Non-mechanical conductance switching in a realistic molecular tunnel junction

Adva Baratz and Roi Baer*

Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, the Hebrew University of Jerusalem, Jerusalem 91904 Israel.
We present a molecular junction composed of a donor (polyacetylene strands) and an acceptor (malononitrile) connected together via a benzene ring and coupled weakly to source and drain electrodes on each side, for which a gate electrode induces intramolecular charge transfer, switching reversibly the character of conductance. Using density functional theory, we show the junction displays a single, gate-tunable differential conductance channel in a wide energy range. The gate field must align parallel to the displacement vector between donors and acceptor to affect their potential difference; for strong enough fields spontaneous intramolecular electron transfer occurs. This event radically affects conductance, reversing the charge of carriers, enabling a spin-polarized current channel. We discuss the physical principles controlling the operation of the junction, and find interplay of quantum interference, charging, Coulomb blockade, and electron-hole binding energy effects. We expect this switching behavior a generic property for similar donor-acceptor systems of sufficient stability.

In recent years, gated molecular junctions, coupled weakly to

source-drain (SD) electrodes, were studied experimentally and analyzed theoretically. The gate shifts differential conductance channels with respect to the chemical potential (Fermi level) of the metallic leads1-15 and also affects nuclear configuration by inducing electron transfer from metal electrode to the molecule.16,17 However, to our knowledge, it has not been widely discussed how to use the gate for inducing internal change of electronic structure within the junction itself, without generating significant nuclear reorganization. A molecular junction that responds readily to such manipulations could be useful for achieving high degree of control and switching capabilities. It is the purpose of this paper to present a conceptual idea towards such an effect, backed up by a careful theoretical analysis of a specific molecular candidate. A rich variety of physical processes (i.e. interference, charging energies, electron-hole binding energy, polarizability and Coulomb blocking) affect the various regimes of transport in this junction. The resulting system displays a single, highly tunable, resonance state, supporting a single differential conductance channel and an on/off switch for spin polarized currents. Our analysis is theoretical and makes use of density functional theory (DFT) based on the first-principles-tuned BaerNeuhauser-Livshits (BNL*)18,19 range-separated hybrid.20,21 This functional allows for good molecular structure prediction while being especially suitable for conductance calculations since its orbital energies were found to closely approximate quasiparticle energies a property not available in the more common density functionals (see supplementary material for comparison of BNL* and B3LYP gaps).22,23 The functional also allows calculation of accurate charge transfer 24 as well as valence25 excitation energies with linear response time-dependent density functional theory (TDDFT). All electronic structure calculations were performed using this BNL* functional18,19,26 within the 6-31G/6-31+G* basis set and Q*

CHEM v3.1 package.27 See supplementary material for details on basis sets, tuning and a comparison to B3LYP.

z y x
Rz

Oxide Gate
Figure 1: Schematic depiction of the molecular junction explored in this paper: two thiol-terminated short trans-polyacetylene (PA) segments ) ), acting as meta substituents on the aromatic ring of a 2-(3-phenylprop-2-ynylidene) malononitrile molecule. The thiol group facilitates bonding to gold metallic source drain electrodes. The PAs are electron donors determining the ionization potential ( ) of the molecule while the MN is an electron acceptor, endowing the electron affinity . The molecular plane is parallel to x-z and lies above a planar gate electrode parallel to the x-y plane. The latter creates an electric field in the vertical direction. The smallest vertical distance between MN and PA is large ( ), facilitating the high tunability of the fundamental gap by . A sufficiently strong induces spontaneous electron transfer from PA to MN. Due to interference effects, electric current cannot flow through the aromatic ring from left to right PAs but must go instead through the MN. Thus also controls the differential conductance channel of the junction.

The active part of the molecular junction is composed of the 2-(3-phenylprop-2-ynylidene) malononitrile molecule, where the malononitrile group (MN) acts as an electron acceptor, and two thiol- terminated short trans-polyacetylene (PA) segments connecting in meta position to the benzene ring acting as electron donors (Figure 1). Configurational stability of the junction, hindering bending and rotary distortions, even under strong gate fields and charge shifts, is achieved by using conjugated PA segments as donors, and CC triple bond connecting the acceptor to the aromatic ring, (see supplementary material for description of stability under gate fields). 1

Email: Roi.Baer@huji.ac.il

the MN acceptor jump discontinuously at . We have carefully checked, that if the sulfur atoms are held in place (as happens when the molecule is connected to the metallic leads), the geometry of the molecule is only slightly distorted by this internal electron transfer.
2 3

In Mullikens theory,33 the energy of electron transfer from ) ) ) donor to acceptor is ) where

is the energy of Coulomb

Figure 2: Graphical depiction of three frontier orbitals dominating the electronic properties of the junction. The occupied orbitals 1 and 3 (localized on the left and right donors) and the unoccupied orbital 2 (localized on the acceptor). The energy of orbital 1 is slightly higher than that of 3.

attraction between the electron and hole. Charge spontane) ously transfers from donor to acceptor once ) so from Figure 3 (left): ) (3)

We now study charge carriers in the molecule. Consider first the creation of a hole by removing an electron, a process involving investment of energy, the ionization potential . In the quasiparticle picture, the hole has a single-particle wave function, described as a frontier DFT orbital on one of the donors (orbitals 1 or 3 of Figure 2). The energy of the hole, , is closely approximated by the DFT highest occupied molecular orbital (HOMO) energy .19,22,23 Similarly, we can add an electron to the molecule, this releases energy of the amount equal to the electron affinity, . In the DFT calculation, the electron quasiparticle wave function is orbital 2 in Figure 2 localized primarily on the MN acceptor. The energy of the electron, , is closely approximated by the lowest unoccupied molecular orbital (LUMO) energy . We note that the donor orbitals 1 and 3 are spatially nonoverlapping, with orbital 1 having slightly higher energy. This non-mixing of these left and right orbitals is due to an interference effect appearing when the PA segments are connected to the benzene ring in the meta positions where they become electronically decoupled: an hole on the left cannot flow through the ring into the right side. 28-32 As we shall see below, this has an important bearing on the differential conductance peaks of the junction. Now consider how a negatively charged gate electrode in the x-y plane below the molecule affects its electronic structure. The electrode creates an electric field in the z direction , or a potential difference between the electron on MN and the hole on PA, displaced by a distance and where is the molecular dielectric constant. Therefore, the gate-field affects the electron-hole energy gap as: ) ) (1)

Using Eqs. 2)- 3) we can estimate the internal dielectric con( ( stant and the electron-hole effective z-displacement , the latter is in agreement with the minimal donoracceptor z-displacement .
Charge on Acceptor (e)
-0.2

-2
-4

Eeb

-0.4
-0.6 -0.8 -1

-6
-8

2
1 0 0 0.2 Eeh 0.4 0.6

-10
-12

-1.2

-14 0 0.2 0.4 0.6 0.8 1

Gate Field (V/)

0.8

Gate Field (V/)

Figure 3: BNL*-DFT spin-polarized LUMO-HOMO (quasi-particle) gap and TDDFT optical gap (left), z-component dipole moment and Mulliken charge on cyano groups (right) vs. gate field.

In Figure 3 (left) we also plot the optical gap , calculated from linear response TDDFT using the same functional. is the first excitation energy corresponding to a transition dipole moment pointing in the z direction. Note that depends linearly on , predicting strong electro-absorption effects for z-polarized light in this junction. It is readily visible in Figure 3 (left) that the exciton binding energy, namely the difference 1.7 eV, is nearly constant. That the value of is close to that of of Eq. 3) is no ( coincidence as both describe electron-hole attraction energy. Once , i.e. the field is strong enough to induce charge transfer, a spin (say) electron moves from one of the donors (orbitals 1 or 3) into the orbital localized on the acceptor (orbital 2). Orbital 2, the previous LUMO, now has its energy spin-dependent: the orbital energy drops abruptly slightly below the HOMO level (due to the electron-hole binding energy discussed above) and it get occupied by an electron while the orbital energy shoots up in energy above some of the other unoccupied levels of the PAs. This latter effect is due to Coulomb repulsion: the energy to add a second electron to the acceptor is much higher now, due to the presences of the first transferred electron. Thus, immediately after the charge transfer orbital 2 is no longer a frontier orbital: both 2

In Figure 3 (left) we plot the DFT-calculated orbital gap vs. the gate field , showing linear dependence, from which: (2)

An abrupt change in the gap occurs at a certain critical value of the field . This critical behavior is due to a spontaneous charge transfer induced by the gate, clearly seen in Figure 3 (right), where the dipole moment and charge on

Dipole Moment (e)

Gap (eV)

the and LUMOs are now donor orbitals and as a result the and gaps become independent of . Further increase of the field lowers the energies of both spin components of orbital 2. The component digs deeper into the occupied levels but the component energy reduces until it resumes its role as the LUMO at making the gap once again field dependent. Thus far, we discussed this donor-acceptor system as a molecule and not as part of a molecular junction. The junction we consider is formed by attaching the molecule to left and right metallic leads of chemical potential . The thiol-terminated PA segments provide for very weak coupling and the molecule preserves much of its chemical and electronic properties: its orbitals and its orbital energies slightly shift to sharp differential conductance resonance channels. We imagine an experimental setup where the energy needed to transfer an electron from the molecule to the metal, i.e. is controlled and kept fixed for all values of the gate field (in our case, ). We assume a symmetric application of the bias potential across the leads, where the chemical potential of the left (right) lead is ( ). In this setup experimental realization of current through a | |. resonance at energy requires a bias of

) is the Greens function corand right PA segments and responding to the DFT Hamiltonian (see ref. 30 for further details and explanations of this method). The calculated ), is plotted in Figure 4 for several values of the gate field . Remarkably, at a very broad energy interval ( ) the system displays only a single transmittance peak (which, under sufficiently large gate field, may split into two spin-polarized components, as discussed below). While there are many occupied and some unoccupied orbitals associated with the PA strands in this energy range (e.g. orbitals 1 and 3 in Figure 2), none of them seem to conduct current. This is due to the strong destructive interference effect associated with the connection of the PA strands in a meta- position on the benzene ring.28-30 The position of the conductance peak, with respect to the HOMO energy (the vertical line in Figure 4 (left)), is almost exactly equal to the gap (Figure 3 (left)), indicating that transmission occurs through the LUMO orbital, i.e. orbital 2 of Figure 2, mainly localized on MN - the electron acceptor part of the molecule. ) peak at low fields corresponds to tunneling Thus, the transmission of electrons through orbital 2. As a result, the source-drain voltage needed for reaching this conducting state is tunable by . This can be seen in the right panel of Figure 4 zooming into the orange strip region of Figure 4 (left). As the gate field increases (by steps of ) the position of the conductance peak drops by steps of . This high tunability of differential conductance facilitates a transistor-like operation mode for the junction, as current is reversibly switched on/off by the gate field.

) through the junction, Figure 4: The calculated transmittance function assuming clamped nuclei, from the zero bias BNL* Hamiltonians (Eq. 4)) at ( different gate fields. On the left, a broad energy view of the transmission channels, from to at several gate fields and on the right a zoom into the energy range of 0.5 to 1.7 eV for gate fields, before the chargetransfer event. The full (dotted) line is the transmission of the () spin states. The vertical line at -1.1eV is the position of the HOMO energy.

We study the differential conductance of the junction using Landauers theory, based on the ground-state DFT Hamilto) (the probabilnian where the peaks of the transmittance ity for an electron of energy to cross the junction from left to right) are directly associated with the differential conductance channels. In weakly bound junctions these position of these peaks are close to the quasiparticle energies which are close to the orbital energies of our DFT Hamiltoni) is thus calculated by:34 an.21,22 The transmittance ) Where ( { ) ) } (4)

Figure 5: Expected differential conductance of the molecular junction in Figure 1 as a function of gate field and source-drain voltage.

) are absorbing potentials35 laid on the left 3

As the gate field approaches the critical value , the differential conductance resonance splits into two resonances at slightly different energies (Figure 4 (right)), each corresponding to a different value of the z-component of spin. As often happens in DFT calculations, the breaking of spin symmetry signals strong correlation effects in the electronic system. At the critical gate field a catastrophic spin-split occurs: one spin resonance (say, spin ) shoots down in energy below the HOMO level (vertical line in Figure 4 (left)), gets occupied by an electron and becomes a hole conducting channel, while the other resonance shoots up in energy and becomes an electron conducting channel. The energy splitting between

these two spin resonances for gate fields slightly above is . As explained above, the drastic change of electronic structure happens because of the intramolecular charge transfer: a electron transfers from one of the frontier orbitals (orbitals 1 or 3 of in Figure 2) of the donors to orbital 2 of the acceptor. Since the acceptor now populates an electron, conductance of electrons is blocked due to Coulomb repulsion (unless is considerably increased). As the field is further increased beyond , the hole differential conductance peak still responds to the field and can be further lowered, resulting in highly controllable spin-polarized differential conductance channel. In summary, we have presented a molecular junction (Figure 1) with well-separated donor acceptor sites for which proper orientation with respect to a gate field allows exceptional control of the conductance and optical properties. The junction is structurally stable under the strong gate fields. It displays a single conductance peak at a broad energy range, allowing meticulous control of conductance over a large source-drain voltage and gate field intervals. The strong electronic response should render the system less sensitive to stray fields and temperature effects. We summarize the conductance properties of the junction in Figure 5, exhibiting gate control of the differential conductance level, allowing a transistor-like operation and the switch into a spin-polarized regime when . Although we here treat a specific system, the principle of operation is generic since it is based on sound physical principles; therefore, other junctions containing similar design elements should exhibit similar conductance behavior. Acknowledgments: We gratefully acknowledge the Israel Science Foundation for supporting this study under grant no. 1020/10.
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