THE JOURNAL OF CHEMICAL PHYSICS 127, 084107 2007

Ab initio study of single-molecule rotation switch based on nonequilibrium Greens function theory
Y. Y. Liang, F. Jiang, Y. X. Zhou, and H. Chena
Physics Department, Fudan University, Shanghai 200433, Peoples Republic of China

R. Note, H. Mizuseki, and Y. Kawazoe

Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Received 18 May 2007; accepted 18 July 2007; published online 28 August 2007 The bistable molecular switches have been studied theoretically based on the rst-principles calculation. The geometry structures of the switches studied in this paper can be triggered between two symmetrical structures by using an external applied electric eld. I-V characteristic curves of the different molecule congurations have been calculated, and distinguishability of these characteristic curves indicates a switching behavior, the performance of which can be improved signicantly by some suitable donors and acceptors. 2007 American Institute of Physics. DOI: 10.1063/1.2771156
I. INTRODUCTION

Since the introduction of the integrated circuit in the 1960s, the number of individual electronic device placed on a single chip has quadrupled every three years approximately. More functionalities can be performed on a chip with more transistors. The fact that the cost of each chip changes little, leads to the conclusion that the denser the integration per chip, the lower the price per function for highperformance computation. The size of these devices becomes smaller and smaller since then. Recent progress has made the fabrication of electronic devices in nanoscale whose characteristic lengths L namely, the de Broglie wavelength, the mean free path, the phase-relaxation length, etc. of the device are smaller than its geometry dimension and new physical processes become dominant in overall transport. For example, the quantized conductance, the quantum Hall effect, and resonant tunneling have been observed experimentally.1 The suggestion of organic molecules as the next generation devices was initially put forward by Aviram and Ratner in 1970s.2 These devices represent the ultimate size limit of functional devices. Recently, the search for the prospective candidates for the silicon based semiconductor devices becomes a worldwide effort.313 The achievements attract the attention from industry. Lots of groups have made their contributions to understanding and modeling the capabilities of molecular devices theoretically and experimentally.1423 As a promising electronic device, molecular switches can be envisioned as future transistors with ultrahigh storage densities. Conformational switches that can be controlled by electric eld have been proposed by several groups.24 For example, Reed and Tour25 and Jiang et al.26 used a molecular switch consisting of three aromatic phenyl rings in series. The two hydrogen atoms of the middle ring are substituted by donor group NH2 and acceptor group NO2, while the
a

whole molecule is adsorbed onto the contact surfaces of gold leads. By adjusting the gate bias, the current can be controlled due to rotation of the middle ring with respect to the side rings. Troisi and Ratner suggested conformational molecular rectiers with the electric-eld-induced conformational change leading to unimolecular rectication of conductance.27,28 Kornilovitch et al. proposed bistable stator-rotor switches in 2002 Refs. 29 and 30 consisting of two functional components: one is the stationary bridge stator as the channel to electronic transport, the other is the rotor, the amide group CONH2 with a large dipole. The molecular devices with the large dipole driven by static electric elds, alternating electric elds, or polarized electric elds are reported recently.3135 In this paper, we simulate the stator-rotor switches by using the rst-principles method. In the calculation, threedimensional lattice is adopted, based on the tight-binding model, to deal with two gold 111 electrodes. The commercially available quantum-chemistry software GAUSSIAN03 Ref. 36 is used to calculate the electronic structure by the density functional theory DFT , with the subroutine of the nonequilibrium Greens function NEGF formulation for the electrode-molecule-electrode systems.37 This paper is organized as follows. In Sec. II, a description of the theoretical formulism and the computational details is given. In Sec. III, the transport characteristics of molecular devices are investigated, and its physical origin is described. Finally, the summary of our work is presented.
II. THEORETICAL FORMULA

Author to whom correspondence should be addressed. Electronic mail: haochen@fudan.edu.cn

In our computation, the metal/organic-molecule/metal sandwich is divided into two parts: one is the molecule bridging the junction, and the other part consists of two semi-innite Au leads source and drain .37 This open system deviates from its equilibrium state with the external electric eld, where the NEGF formalism is powerful.1,38 The retarded Greens function is dened as
2007 American Institute of Physics

0021-9606/2007/127 8 /084107/6/$23.00

127, 084107-1

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R 1

J. Chem. Phys. 127, 084107 2007

G R = E +S M F M M

R 1 , 2

where E+ is the energy plus an innitesimal imaginary part for example, 105 or 106 . The orbital overlap matrix S M and the Fock matrix FM subscript M means molecular part are extracted from the DFT calculation for the organic molR ecule and 1,2 represents the retarded self-energy for left and right leads, respectively. For simplicity, we neglect the scatR tering by the vibration of molecule. 1,2 is expressed as
R i

repeated until the self-consistent density matrix is achieved with the convergency criteria satised. GAUSSIAN03 designed for calculations of isolated system in equilibrium is extended to calculate the current of a circuit, where the NEGF formulism is added as a subroutine. After iterations, the convergence criterion is achieved. The DOS spectrum is calculated as DOS = 1 Tr i GR GA S M , M M 2 4

= E+S Mi

F Mi gR i

E+SiM FiM , gR i

is calculated by using where the surface Greens function the tight-binding methods developed since 1970s.39 The Fock matrix F Mi and the overlap matrix S Mi are extracted from the extended molecule where three gold surface atoms connect the molecule on both sides.37 Two effects take place when the molecular circuit formed: broadening of the discrete levels due to the hybridization with the delocalized metallic wave functions and the shift of the energy levels caused by the charging effect. The broadening of the molecule levels makes it possible that a fractional amounts of electrons ow into the molecule from two leads, increasing the repulsion interaction between electrons and lifting the energy levels up. The density matrix of this open system can be used to describe this charging effects, =

and the projected DOS PDOS on the molecular orbitals is calculated as41 PDOS E = 1 Tr i GR GA S M M M 2
orbital ,

where the trace is taken with respect to the indices of the molecular orbital. For the transport problem, we are interested in the I-V characteristics of the open system and the temperature is low we set T = 0 K . The current through metal/organic-molecule/metal system is evaluated from the Bttiker-Landauer formula1,40 I= 2e h
1

dET E,V ,
2

6
A

T E,V = Tr

1G

2G

dE GR f 1 M

+ f2

GA /2 M

where GA = GR is the advanced Greens function, 1 2 R A = i 1 2 1 2 , and f 1 f 2 is the Fermi distribution for the left right lead being in equilibrium. f i E = 1 / e E i /kT + 1 1 with the chemical potential i = EF 2 eV for source and drain and EF is the Fermi level of the gold lead. The zero point of the electronic potential is set at the center of the metal/molecule/metal system. Theoretically, Fermi level E f can be determined if we know the total density of states DOS and the exact electron number of the charged molecule. Unfortunately, the DOS inside the gap between the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital LUMO is relatively small, making the precise prediction of EF very sensitive to the level broadening and charged electrons. It is suggested that the Fermi level EF is regarded as a tting parameter near the gold work function when trying to explain the experimental I-V curves.14 In the present work, we set EF to be 5.1 eV.18,37 The total Fock operator, retarded Greens function, and density matrix will change due to charging effect in this open system. In order to describe these quantities accurately and make the calculation rigorous, self-consistent method is resorted to. Initially, a guess density matrix obtained from an isolated molecule calculated by GAUSSIAN03 is input. Corresponding Fock matrix is generated from this guess density matrix. Taking the self-energy of two leads into consideration, the retarded Greens function GR is solved from Eq. M 1 . The renewed density matrix is obtained from Eq. 3 as a new input of the next calculation loop. This procedure is

where T E , V is the transmission function. Intuitively, this means that the current is proportional to the integration of transmission function over energy ranging from one quasiFermi level to the other. The basis set we use for the geometry optimization and the electronic structure calculation in this paper is LanL2DZ.4244 It associates with the effective core potential which is specially suited for fth-row CsAu elements with considering the Darwin relativistic effect. In the DFT calculation, the exchange potential is Becke-3 hybrid exchange functional and the correlation potential is Perdew-Wang-91 gradient-corrected correlation functional.45,46 In the optimization calculation, the net charge of the molecule is 0 and the spin multiplicity is 1.

III. RESULTS AND DISCUSSIONS

The optimized geometry structures for the molecular switch with two states are shown in the inset of Fig. 1. Two hydrogen atoms are substituted by sulfur atoms which serve as alligator clips connecting to Au leads.47 In our calculation, the sulfur atom sits on the hollow position of its three nearest-neighboring surface gold atoms.37 The distance between the gold surface and sulfur atom is 1.9 Ref. 48 shown in Fig. 4 . The molecule can be divided into two parts, one is a phenoxazinyl group stator , and the other rotor is an amide CONH2 group which possess a large dipole. These two groups are connected through a bond. It is found that there exist two chiral states state 0 and state 1, as dened in the inset of Fig. 1 corresponding to its bistable conformation when external electronic eld is off. The dipole moment of the rotor interacting with the external electric

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FIG. 3. Au-lead/molecule/Au-lead open system 1 and its energy level diagram 2 .

FIG. 1. Color online Potential energy surface of the isolated molecule as a function of dihedral shown in inset without bias. The arrows indicate the bistable structures. We dene the left state as 1 and the right one as 0. The inset shows geometries of two states.

eld makes this switch controllable. In this way, the switch can be trigged by the electric eld between two states. The applied electric elds have two impacts, one is to drive electrons to ow, the other is to ip the molecular switch. To estimate its ipping threshold, the potential energy surface at every dihedral angles 1234 dened in the inset of Fig. 1 for two bistable structures, respectively is illustrated in Fig. 1 without external electric eld. In the estimation, all of the internal coordinates at each dihedral angle have been fully optimized. A double-well electronic structure is presented with two equivalent minima separated by an energy barrier height of 0.13 eV. The potential energy surface and the height of barrier change with the applied electric elds. In Fig. 2, potential energy surface under different static elds is presented. When eld is applied, the switch will ip from state 0 into lower energy state 1. Also, an alternating electric eld at microwave frequencies can be applied to trigger the switch.31 Figure 3 gives Au-lead/molecule/Au-lead open system

and its energy level diagram with bias which drives the system out of equilibrium. 1 2 represents the quasi-Fermi level of the left right Au lead. The direction of bias is from right to left shown in Fig. 3, with 1 greater than 2. If one energy level lies between two quasi-Fermi levels see Fig. 3 2 , the left lead would like to see more electrons occupying this level and keep charging them in, while the right one would like to see fewer electrons and keep pulling them out, or equivalently, more holes pump into this level from the right lead. In this case, the energy level acts as a channel, and the current ows through this channel. The calculated I-V characteristics for these two structures are presented in Fig. 4. The current curves of two states can be distinguished, indicating switch behavior. At low voltages, two current curves are identical, and the currents increase linearly. Above 2.4 V, the current of state 1 is greater than that of state 0. Two curves cross at 3.8 V. Exceeding this voltage makes current of state 0 is greater than that of state 1. In Fig. 5, isodensity surfaces of two states without bias have been depicted. With bias applied, the distribution of electron will change because of the hopping of electrons and holes into the molecule from two leads. The dark area is occupied by the electrons, and the white area is occupied by holes. We nd that electrons are rich around the left S atom and the ring nearest to the left lead. Holes mainly occupy the right S atom and the ring close to right lead. This can be

FIG. 2. Color online Potential energy of the isolated molecule under different voltages. The distance between leads is approximately 10 . When bias exceeds 10 V, one well disappears. The switch will be triggered from one state to the other. The data are offset for visibility.

FIG. 4. Color online The I-V characteristics for two states; the geometries of two states and the direction of the applied eld are depicted in inset.

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FIG. 5. Color online Isodensity surface of state 1 1 and state 0 2 without bias; their geometry structures are corresponding to the inset of Fig. 4. The dark part indicates the area where electrons are occupied with applied bias and the white one shows the area the holes accumulate.

FIG. 7. Color online PDOS of state 0 and state 1 under different biases. The solid curves are PDOS of HOMO, and the dashed curves are PDOS of LUMO. 1 , 2 , and 3 correspond to state 1 whose biases are 3.6, 2.4, and 1.2 V, and 5 , 6 , and 7 correspond to state 0 whose biases are 1.2, 2.4, and 3.6 V, respectively. The bias is zero in 4 .

understood from Fig. 3, since electrons come from the left lead and holes come from the right one. The electrons diffuse from the left lead to the right and holes diffuse from the right to the left through the molecule. Comparing Figs. 5 1 and 5 2 , we can nd that in stator fragments of two states the electron and hole distributions are similar, while, the distributions are totally different in rotor fragments. Driven by the bias in rotor of state 1 electrons originally distributing in oxygen atom move toNH2 Fig. 5 1 , while they move fromNH2 to oxygen atom in Fig. 5 2 . The different distributions make the corresponding electronic structures changed. In order to explain the physical origin of its switch behavior, DOS, PDOS, and transmission function spectra at different voltages have been evaluated based on Eqs. 4 , 5 , and 7 , respectively. In Fig. 6, DOS spectra of the two states in equilibrium are presented, where spectrum of state 0 is offset for visibility. It is trivial that these two spectra are identical for the geometries of two states are symmetrical.

Useful information can be read from DOS spectra, for instance, LUMO and HOMO levels of the systems, as depicted in Fig. 6, are 3.5 and 7.3 eV, respectively. The dashed line denoting the Fermi level is close to LUMO, which indicates LUMO-based conduction at low bias. Under different voltages, the positions of LUMO and HOMO will shift due to the charging effect as mentioned above. Figures 7 and 8 show the PDOS spectra and transmission function under different voltages, respectively. In Fig. 7, at low bias, with the increasing of voltage, the position of HOMO and LUMO of state 1 changes signicantly, moving closer to the Fermi level. The HOMO-LUMO gap decreases which facilitates the transportation of electrons and holes from one lead to the other through LUMO and HOMO. In Fig. 8 2 , the tail of LUMO lies between 1 and 2, where the current increases abruptly with the increase of the bias. For state 0, HOMO and LUMO shift slightly. HOMO moves

FIG. 6. Color online DOS at 0 V of two symmetrical are depicted. DOS of state 0 has been offset for visibility. Two arrows indicate the positions of HOMO and LUMO, respectively, and the dashed line indicates the Fermi level, EF = 5.1 eV.

FIG. 8. Transmission of two states at different biases. The dashed lines represent the Fermi level EF; the solid lines are the quasi-Fermi levels at different biases. 1 , 2 , and 3 correspond to biases of 3.6, 2.4, and 1.2 V in state 1 and 5 , 6 , and 7 correspond to biases of 1.2, 2.4, and 3.6 V in state 0, respectively. In 4 , the bias is off.

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FIG. 9. Color online I-V characteristics for donor OH, and their geometries of two states.

FIG. 11. Color online I-V characteristics for acceptor CN, and their geometries of two states.

close to the Fermi level while LUMO moves away keeping HOMO-LUMO gap almost constant at low bias. If the bias increases further, as shown in Fig. 7 1 , the HOMO-LUMO gap of state 1 increases, and HOMO is closer to the Fermi level changing the LUMO-based conduction into the HOMO-based one. After that, the HOMO-LUMO gap of state 1 will be greater than the gap of state 0 with current smaller than state 0. The charging effect plays an important role in the distinguishability of the molecular switch. The switch has two chiral states which share very similar electronic structure originally. The charging effects, which change the electronic structures in different way, cause the I-V curves distinguishable. It seems that the current ratio of two states getting in Fig. 4 is too small to be used in electronic devices. The maximum value of this ratio Istate1 / Istate0 is about 2 at 2.8 V. To improve the performance of the switch, we compare the I-V characteristics for electron donor group OH and NH2, and electron acceptor CN.23 Figures 911 present their I-V characteristic curves. Their geometry structures after optimization are displayed in the insets. In these

three gures, the current through state 1 is signicantly higher than the current through state 0, and the maximum current ratio of the two states is about 5. This suggests that the switch performance can be improved. It is an open question to nd suitable donors or acceptors that will improve the rectication signicantly at the cost of accessibility of synthesis.
IV. SUMMARY

We evaluate the stator-rotor conformational molecular switch based on the rst-principles method. The stator-rotor switch shares the following common features: two equivalent stable states, distinguishable I-V curves, and switchability. The I-V curves of these two states are distinguished due to the charging effect and the switch can be triggered by the external electronic eld. The charging effect affects the electronic structures of the two states in the different way, it is the main factor making the I-V characteristics distinguishable. The use of donors or acceptors can improve the performance of switch. The molecular switch may be useful in the future molecular circuit.
ACKNOWLEDGMENTS

This work was supported by the National Natural Science Foundation of China under Grant Nos. 10574024 and 90606024, the MOST of China 973 Project No. 2006CB921300 , and Fudan High-end Computing Center. The authors gratefully acknowledge SR8000 supercomputer resources from the Center for Computational Materials Science of the Institute for Materials Research, Tohoku University.
1

FIG. 10. Color online I-V characteristics for donorNH2, and their geometries of two states.

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