Tuning Molecular Orbitals in Molecular Electronics and Spintronics

• Published in: Accounts of chemical research 2010-01, Vol.43 (1), p.111-120
• Main Authors: Kim, Woo Youn, Kim, Kwang S
• Format: Article
• Language: English
• ISSN: 0001-4842; 1520-4898
• DOI: 10.1021/ar900156u

With the advance of nanotechnology, a variety of molecules, from single atoms to large-scale structures such as graphene or carbon nanotubes, have been investigated for possible use as molecular devices. Molecular orbitals (MOs) are a key ingredient in determining the transport properties of molecules, because they contain all the quantum mechanical information of molecular electronic structures and offer spatial conduction channels for electron transport. Therefore, the delicate modulation of the MOs enables us to tune the performance of electron transport through the molecule. Electric and magnetic fields are powerful and readily accessible means for that purpose. In this Account, we describe the effects of external fields on molecular electronic and spintronic devices. Quantum transport through a molecule that connects source and drain electrodes depends strongly on the alignment of molecular energy levels with respect to the chemical potentials at both electrodes. This dependence results from the energy levels being exploited in resonant tunneling processes when the molecule is weakly coupled to the electrodes in the molecular junction. Molecular energy levels can be shifted by the Stark effect of an external electric field. For a molecule with no permanent dipole moment, the polarizability is the primary factor determining the energy shift of each MO, according to the second-order Stark effect; more polarizable MOs undergo a larger energy shift. Interestingly, even a small shift may lead to a completely nontrivial result. For example, we show a magnetic on−off switching phenomenon of a molecule controlled by an electric field. If a molecule has a nonmagnetic ground state but a highly polarizable magnetic excited state with an energy slightly above the ground state, the magnetic excited state can have lower energy than the ground state under a sufficiently strong electric field. A magnetic field is normally used to control spin orientation in a ferromagnetic system. Here we show that the magnetic field can also be used to control MOs. A graphene nanoribbon with zig-zag-shaped edges (ZGNR) has a ferromagnetic spin ordering along the edges, and the spin states have unique orbital symmetries. Both spin polarizations and orbital symmetries can simultaneously be controlled by means of an external magnetic field. The ZGNR spin-valve devices incorporating this effect are predicted to show an extreme enhancement (compared with conventional devices) of magnetor