Molecular Electronics by Chemical Modification of Semiconductor Surfaces

TL;DR

This review discusses how chemical modifications of semiconductor surfaces with molecular monolayers influence electronic device performance, focusing on energy level alignment, interface passivation, dipole insertion, and charge rearrangement.

Contribution

It provides a comprehensive overview of controlling interface properties through chemistry to optimize hybrid semiconductor/molecular electronic devices.

Findings

Molecular monolayers can tune energy level alignment at interfaces.

Chemistry at interfaces affects charge transport and device characteristics.

Practical tools are outlined for distinguishing electrostatic and tunneling barriers.

Abstract

Inserting molecular monolayers within metal / semiconductor interfaces provides one of the most powerful expressions of how minute chemical modifications can affect electronic devices. This topic also has direct importance for technology as it can help improve the efficiency of a variety of electronic devices such as solar cells, LEDs, sensors and possible future bioelectronic devices, which are based mostly on non-classical semiconducting materials (section 1). The review covers the main aspects of using chemistry to - control alignment of energy levels at interfaces (section 2): - passivate interface states (section 3), - insert molecular dipoles at interfaces (section 4), - induce charge rearrangement at and around interfaces (section 5). After setting the stage, we consider the unique current-voltage characteristics that result from transport across metal / molecular monolayer / semiconductor interfaces. Here we focus on the interplay between the monolayer as tunneling barrier on the one hand, and the electrostatic barrier within the semiconductor, due to its space-charge region (section 6), on the other hand, as well as how different monolayer chemistries control each of the these barriers. Section 7 provides practical tools to experimentally identify these two barriers, and distinguish between them, after which section 8 concludes the story with a summary and a view to the future. While this review is concerned with hybrid semiconductor / molecular effects (see Refs. 1,2 for earlier reviews on this topic), issues related to formation of monolayers and contacts, as well as charge transport that is solely dominated by molecules, have been reviewed elsewhere[3-6], including by us recently[7].