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Control of electron transport through Fano resonances in molecular wires

T. A. Papadopoulos, I. M. Grace and C. J. Lambert1

Department of Physics, Lancaster University, Lancaster, United Kingdom
Using a first principles approach, we study the electron transport properties of two molecules of
length 2.5nm which are the building blocks for a new class of molecular wires containing fluorenone
arXiv:cond-mat/0609109v1 [cond-mat.mtrl-sci] 6 Sep 2006

units. We show that the presence of side groups attached to these units leads to Fano resonances close
to the Fermi energy. As a consequence electron transport through the molecule can be controlled
either by chemically modifying the side group, or by changing the conformation of the side group.
This sensitivity, which is not present in Breit–Wigner resonances, opens up new possibilities for
novel single-molecule sensors.

The ability to position single molecules in electrical nances, have been discussed in several contexts recently.
junctions [1, 2, 3, 4, 5, 6] and demonstrations that molec- Ref [18] deals with Fano resonances in 1-d waveguides,
ular and nanoscale structures are capable of basic elec- applied to GaAS heterojunctions. Ref. [19] analyses a
tronic functions such as current rectification, negative generic model of a double quantum dot. Refs. [20, 21]
differential resistance and single electron transistor be- address inelastic scattering, which can be an issue at fi-
haviour [7, 8, 9, 10, 11, 12] suggest that single-molecule nite bias, but is not the focus of attention in our paper.
electronics may play a key role in the design of future na- Ref. [22] is concerned with low temperature transport be-
noelectronic circuits. However, the goal of developing a low the Kondo temperature. ’Conductance cancellation’
reliable molecular-electronics technology is still over the in 1-d tight-binding chains has also been noted [23] and
horizon and many key problems, such as device stability, a Hückel model of resonant transport recently considered
reproducibility and the control of single-molecule trans- [24].
port need to be solved. In addition, since contacting None of the above papers contain ab initio, material-
molecules via break junction and SPMs is not a scal- specific calculations, which treat the metallic electrodes
able technology, the question of wiring large numbers of in a realistic manner. Recently, this limitation has been
molecules on a single chip still needs to be addressed. removed by state-of-the-art calculations on di-thiol ben-
One approach to developing a scalable technology in- zene [25], which contain many examples of Fano reso-
volves placing molecules between arrays of pre-formed, nances. Depending on specific conditions, these can take
lithographically-grown contacts. Such an approach re- on a wide variety of shapes, ranging from Breit-Wigner
quires the length of the molecules to match the spacing type line shapes to strongly asymmetric profiles. How-
between the contacts and since in practice, the spacing ever the Fano resonances are neither controlled nor engi-
between such contacts can only be reliably controlled on neered into the molecule. They arise from a complicated
the scale of 1–10nm, it is desirable to synthesize families interaction between the molecule and contacts and can-
of molecular wires with this range of lengths. not be identified with a particular section of the molecule.
Recently [13, 14, 15] a family of rigid molecules has The aim of this Letter is to demonstrate that there are
been synthesized with lengths up to 10nm. These are advantages in engineering molecules to possess Fano res-
π–conjugated oligomers based on rigid-rod-like aryle- onances associated with specific parts of the molecule,
neethynylene backbones, containing fluorenone units. which can be modified externally to achieve control
The presence of terminal thiol groups allow assembly over transport. Through an ab initio simulation of the
onto gold surfaces and therefore make them ideal for use molecules in Fig. 1, we demonstrate that Fano resonances
in single-molecule device fabrication. In this Letter we near the Fermi energy can be controlled by altering the
investigate the properties of the smallest of these molec- properties of the attached side group. This is in marked
ular wires, of length 2.5nm, since these form the build- contrast with the behaviour of Breit-Wigner resonances,
ing blocks of the longer wires. The central part consists which are relatively insensitive to the state of the side
of a single fluorenone unit, which could be chemically group. These results suggest that the control of Fano res-
modified, e.g. by replacing the oxygen with pyridine or onances opens intriguing possibilities for single-molecule
bipyridine rings, as shown in Fig. 1. sensing.
In many molecular devices, electron transport is dom- To compute electron transport properties, we use a
inated by conduction through broadened HOMO or combination of the DFT code SIESTA [26] and a Green’s
LUMO states, leading to Breit–Wigner resonances [16]. function scattering approach, as encapsulated in the
In contrast, for this family of molecules, we find that molecular electronics code SMEAGOL [27]. Initially the
transport is dominated by Fano resonances [17] associ- isolated molecule is relaxed to find the optimum geome-
ated with the presence of side groups, such as the oxygen try and the molecule is then extended to include surface
atom or bi-pyridine. Generic properties of Fano reso- layers of the gold leads, so that charge transfer at the




FIG. 1: The ground state geometry of the 2.5nm molecules 10
extended to self-consitently include 8 layers of gold on the
(111) surface, each containing 9 Au atoms. Colour codes: -2 -1 0 1 2
C(grey), H(white), N(dark grey) and O(black). a) The top E (eV)
molecule contains a single oxygen atom attached to the central
fluorenone unit and b) the oxygen has been replaced by a bi-
pyridine unit. FIG. 2: Black line: Electron transmission coefficient versus
energy for the molecule having attached an oxygen atom as
a side group. Dashed line: Oxygen bonds removed from the
gold-molecule interface is included self-consistently. The
number Ng of incorporated gold layers is increased until
computed transport properties no longer change with in-
creasing Ng . We find that this occurs for Ng = 8 layers of controlling single-molecule transport. To explore this
gold, each consisting of 9 atoms on the (111) plain. Us- possibility in greater detail and to demonstrate that Fano
ing a double–ζ basis plus polarization orbitals, Troullier– resonances are a generic feature of molecular wires with
Martins pseudopotentials [28] and the Ceperley–Alder attached side groups, we examine the molecule shown in
LDA method to describe the exchange correlation [29], Fig. 1b, in which the oxygen has been replaced by a bi-
an effective tight-binding Hamiltonian of the extended pyridine unit. Recent STM experiments on related wires
molecule is obtained, from which a scattering matrix have shown that it is possible to change the rotational
and electron transmission coefficient T (E) are computed. conformation of attached side groups [31] and therefore
The zero-bias electrical conductance is then given by the we examine transport properties as a function of the an-
Landauer formula G = (2e2 /h)T (EF ), where EF is the gle of rotation θ of the bi-pyridine side group. (We define
Fermi energy [30]. the angle θ = 90◦ when the two rings lie parallel to the
For the molecule shown in Fig. 1a, which has an oxy- molecule axis and θ = 0◦ when they lie perpendicular to
gen atom attached to the fluorenone unit, the transmis- it.) The computed transmission through this molecule
sion coefficient T(E) is shown in Fig. 2 (black line). For is shown in Fig. 3 for five values of θ. This demon-
E ≈ 1.2eV , this exhibits a typical Breit–Wigner res- strates that Fano resonances persist when one side group
onance. As expected, since the molecule and contacts (namely the oxygen atom) is replaced by another and
are symmetric, the maximum value of this peak is unity. furthermore, the position of the Fano resonance is sensi-
However in the vicinity of the Fermi energy (EF = 0) tive to the conformation of the side group. In contrast,
transport is dominated by the presence of an asymmetric the Breit–Wigner peak at 1.25eV is almost unaffected by
Fano resonance [17], comprising a resonant peak followed such changes.
by an anti-resonance. To demonstrate that the Fano resonance is associated
We now demonstrate that anti-resonances arise from with localized states on the side group, we examine the
quasi-bound states associated with the side groups of the energy spectrum of the isolated molecule. Fig. 4 shows
molecules in Fig. 1. For the molecule of Fig. 1a, this is how the energy levels of the isolated molecule depend
demonstrated by the simple theoretical trick of artificially on the rotation angle θ. This shows that while most of
setting the hopping matrix elements connecting the oxy- the levels remain unaffected, one of them is sensitive to
gen atom to the fluorenone unit to zero. This yields the changes in θ, varying from 1.57eV at θ = 90◦ to 0.0eV
transmission coefficient shown by the red line in Fig. 2, at θ = 0◦ . To demonstrate that this level belongs to the
which shows that artificial removal of the chemical bonds fluorenone unit and bi-pyridine, Fig. 5 shows the local
to the oxygen destroys the Fano resonance, whereas the density of states (LDOS) for two different energy values
remainder of the transmission spectrum remains largely when θ = 30◦ (ground state of the molecule) and θ =
unaltered. 75◦ . Energies E = 2.0eV clearly correspond to states
The ability to manipulate Fano resonances, by chem- delocalized along the backbone, with almost no weight on
ical means or otherwise, opens up new possibilities for the bi-pyridine. This state is responsible for the Breit–



0 FIG. 5: Constant LDOS surface for a) 30◦ rotation and energy
-4 o
10 45
o values of 1.46eV and 2.00eV . b) 75◦ rotation and energy
o values of 0.54eV and 2.00eV .
-6 B ...
10 -1.5 -1 -0.5 0 0.5 1 1.5 H 1
E (eV) V W
A ... ... ...
0 1 2 ... N N + 1
FIG. 3: Transmission against energy for the bi-pyridine at-
tached molecule for rotation angles of 0◦ to 90◦ FIG. 6: A backbone of sites labelled 1 to N coupled to left
and right leads by matrix elements V, W and to a side group
of sites by H1 .

9 0 through a single backbone state Φm (k), with a resonant

7 5 energy ε0 . In this case, the relevant self-energy Σ is

6 0
ωω ∗
4 5
q (o)

E − ε0 + iΓ
3 0 where ω = hΨ|H1 |Φi. In this expression, Γ = Γ1 +
1 5
Γ2 is the broadening due to coupling of the back-
bone to the leads, with Γ1 = |V Φm (1)|2 N0 (E), Γ2 =
0 |W Φm (N )|2 NN +1 (E) and N0 (E) (NN +1 (E)) the local
0 0 .5 1 1 .5 2 density of states for the left (right) contacts. This yields
E (e V ) for the transmission coefficient,

4Γ1 Γ2
FIG. 4: Rotation angle θ dependence of the energy levels of T =  2 . (1)
ωω ∗
the isolated molecule. The Fano eigenstates are represented E − ε0 − E−ε + Γ2
by triangles while the circles represent the Breit–Wigner en-
ergy levels. Equation (1) shows that when ω = 0, no anti-resonance
occurs and the transmission coefficient exhibits a simple
Breit–Wigner peak. More generally, eq. (1) shows that
Wigner resonances in figures 2 and 3. On the other hand, transmission is a maximum at energies E = ε± , where
for E = 1.46eV and E = 0.54eV the orbitals are found ε± are the roots of equation (E − ε0 )(E − ε) − ωω ∗ = 0
to be localized on the central unit. and vanishes when E = ε. For small ω, a Breit–Wigner
To capture the generic features of this combination of peak of width Γ occurs in the vicinity of ε+ ≈ ε0 . In ad-
a Fano resonance and nearby Breit–Wigner resonance, dition a Fano peak occurs in the vicinity of ε− ≈ ε with

we now develop a model of the system sketched in Fig. 6, width (εΓωω
0 −ε)
2 . A comparison between eq. (1) and the ab

which consists of a backbone A composed of atomic or- initio results of Fig. 3 is shown in figure 7. This demon-
bitals numbered i = 1, 2, . . . , N , coupled to a side group strates that with an appropriate choice of parameters,
B by matrix elements H1 . (The geometric arrangement eq. (1) captures the essential features of Fano resonances
of the sites is irrelevant, provided A-sites are weakly cou- in aryleneethynylene molecular wires.
pled to B-sites.) Sites i ≤ 0 belong to the left lead and In summary we have shown that transport through
sites i ≥ N +1 to the right lead. These are coupled to the a new class of molecular wires, composed of fluorenone
ends of the backbone via weak hopping elements V, W . subunits with side groups, is dominated by Fano reso-
In the absence of coupling to the side chain, we as- nances rather than Breit–Wigner resonances. As a con-
sume that transmission through the backbone takes place sequence electron transport through the molecule can be

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