Voltage-Dependent Barrier Height of Electron Transport through Iron Porphyrin Molecular Junctions

• Published in: Journal of physical chemistry. C 2021-03, Vol.125 (13)
• Main Authors: Nawarat, Poomirat, Beach, Kory, Meunier, Vincent, Terrones, Humberto, Wang, Gwo-Ching, Lewis, Kim Michelle
• Format: Article
• Language: English
• Subjects: charge transport; electrodes; gold; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecules; physical and chemical processes
• ISSN: 1932-7447; 1932-7455

Electron transport through iron porphyrin (FeP) molecules self-assembled on a gold (Au) substrate was investigated using conductive atomic force microscopy (AFM) to measure current–voltage (I–V) characteristics. In the direct tunneling region (|V| ≤ 0.1 V), the Simmons model was used to characterize the electron transport. Furthermore, the energy barrier between the Fermi energy level of Au and the highest occupied molecular orbital (HOMO) level of the FeP molecule was determined to be between 0.3 and 0.6 eV; the range of the electron attenuation coefficient was 0.6–0.8 Å–1. Instead of a constant barrier height, a voltage-dependent barrier height was adapted to simulate the experimental I–V curves over the entire voltage range (|V| ≤ 2 V) using the Simmons model for the intermediate case. The voltage-dependent barrier height is supported by a previously predicted response of molecular-projected self-consistent Hamiltonian orbitals. The dependence showed that the HOMO level relative to the Fermi energy level of the Au electrode decreased as the bias voltage increased. To verify the deposition of the FeP on the Au substrate, Raman spectroscopy and AFM analysis were performed.