Probing molecule-semiconductor interfaces through Metal Molecule Semiconductor transport characteristics

Electron transfer processes at molecule-semiconductor interfaces involve a complex mixture of thermionic, tunneling and hopping events. Traditionally these processes have been modeled in a piece-meal fashion, relying on phenomenological treatments such as Simmons and Richardson equations that are not vetted in atomistic systems and do not flow seamlessly into each other. We present a unified modeling approach, based on the Non-equilibrium Greens function (NEGF) formalism that allows us to integrate diverse transport regimes and establish a comprehensive quantitative theory. By comparing our simulations with experiments on a metal-molecule-semiconductor junction (varying molecular lengths ~1-3nm), we identify the role of molecular monolayers in tuning the semiconductor band-bending, and thereby overall device conductivity. We find that the principal role of molecules is to act as a voltage divider, altering the Schottky barriers, thereby modulating current levels, voltage-asymmetries and crossover from Schottky to tunneling transport. While this provides an appealingly simple explanation for our observed experimental trends, the calculated shifts in crossover voltages are insufficient to explain the experiments quantitatively. Quantitative correspondence with experiments requires invocation of an additional voltage divider arising from molecular dipoles that further tunes semiconductor band-bending. The extracted dipole moments are rationalized using ab-initio calculations for each molecule, along-with a dilution of packing fraction for the shortest molecular lengths. The methodology described herein can be used to better understand and predict transport characteristics of such junctions.