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Identification of a positive-Seebeck-coefficient
exohedral fullerene†
Published on 27 June 2016. Downloaded by University of Lancaster on 30/06/2016 [Link].

Cite this: DOI: 10.1039/c6nr02291j

Nasser Almutlaq,‡a,b Qusiy Al-Galiby,‡a,c,d Steven Bailey‡a,c and Colin J. Lambert*‡a,c

If fullerene-based thermoelectricity is to become a viable technology, then fullerenes exhibiting both posi-
tive and negative Seebeck coefficients are needed. C60 is known to have a negative Seebeck coefficient and
therefore in this paper we address the challenge of identifying a positive-Seebeck-coefficient fullerene. We
investigated the thermoelectric properties of single-molecule junctions of the exohedral fullerene C50Cl10
connected to gold electrodes and found that it indeed possesses a positive Seebeck coefficient. Further-
more, in common with C60, the Seebeck coefficient can be increased by placing more than one C50Cl10 in
series. For a single C50Cl10, we find S = +8 µV K−1 and for two C50Cl10’s in series we find S = +30 µV K−1.
Received 18th March 2016, We also find that the C50Cl10 monomer and dimer have power factors of 0.5 × 10−5 W m−1 K−2 and 6.0 ×
Accepted 27th June 2016
10−5 W m−1 K−2 respectively. These results demonstrate that exohedral fullerenes provide a new class of
DOI: 10.1039/c6nr02291j thermoelectric materials with desirable properties, which complement those of all-carbon fullerenes,
[Link]/nanoscale thereby enabling the boosting of the thermovoltage in all-fullerene tandem structures.

Introduction all-fullerene device, it will necessary to boost the thermo-

voltage in a tandem arrangement, by placing materials with
Tuning the thermoelectric properties of single molecules is of Seebeck coefficients of opposite signs in series. Since C60 is
great interest, because they are potential building blocks for found to have a negative Seebeck coefficient, in the present
new materials with enhanced electrical and thermal function- paper we address the challenge of identifying a fullerene with
ality. When a single molecule is connected across a nanogap a positive Seebeck coefficient. Recent experiments on the
between two electrodes, whose temperatures differ by an endohedral fullerene13 Sc3N@C80 demonstrated that the
amount ΔT, the resulting voltage difference ΔV = −SΔT is Seebeck coefficient of this material could be either positive or
determined by the Seebeck coefficient (S) of the junction. This negative, depending on the applied pressure. Although this
molecular-scale Seebeck effect has stimulated a recent out- compound does not meet our challenge, because the sign of
pouring of fundamental research aimed at controlling and the Seebeck coefficient is variable, it does suggest that chemi-
increasing the efficiency of organic thermoelectric materials, cal modification may solve the problem of identifying positive-
using combinations of mechanical, electrostatic, chemical and Seebeck-coefficient fullerenes. Therefore in the present paper
electrochemical gating.1–23 we examine for the first time the possibility of controlling ther-
As an example of such control, recent scanning tunneling moelectricity in exohedral fullerenes. In particular, we study
microscope (STM) experiments10 measured the conductance the exohedral decachlorofullerene C50Cl10, which is chemically
and thermopower of C60 molecules and found that compared stable and was first fabricated in milligram quantities in
with a single C60, the Seebeck coefficient could be almost 2004.24,25 Our aim is to explore the potential for thermoelectri-
doubled by placing C60s in series to form dimers. These experi- city of molecular junctions formed from one or two decachloro-
ments suggest that thin molecular films of fullerenes may be fullerenes attached to gold electrodes and to determine if their
excellent thermoelectric materials. However to build a usable properties can be controlled by mechanical gating.
To compute the thermoelectric properties of such junc-
tions, we note that in the linear-response regime, the electric
a
Department of physics, Lancaster University, Lancaster LA1 4YB, UK. current I and heat current Q̇ passing through a device is
E-mail: [Link]@[Link], qusiyalgaliby@[Link]
b
related to the voltage difference ΔV and temperature difference
Department of Physics, Northern Border University, Saudi Arabia
c ΔT by eqn (1)
Quantum Technology Centre, Lancaster University, Lancaster LA1 4YB, UK
d
Department of physics, College of Education, Al-Qadisiyah University, Diwaniyah, 0 1

 e
58002, IRAQ 2
2 B e L0 L1
ΔV 
† Electronic supplementary information (ESI) available. See DOI: I
¼ @ T C ð1Þ
10.1039/c6nr02291j Q̇ h eL1 1 A ΔT
L2
‡ These authors contributed equally. T

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where T is the reference temperature and

ð1

@f ðE; T Þ
Ln ¼ ðE  EF Þn TðEÞ  dE ð2Þ
1 @E

In this expression e = −|e| is the electronic charge, T (E) is

the transmission coefficient for electrons of energy E, passing
through the molecule from one electrode to the other and
f (E,T ) is Fermi distribution defined as f (E,T ) = [e(E−EF)/kBT + 1]−1
where kB is Boltzmann’s constant.
When ΔT = 0, eqn (1) yields for the electrical conductance


Published on 27 June 2016. Downloaded by University of Lancaster on 30/06/2016 [Link].

I Fig. 1 Optimized geometries for exohedral-fullerene (C50Cl10)24,25 left

G¼ , and fullerene (C60) right.
ΔV ΔT¼0

2e2
G¼ L0 ð3Þ
h perties, when placed between two gold electrodes, we used the
Similarly when I = 0 eqn (1) yields for the Seebeck coeffi- density functional theory (DFT) code SIESTA26 which employs

 Troullier–Martins pseudopotentials27 to represent the poten-
ΔV
cient S ¼  , tials of the atomic cores, and a local atomic-orbital basis set. A
ΔT I¼0
double-zeta polarized basis set was used for all atoms and the
1 L1 generalized gradient approximation (GGA-PBE) for the
S¼ ; ð4Þ
jejT L0 exchange and correlation functionals.28,29 The Hamiltonian
and overlap matrices were calculated on a real-space grid
whereas the Peltier coefficient (Π), and the electronic contri-
defined by a plane-wave cut-off of 150 Ry. Each molecule was
bution to the thermal conductance (κe) are given by
relaxed to the optimum geometry until the forces on the atoms
1 L1 were smaller than 0.02 eV Å−1 and in case of the isolated mole-
Π¼ ð5Þ
jej L0 cules, a sufficiently-large unit cell was used.


2 ðL1 Þ2
κe ¼ L2  ð6Þ
hT L0
Results and discussion
From the above expressions, the electronic thermoelectric
figure ZTe = S2GT/κe is given by For the dimers, we varied the distance between two molecules
from 1.2 to 5 Å and computed their binding energy as a func-
ðL1 Þ2 tion of distance. As shown in Fig. 2, for a C60 dimer, the
ZTe ¼ ð7Þ
L0 L2  ðL1 Þ2 optimum separation of the C60s is 3.5 Å and the binding
energy is (∼−0.05 eV), while for the C50Cl10 dimer, the
For E close to EF, if T (E) varies approximately linearly with E
optimum C50Cl10 separation is 3.2 Å and the binding energy is
on the scale of kBT then these formulae take the form1,2
(∼−0.03 eV).

2
2e Next, each relaxed molecule or dimer was placed between
GðTÞ  TðEF Þ; ð8Þ
h two gold (111) electrodes, as shown in Fig. 3a and b. After geo-

 metry relaxation, the distance between each molecule and the
dln TðEÞ
SðTÞ  αjejT ; ð9Þ gold electrode was found to be 2.2 Å and the charge trans-
dE E¼EF ferred between the chlorine atoms and fullerene C50 is shown
κe  αTG ð10Þ in Table S1 of the ESI.† Fig. 3a and b, show optimum configur-

2 2
kB π
where α ¼ ¼ 2:44  108 W Ω K2 is the Lorentz
e 3
number. Eqn (9) demonstrates that S is enhanced by increas-
ing the slope of ln T(E) near E = EF.

Methods
Fig. 1 shows a comparison between, the fullerene C60 (right)
and the exohedral-fullerene C50Cl10 (left), which consists of a Fig. 2 DFT calculation of the binding energy as a function of distance
smaller fullerene C50 surrounding by 10 equatorial chlorines. between (left) two C60 and (right) two C50Cl10. The inset figures show
To undertake a comparative study of their thermoelectric pro- the optimum structure for the dimer.

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Fig. 3 Left panel shows an example of an optimized junction configur-

ation for the systems containing (a) single C60 and (b) a C60 dimer
placed between two gold electrodes. Right panel, (c) shows a DFT cal-
culation of their transmission coefficients T (E) as a function of energy E
relative to the DFT-predicted Fermi energy EDFT
F .

ations of single and dimer C60 junctions, in which the distance

Fig. 5 The left column, (a and c) show the of transmission coefficients
between two C60s is d = 3.5 Å and the distance between the T (E) between the monomers and dimers in Fig. 3 and 4. The right column
C60s and electrodes is r = 2.2 Å. To compute their thermoelec- (b and d) shows their room-temperature electrical conductance (G).
tric properties, we used the quantum transport code Gollum,30
which combines the Hamiltonian provided by the DFT code
SIESTA with a Green’s function scattering formalism. Fig. 3d
shows the transmission coefficient T (E) as a function of energy
E for the junctions in Fig. 3a and b.
For both the monomer and the dimer, in agreement with
ref. 10, electrons near the Fermi energy transmit through the
tail of the LUMO. Furthermore the dimer transmission (red
line) is much smaller than that of the monomer, due to the
increase in length of the molecular bridge, leading to a higher
slope at the Fermi energy and a higher thermopower for the
dimer.
Fig. 4a and b show the corresponding C50Cl10 junctions,
whose optimum dimer separation is d = 3.2 Å and optimum
distance between the C50Cl10s and electrodes is r = 2.2 Å.
Fig. 4c shows the transmission coefficient T (E) of the
monomer (blue) and dimer (red) and as expected the trans-
mission of the dimer is lower than that of the monomer. Fig. 5
shows a comparison between the transmission coefficients
and corresponding room-temperature electrical conductances
Fig. 6 The left column, figures (a and c) show the room-temperature
Seebeck coefficient (thermopower S) and power factor (σS2) over a
range of Fermi energies EF relative to the DFT-predicted Fermi energy
EDFT
F for the monomers in Fig. 3a and 4a. The right column, (b and d)
shows the room-temperature Seebeck coefficient and power factor
(σS2) for the dimers in Fig. 3b and 4b.

of the C50Cl10 and C60 monomers and dimers, while Fig. 6a–d
show the comparison between their room-temperature
Seebeck coefficients (thermopower) S and power factors (σS2).
The optimum separation of d = 3.2 Å for the C50Cl10 dimer
and d = 3.5 Å for the C60 dimer is chosen for illustrative pur-
Fig. 4 Left panel shows an example of an optimized junction configur-
poses. In the STM experiment of ref. 10, in which the conduc-
ation for the systems containing (a) single and (b) dimer fullerene-
C50Cl10 placed between two gold electrodes. Right panel, (c) shows DFT
tance and Seebeck coefficient of a C60 dimer was measured,
calculation of transmission coefficient as a function of energy for the one C60 molecule was located on the gold substrate and the
structures in Fig. 4a and b. other was attached to the STM tip. The distance between them

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was then varied by varying the position of the STM tip and and A = 2.1 nm2 are used, whereas for single (dimer) C50Cl10
many hundreds of curves of conductance and Seebeck coeffi- we assign values L = 1 (1.85) nm and A = 2.1 nm2. From the
cient versus d were obtained. These curves all differ, because results of Fig. 6a and b, the temperature dependence of the
the tip shape, the motion of the tip and the orientations of the power factors P = S2GL/A computed using the DFT-predicted
molecules vary from measurement to measurement. Since Fermi energy are shown in Fig. 7c and d. These results show
these details are not known, this variation cannot be calcu- that C60 monomer and dimer have room-temperature factors
lated. Nevertheless as an indication of how transport pro- of 8.8 × 10−5 W m−1 K−2 and 6.3 × 10−5 W m−1 K−2 respectively,
perties depend on the dimer separation d, Fig. S3† shows whereas the C50Cl10 monomer and dimer have power factors of
transmission curves for various values of d. 0.5 × 10−5 W m−1 K−2 and 6.0 × 10−5 W m−1 K−2 respectively.
It is well-known1 that DFT can give an inaccurate value for
Published on 27 June 2016. Downloaded by University of Lancaster on 30/06/2016 [Link].

the Fermi energy and therefore Fig. 6a–c show results for a
range of Fermi energies EF relative to the DFT-predicted Fermi
energy EDFTF . Fig. 6a demonstrates that both the magnitude Conclusion
and sign of Seebeck coefficient S is changed by replacing the
C60 with C50Cl10. For example at the DFT-predicted Fermi In conclusion, we have demonstrated that the exohedral fuller-
−1
F , the Seebeck coefficient of single C60 is −21 µV K
energy EDFT ene C50Cl10 provides a thermoelectric material with a positive
−1
and for C60 dimer, it increases to −56 µV K . On the other Seebeck coefficient of opposite sign to that of C60. Further-
hand the Seebeck coefficient of the single C50Cl10 is +8 µV K−1 more, in common with C60, the Seebeck coefficient can be
and while for C50Cl10 dimer, it increases to +30 µV K−1. This increased by placing more than one C50Cl10 in series. For a
increase occurs, because moving from the monomer to the single C50Cl10, we find S = +8 µV K−1 and for two C50Cl10’s in
dimer decreases the transmission coefficient at the centre of series we find S = +30 µV K−1. These are comparable with the
the HOMO–LUMO gap and since the value of T (E) near the Seebeck coefficients of pristine C60, which we predict to be S =
LUMO resonance remains close to unity for both the −21 µV K−1 and S = −56 µV K−1 for a C60 monomer and C60
monomer and the dimer, the slope of the transmission coeffi- dimer respectively. Fullerenes smaller than C60 are predicted
cient is larger for the latter. Consequently, the Seebeck coeffi- to have unusual electronic, magnetic, and mechanical pro-
cient is increased. perties that arise mainly from the high curvature of their mole-
For a bulk material, the power factor P is defined by as P = cular surface.31–37 Our paper demonstrates that
S2σ, where σ is the electrical conductivity. The notion of con- thermoelectricity should be added to this list of fascinating
ductivity is not applicable to transport through single mole- properties and that exohedral fullerenes provide a new class of
cules, but to compare with literature values for bulk materials, thermoelectric materials with desirable properties, which
we define σ = GL/A, where L and A are equal to the length and complement those of all-carbon fullerenes.
the cross-sectional area of the molecule respectively. In what The field of molecular thermoelectrics is in its infancy and
follows, for single (dimer) C60 the values L = 1.13 (2.12) nm ongoing studies are needed to highlight how chemical modifi-
cations of molecules can be used to tune the thermopower and
reverse its sign. C50Cl10 is only one of a large number of avail-
able exohedral fullerenes and it remains to be seen what levels
of performance are attainable. For C50Cl10, the change in sign
arises because the Fermi energy is located above the LUMO
resonance, whereas in C60, it is located below the LUMO reson-
ance. The geometrical and electronics structure C50Cl10 is very
different from that of C60 and therefore it is not possible to
consider a smooth change, which connects the electronic
structure of one with the other. For the future it would be of
interest to study exhohedral fullerenes obtained by adding e.g.
metal atoms to the outside of the cage, without changing the
number of carbon atoms. Since the Seebeck coefficient is an
intrinsic property, studies of single molecules inform the
design of thin film materials formed from monolayer of multi-
layers of molecules. The increase in Seebeck coefficient for the
dimer compared with the monomer suggests that performance
can be increased by increasing the number of layers in such
molecular films, at least until the film thickness reaches the
Fig. 7 The left column (a and c) show the Seebeck coefficients S and
inelastic scattering length. The value of this length is not
power factors σS2 as a function of temperature at DFT-predicted Fermi
energy EDFT for the monomers in Fig. 3a and 4a. The right column, (b
known for fullerene films, but at room temperature, it can be
F
and d) show the Seebeck coefficient and power factors for the dimers in as much as 3 nm in monomer, dimer and trimer porphyrin
Fig. 3b and 4b. molecules of in OPEs.38,39

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Acknowledgements 13 L. Rincón-García, A. K. Ismael, C. Evangeli, I. Grace,

G. Rubio-Bollinger, K. Porfyrakis, N. Agraït and
This work was supported by the European Commission (EC) C. J. Lambert, Molecular design and control of fullerene-
FP7 ITN “MOLESCO” ( project no. 606728) and UK EPSRC based bi-thermoelectric materials, Nat. Mater., 2016, 15,
(grant no. EP/M014452/1 and EP/N017188/1), the Higher Edu- 289–293.
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of Education, Northern Border University, Saudi Arabia. power of crown-ether-bridged anthraquinones, Nanoscale,
2015, 7, 17338–17342.
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