Electron tunneling through alkanedithiol self-assembled monolayers in large-area molecular junctions

The electrical transport through self-assembled monolayers of alkanedithiols was studied in large-area molecular junctions and described by the Simmons model [Simmons JIG (1963) J Appi Phys 34:1793-1803 and 2581-2590] for tunneling through a practical barrier, i.e., a rectangular barrier with the image potential included. The strength of the image potential depends on the value of the dielectric constant. A value of 2.1 was determined from impedance measurements. The large and well defined areas of these molecular junctions allow for a simultaneous study of the capacitance and the tunneling current under operational conditions. Electrical transport for octanedithiol through tetradecanedithiol self-assembled monolayers up to 1 V can simultaneously be described by a single effective mass and a barrier height. There is no need for additional fit constants. The barrier heights are in the order of 4-5 eV and vary systematically with the length of the molecules. Irrespective of the length of the molecules, an effective mass of 0.28 was determined, which is in excellent agreement with theoretical predictions.