-axis and the contractions of b and c, because
actually such a deformation predicts a slight intermolecular expansion in the layer and
lattice contractions along the other two axes for K-doped pentacene and picene.6,7 The
structural deformation produces a very large π-π overlap between molecules in highly
K-doped pentacene and picene.6,7 As a consequence, our analyses for the X-ray
diffraction pattern of K2.9picene with Le Bail fit and simple index assignments showed
a-axis expansion and b/c-axis contraction, suggesting the intralayer intercalation of K
atoms in picene crystals. Since details of unit cell reduction is not clear, the further
investigation is now in progress.

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Figure S7 (a) Rietveld refinement of the X-ray diffraction pattern for picene
at 295 K. (b) Le Bail refinement of the X-ray diffraction pattern for Kxpicene
at 295 K; the K2.9picene sample shows a Tc of 7.1 K. The X-ray diffraction
pattern was measured at KEK-PF, Tsukuba with synchrotron radiation of λ
= 0.99937 Å. Black circles and red line are the observed and calculated
diffraction patterns, respectively, and the blue line is the difference
between the observed and calculated patterns. Green vertical bars
correspond to the predicted peak positions.

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References

1. Okamoto, H. et al. Air-assisted high-performance field-effect transistor with

thin films of picene, J. Am. Chem. Soc. 130, 10470-10471 (2008).

2. Kawasaki, N. et al. Trap states and transport characteristics in picene thin

film field-effect transistor, Appl. Phys. Lett. 94, 043310-1 – 043310-3 (2009).

3. Kaji, Y. et al., High-performance C60 and picene thin film field-effect

transistors with conducting polymer electrodes in bottom contact structure,
Organic Electronics. 379, 223 – 229 (2009).

4. Dresselhaus, M. S., Dresselhaus, G. & Eklund, P. C., Science of fullerenes

and carbon nanotubes (Academic Press, 1996).

5. De, A., Ghosh, R., Roychowdhury, S. & Roychowdhury, P. Structural analysis

of picene, C22H14, Acta Cryst. C41, 907-909 (1985).

6. T. Kosugi, T. Miyake, S. Ishibashi, R. Arita, H. Aoki, unpublished data.

7. Hansson, A., Bohlin, J. & Stafstrom, S. Structural and electronic transitions in

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