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Structural characterisation of single crystals and thin films ofa,v-dihexylquaterthiophene
Massimo Moret,*a Marcello Campione,*a Alessandro Borghesi,a Luciano Miozzo,a Adele Sassella,a
Silvia Trabattoni,a Bernard Lotzb and Annette Thierryb
Received 24th March 2005, Accepted 19th May 2005
First published as an Advance Article on the web 31st May 2005
DOI: 10.1039/b504233j
Single crystals and thin films of the p-type organic semiconductor a,v-dihexylquaterthiophene
have been studied using X-ray diffraction and TEM, respectively. The single crystal analysis
reveals the presence of monomolecular layers of quaterthiophene cores with terminally bound
hexyl chains. A herringbone molecular packing akin to that exhibited by the parent
quaterthiophene molecule is observed. Electron diffraction of thin films on silica clearly shows the
crystalline polymorph of the solution-grown crystals and the crystallites deposited by organic
molecular beam deposition are identical. However, thin film crystallites are severely affected by
multiple twinning.
Introduction
In field effect transistors that include active organic layers,
alkyl-substituted oligothiophenes have superior properties
compared to the non-substituted ones: easier processability
of the material, enhanced performance of the devices.1–3
Previous studies have demonstrated promising performance of
electronic devices based on these materials. The structure and
morphology of thin films, kinetically grown from the vapour
phase, have been reported.1,4 In organics, the conduction
mechanism involves charge transport across p–p stacked
molecules. A high charge mobility thus requires high conjuga-
tion along the main molecular axis and favourable molecular
stacking.5 The typical herringbone organisation, present for
example in all crystalline structures of non-substituted
oligothiophenes, minimizes the repulsion between p orbitals
and favours p–p interactions between neighbour molecules. In
this respect, dialkyl-substituted oligothiophenes are among the
most promising p-type organic materials. They are able to self-
assemble in close packed crystalline structures and are soluble
in common organic solvents.
Since for solid organic semiconductors the carrier mobility
depends critically on the molecular order and on the p–p
interactions, a thorough understanding of the structural
properties in the condensed phase of a,v-dialkyl terminated
oligothiophenes is mandatory.2a,3,6 Particular attention has
been devoted to a,v-dihexylquaterthiophene (a,v-DH4T) for
which many experimental findings indicate considerable order
in the crystalline phase.1,3,7 Recently, Katz et al.1 established
the conditions for growing highly crystalline thin films of
a,v-DH4T. Electron diffraction of films deposited at 100 uCon carbon grids displays a single crystal-like pattern. Detailed
knowledge of the molecular organisation in the crystal is
necessary for the fundamental interpretation of the physical
properties in the solid state of semiconducting organic
materials.5 However, the crystalline structure, and hence the
molecular conformation and packing in the solid state, have
not yet been determined for a,v-DH4T. This motivated us to
study the growth of a,v-DH4T single crystals from solution
in order to determine the molecular and crystal structure,
opening the possibility to better understand the structural
features of thin films.
Results and discussion
The existence of a liquid crystal mesophase above 84 uChinders the growth of large single crystals of a,v-DH4T from
the vapour phase.3,8 Platelet crystals several millimetres
long and hundreds of micrometres thick were obtained from
anisole solutions. The present combined single crystal X-ray
diffraction study of a,v-DH4T and transmission electron
microscopy (TEM) characterisation of its thin films on silica
provide fundamental information on structural features and
self-assembling properties of these systems for bulk crystals
and for thin films. It demonstrates also that the crystalline
polymorph of the solution-grown crystals and the crystallites
deposited by organic molecular beam deposition (OMBD)
(under the experimental conditions of the present work) are
identical.
Crystal and molecular structures
The a,v-DH4T molecule crystallizes in the monoclinic space
group P21/a with one half molecule in the asymmetric unit;
pairing through an inversion centre (Wyckoff position a)
between atoms C(1) and C(1a) with another independent half
molecule completes the molecule (Fig. 1), giving rise to two
molecules per unit cell.
With the present unit cell choice, the molecular packing is
consistent with that of the low temperature polymorph of
quaterthiophene (4T/LT),9 i.e. a herringbone (HB) packing of
a,v-DH4T molecules in the ab plane. HB layers are stacked
along the [001] direction to generate the 3D motif of the crystal
structure (Fig. 2). As previously reported1,8 the c axis length is*[email protected] (Massimo Moret)[email protected] (Marcello Campione)
PAPER www.rsc.org/materials | Journal of Materials Chemistry
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compatible with a 4T central unit plus two terminal fully
extended hexyl chains, with the long molecular axis slightly
tilted with respect to the (001) plane. Characterisation of the
crystalline samples of a,v-DH4T has been previously per-
formed on thin films by using selected-area TEM electron
diffraction and X-ray diffraction.1,4,8 The unit cell lengths
found by Katz et al.1,8 are in good agreement with those
reported in the present paper. We are therefore dealing with
the same crystal polymorph. In contrast, partial crystal data
published by Garnier et al.4 based on X-ray powder diffraction
are not consistent with our cell parameters, crystal symmetry
and crystal density.
The molecular structure of a,v-DH4T is closely related to
that of the unsubstituted nT oligomers (n 5 2–8)2c,10 and
a,v-dimethylquaterthiophene (a,v-DM4T),11a previously
characterized by X-ray diffraction. It differs significantly from
that of c-dihexylquaterthiophene11b due to the position of the
alkyl groups. Intramolecular features for the a,v-DH4T
molecule remind those of the unsubstituted oligomers. The
thienyl rings display the usual flat all-anti conformation with a
dihedral angle between a central thienyl ring and an outer one
of 2.3(5)u, compatible with a high degree of p conjugation.
Structural features of interest are due to the co-presence in the
molecule of a rigid quaterthiophene core and two flexible
terminal hexyl chains in a and v positions. As discussed later,
the conformation adopted by the alkyl chains relative to the
thiophene moiety is highly relevant in determining the
molecular packing. In crystals of a,v-DH4T, monomolecular
layers parallel to the (001) plane (Fig. 2) correspond to the
largest macroscopic face exhibited by the crystals (i.e. the faces
with the slowest growth rate). Each (001) layer contains a HB
packing of molecules typical of most planar molecules12 and
in particular of oligothiophenes.2c A helpful geometrical
descriptor of the HB pattern is the angle between the least-
squares plane of the quaterthiophene moiety of two adjacent
molecules. The value found for a,v-DH4T is 62.8(1)u, very
close to the values of 63.1u and 62.1u determined for 4T/LT9
and a,v-DM4T,11a respectively. This result indicates only
minor perturbations of the 4T core HB packing caused by the
presence of the alkyl substituents in a/v positions. The analogy
between a,v-DH4T and 4T/LT crystals is further evidenced by
the tilt angle of the rigid core (i.e. the axis passing through the
a,v carbon atoms of the 4T core) with respect to the normal of
the (001) plane. The tilt angle is 24.2u and 24.8u for a,v-DH4T
and 4T/LT, respectively. The situation is very different
for a,v-DM4T, which is the archetypal structure for the
a,v-dialkyloligothiophenes, with methyl end groups.11a The
molecules are tilted in opposite directions in successive layers
(at + and 223.3u to the layer normal), thus generating a double
layer sequence in which the molecules are arranged in a
herringbone manner, too. The marked difference between
a,v-DM4T and a,v-DH4T highlights the impact of the alkyl
side chains on the crystal packing. Chain length, odd/even
number of carbon atoms (and also presence of impurities) that
are known to affect the growth of n-alkanes13 appear to play a
similar role in the growth of a,v-dialkyloligothiophenes.
The hexyl chains attached in the a position to the two outer
thienyl rings of a,v-DH4T exhibit an all-trans conformation,
that is, a flat zigzag of carbon atoms (rms deviation from least-
squares plane of fitted atoms C(9)–C(14) 5 0.0221 A). The
plane of the C6 chains makes an angle of y6u with the
pertinent thienyl ring, hence the alkyl groups are well aligned
with the 4T core. The chain conformation is well determined
and shows no trace of disorder even if the mobility of the alkyl
chains at room temperature is high. As expected, anisotropic
displacement parameters of the chain carbon atoms increase
when moving from C(9), closest to the molecule centre of
mass, to the terminal atom C(14) (Fig. 1), with a significant
component normal to the plane of the zigzag.
As already mentioned, the HB pattern is a ‘‘strong’’ packing
motif. It is present in several rod-like organic p-conjugate
molecules,12 in the low temperature polymorphs of 4T9 and
6T14 and is preserved with little change also in the high
temperature polymorphs of 4T15 and 6T.16 In the present case,
the oligothiophene core dictates the basic packing require-
ments that take precedence over the hexyl chain ones, but the
4T-like herringbone is compatible with an efficient packing of
the hexyl chains, too. This is achieved through a conformation
of the alkyl chains in which the ipso methylene group C(9) is
staggered relative to the sulfur S(2) and not to the b aromatic
carbon C(7). The latter conformation has been suggested in
previous attempts to infer the molecular conformation and
solid state or mesophase packing of alkyl-substituted oligo-
thiophenes.3,8,17 Moreover, the S(2)–C(8)–C(9) bond angle
(122.0(13)u) is not significantly different from the 120.5(6)uangle of a,v-DM4T. It is however significantly smaller than
that predicted by molecular mechanics modelling3 with the
‘‘correct’’ S-staggering. A brief survey of the a,v-DH4T
geometry with molecular mechanics18 did not reveal any
significant anomaly or strain for this intramolecular bond
parameter.
At this stage, it may be worth comparing structures
predicted by molecular modelling and experimentally observed
crystal structures. The apparently minor variations in the
chain conformation just mentioned cause indeed dramatic
variations of the molecular ‘‘shape’’ and length, and hence of
Fig. 1 ORTEP drawing (ellipsoids at 30% probability level) and labelling scheme for the centrosymmetric a,v-DH4T molecule. Hydrogen atoms
were given arbitrary radii. The all-anti and all-trans conformations for the quaterthiophene and hexyl moieties, respectively, are shown. Bond
distances: S(1)–C(1) 1.753(8), S(1)–C(4) 1.729(12), S(2)–C(5) 1.755(11), S(2)–C(8) 1.694(15), C(1)–C(1a) 1.47(2), C(1)–C(2) 1.335(13), C(2)–C(3)
1.428(15), C(3)–C(4) 1.383(15), C(4)–C(5) 1.422(14), C(5)–C(6) 1.383(14), C(6)–C(7) 1.401(15), C(7)–C(8) 1.378(18), C(8)–C(9) 1.503(19), C(9)–
C(10) 1.39(2), C(10)–C(11) 1.50(2), C(11)–C(12) 1.45(2), C(12)–C(13) 1.54(2), C(13)–C(14) 1.39(3).
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the magnitude of the molecular tilt within the layers. The
experimental molecular conformation is significantly more
straight than the predicted ones. The latter display a kinked
shape arising from the staggering of the C6 chain relatively to
the C(b)–H moiety17 and/or the wider S–C(a)–C(chain) angle.3
The linear shape taken by the a,v-DH4T molecule makes it
very similar to an n-alkane, as previously anticipated. Given
the proper overall molecular conformation an even nT central
unit (n 5 4 in this case) terminated by two a,v (even
numbered) alkyl chains is nearly equivalent to an even
n-alkane in terms of symmetry and molecular packing. As
for the lateral packing of the alkyl chains, a good arrangement
of the chains can usually be achieved only if a hydrogen atom
of one molecule fits into a hollow formed by H atoms of an
adjacent molecule. For chains a,v-connected to 4T cores and
HB packed, a shift along the chain axis is needed to fulfil this
condition. As shown in Fig. 2, neighbour chains are shifted
along their major axis in order to match nearby convex parts
with neighbour hollows. In the present case, the shortest
distances between H atoms belonging to different chains
(y2.6 A) is within accepted van der Waals distances19 and is
analogous to those found in e.g. n-C20H42.20
Normal-paraffin crystals adopt a stacking of molecular
layers with parallel chains. In the so-called oblique structure
(triclinic and monoclinic system) the chains are nearly parallel
to the c axis and tilted with respect to the molecular layers.
Therefore, in the presence of the HB pattern determined by the
oligothiophene core and the concomitant steric requirements
of the paraffinic moieties, packing efficiency for a,v-DH4T
results in a crystal having a density which is exactly that arising
from the average of n-hexane21 and 4T/LT9 (weighted on the
basis of type and number of involved atoms). This is an
indirect but simple proof that the packing of the hexyl ends in
a layer is similar to that of the crystalline free paraffins (note
however that the melting temperature of n-hexane is 294.3 uC,
whereas when attached to the 4T moieties the hexyl substituent
is ‘‘crystalline at room temperature’’).
The monomolecular layers just described cannot stack
exactly one above the other because protruding terminal
CH3 groups of one layer would impinge in protruding CH3
groups of the adjacent layers instead of fitting into hollows.
This potential steric conflict is relieved by a lateral displace-
ment of successive lamellae and a slight misalignment of c*
(perpendicular to the (001) plane) relative to the c axis. The
resulting distance between the plane defined by methyl C
atoms of molecules belonging to adjacent layers is 2.82 A,
larger than the value of 2.58 A found in the short chain
n-hexane21 at low temperature but well within the range of
2.70–2.85 A observed in the longer alkanes n-C18H38,22
n-C20H42,20 and n-C24H5023 (all crystalline at room tempera-
ture). The subtle role exerted by the terminal chains is
exemplified by the different bilayered crystal packing adopted
by a,v-DM4T. Similar bilayered packings are observed in
polymorphs and polytypes of n-alkanes, the ‘‘best’’ packing of
layers depending on many subtle parameters (structural,
chemical, thermodynamical, and kinetic factors).13
Thin film structural characterisation
Organic thin films are essential in the design of devices. The
aforementioned structural characterisation of bulk a,v-DH4T
single crystals is a crucial prerequisite in the analysis of
molecular arrangements observed in thin films of a,v-DH4T
Fig. 2 View down the b axis of the a,v-DH4T crystal structure
highlighting the monomolecular layered structure parallel to (001).
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deposited in ultra-high vacuum (UHV) on inert substrates to
be described now. These thin films grown on silica exhibit an
island-like morphology in the full range of nominal thicknesses
so far observed, with some fluctuations in thickness.
Fig. 3 shows an AFM image of the surface of a 10 nm thick
film of a,v-DH4T deposited under UHV at room temperature
on silica. From the image contrast and the cross-sectional
profile reported in Fig. 3, different layers can be distinguished.
The zero level in the cross-sectional profile represents the bare
substrate surface, and shows up with the darkest contrast in
the AFM image. The same profile reveals terraces about
11.6 nm high, a value that is close to the average film thickness
(10 nm), 14.6 nm and 17.5 nm. The height difference between
different terraces is within experimental error equal to one or
multiples of the c 6 sin b value of the single crystal structure.
A preliminary study carried out by electron microscopy for
a,v-DH4T thin films was reported in reference 24. A more
thorough investigation of these thin films reveals two
characteristic selected area electron diffraction patterns, as
shown in Fig. 4a and c. The sharpness and organisation of the
diffraction spots indicates that we are dealing with well-
ordered crystalline domains.
A simulated pattern with the zone axis [201] parallel to the
electron beam is shown in Fig. 4b. The calculated positions of
the diffraction spots are in excellent agreement with the
experiment (Fig. 4a). It is worth noting that some weak
diffraction spots appear in the experimental patterns whereas
they are absent in the simulated ones. This is frequently
observed in electron diffraction, and is usually associated with
multiple scattering, which is more likely for thicker specimens.
The contact plane associated with a [201] zone axis is (1 0 12).
The (1 0 12) plane is not a natural cleavage or growth plane for
a,v-DH4T single crystals, since it intersects the molecules. This
analysis therefore indicates that we are not dealing with a
single crystalline domain, but rather with some more complex
crystal. The analysis becomes straightforward when noting
that the (1 0 12) plane is normal to the long axis of the DH4T
molecule. This suggests that the crystals are actually multiple
twins with a (24 0 11) twin plane. This plane is indeed a
‘‘natural’’ twin plane. In addition, it contains the b axis. As a
result of the twinning, two c axis orientations relative to the
substrate are generated at + and 223.3u. Note that this
twinning does not therefore affect the diffraction pattern as
seen along the [201] zone axis. As a result of twinning, the rigid
core of the a,v-DH4T molecules stands up normal to the
substrate. In the composite twin, the (001) ‘‘natural’’ cleavage
plane is tilted by 21u from the substrate plane alternately
clockwise and anticlockwise. A side view along b of the
orientation of the molecules for this corrugated contact plane
is represented in Fig. 5. The micro-twinning with a twinning
plane parallel to the long axis of the rigid core of the molecules
gives rise to an apparent macroscopic contact plane different
from a natural cleavage plane. A similar example has been
reported previously.25 In that case another highly conjugate
rigid molecule, sexiphenyl, was deposited on GaAs at high
temperature (150 uC).
Fig. 4c reports another type of diffraction pattern occasion-
ally obtained on the same sample. In this case, we are dealing
with a ‘‘real’’ (untwinned) single crystal. The zone axis is now
[105]. The corresponding simulated diffraction with the zone
Fig. 3 10 6 10 mm2 AFM image of the surface of a 10 nm thick film
of a,v-DH4T deposited on silica at room temperature, and cross-
sectional profile along the white line.
Fig. 4 (a and c) Experimental electron diffraction patterns for two
different islands of a a,v-DH4T thin film deposited on silica. (b and d)
Calculated electron diffraction patterns with zone axes [201] and [105]
parallel to the electron beam, respectively. The calculation is based on
our crystalline structure for a,v-DH4T grown from solution.
Fig. 5 Structure of the twinned domains of a,v-DH4T grown on
silica as viewed along the b axis of the unit cell.
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axis [105] parallel to the electron beam is reported in Fig. 4d.
The contact plane corresponding to the zone [105] is the
‘‘natural’’ and expected (001) plane. The molecular axis is at an
angle of 23.3u to the substrate normal. A side view along b of
the orientation of the molecules relative to the substrate is
represented in Fig. 2. As a consequence also the steps in these
single crystalline domains should be 28.5 A high. Contrary to
the previously described case the surface of the contact plane is
molecularly flat and smooth.
In the light of the above results, the UHV deposition of
a,v-DH4T on inert substrates gives rise to crystalline domains
with the same crystalline structure as determined for solution
grown single crystals. The a,v-DH4T thin films are composed
of island-like domains. These islands correspond to two
orientations of the molecules relative to the substrate surface.
In one type of domain a multiple twinning parallel to (24 0 11)
generates a corrugated contact plane. The molecules are
standing up normal to the substrate surface. Another type of
domain is made of single crystals with a (001) contact plane
and the molecules tilted by 23.3u to the substrate surface. The
growth of the different domains is probably kinetically
controlled and depends on the substrate temperature and the
rate of evaporation. Further experiments are needed to
understand the origin of this behaviour.
Conclusion
We have determined the crystal structure of a,v-DH4T and
the morphology and structure of thin films vapour-deposited
on silica. The main feature of the crystal structure is the
herringbone packing of the molecules, which is similar to that
of other archetypal oligothiophenes. It gives rise to a mono-
molecular layered structure, i.e. to a 2D system in which
carrier mobility is characterized by negligible interchain
transfer integrals between molecules lying in adjacent layers.5
The present results are useful to correctly interpret experi-
mental data such as partial structural data obtained from
diffraction and optical spectroscopy which strongly depends
on the transition dipole orientation.26 Hence, some previous
attempts to figure out molecular conformation and orientation
for alkyloligothiophenes in crystals and mesophases have to be
re-examined in the light of the above results.2a,8,17 Considering
the structural similarities between alkyloligothiophenes and
n-alkanes,27 further work will be devoted to crystal growth
mechanisms in relation with polymorphism and twinning. As a
matter of fact, potential applications in opto-electronics of
efficient thin films require a strict control of the molecular
organisation throughout the film thickness. It is known from
the literature that devices exhibit better performances when
a,v-DH4T is used as active layer instead of 4T. Since these two
materials display the same packing of the conjugate cores, the
enhanced carrier mobility of thin film devices of a,v-DH4T is
principally attributable to a different mechanism of growth,
leading to the formation of uniform and well-connected
crystalline domains. Therefore, mastering the growth of films
based on promising active polymorphs with uniform orienta-
tion and entirely uniform thickness at the molecular level is
mandatory to reach valuable macroscopic characteristics for
organic films.
Experimental
a,v-DH4T crystals were grown from an anisole solution at
room temperature with a novel technique (described in a
forthcoming paper28) that did succeed in producing single
crystals suitable for a complete X-ray diffraction study. A
Bruker SMART CCD area-detector diffractometer was used
to collect data using Mo-Ka radiation (l 5 0.71073 A) with
the v-scan method, within the limits h ¡ 24u. Data were
corrected for Lorentz, polarisation and absorption effects
using the SADABS program. The structure was solved by
direct methods (SIR9729) and refined by full-matrix least-
squares on Fo2 (SHELX-9730). Anisotropic displacement para-
meters were assigned to all non-hydrogen atoms. Hydrogen
atoms were located by difference Fourier maps and sub-
sequently introduced in the refinement as isotropic scatterers
in idealized positions. No solvent accessible voids were
revealed by PLATON.31 ORTEP and packing figures were
generated with PLATON and SCHAKAL,32 respectively. A
summary of crystallographic data and refinement parameters
are listed in Table 1.
a,v-DH4T thin films were grown by means of OMBD,
starting from a,v-DH4T microcrystalline powder33 in a
Knudsen effusion cell at 190 uC, keeping the substrate
temperature at 25 uC. The pressure in the growth chamber
was kept below 8 6 1028 Pa. The film nominal thickness was
monitored by means of a quartz oscillator and was set to
10 nm. The substrate adopted was silica 1 mm thick and
1 6 1 cm2 in size, with a surface roughness of about 0.4 nm, as
measured by AFM over a 10 6 10 mm2 area. Before the
introduction in the growth chamber the substrates were
cleaned using various solvents and blown with dry nitrogen.
AFM images were obtained with a Nanoscope IIIa (Digital
Instruments) in Tapping2 mode using silicon cantilevers. For
electron microscopy observation the a,v-DH4T films were
backed with a thin carbon film. The a,v-DH4T/carbon system
Table 1 Summary of crystal data and refinement parameters fora,v-DH4T
Formula C28H34S4
Formula weight/g mol21 656.16Crystal system monoclinicSpace group P21/a (No. 14)a/A 6.049(5)b/A 7.814(7)c/A 28.532(25)b/u 92.39(2)V/A3 1347(2)Z 2T/K 298Dc/g cm23 1.229m/mm21 0.367Crystal size/mm3 0.25 6 0.22 6 0.18Minimum relative transmission 0.64h Range/u 2.7–24.1Crystal decay (%) 0Index ranges, h k l 26/6 28/8 232/32Reflections collected 7882Unique reflections, R(int) 2089, 0.156Data/parameters 2089/145Goodness-of-fit on Fo
2 0.905R1, wR2 [Fo . 4s(Fo)] 0.1230, 0.3082R1, wR2 [all data] 0.2013, 0.3740Max. diff. peak/hole/e A23 0.709/20.604
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was floated on a dilute HF solution and transferred on copper
grids. A Philips CM12 electron microscope working at a
voltage of 120 kV was used. Diffraction patterns were obtained
at a spot size of 50 nm, using a condenser aperture of 50 mm
and a selected-area aperture of 30 mm. Indexation of the
experimental diffraction patterns was carried out using the
program Cerius2 (Accelrys) on the basis of the crystal
structure here reported.
Acknowledgements
The authors kindly acknowledge Dr. F. Garnier and
Prof. A. Papagni for providing the a,v-DH4T molecules.
M. C. acknowledges the EEC contract Eurofet Nu RTN2-
2001-00382 for partial financial support, and Prof. P. Fantucci
for the availability of the program Cerius21. M. M. thanks
Dipartimento di Chimica Strutturale e Stereochimica
Inorganica (Universita degli Studi di Milano) for availability
of the X-ray diffractometer.
Massimo Moret,*a Marcello Campione,*a Alessandro Borghesi,a
Luciano Miozzo,a Adele Sassella,a Silvia Trabattoni,a Bernard Lotzb andAnnette Thierryb
aDepartment of Materials Science, Universita degli Studi di MilanoBicocca, Via R. Cozzi 53, I-20125 Milano, Italy.E-mail: [email protected];[email protected] Charles Sadron – CNRS, 6 rue Boussingault, F-67083,Strasbourg Cedex, France
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