Electronic Tuning of Monolayer Graphene with Polymeric Zwitterists

Work function engineering of two-dimensional (2D) materials by application of polymer coatings represents a research thrust that promises to enhance the performance of electronic devices. While polymer zwitterions have been demonstrated to significantly modify the work function of both metal electrodes and 2D materials due to their dipole-rich structure, the impact of zwitterion chemical structure on work function modulation is not well understood. To address this knowledge gap, we synthesized a series of sulfobetaine-based zwitterionic random copolymers with variable substituents and used them in lithographic patterning for the preparation of negative-tone resists (i.e., zwitterists) on monolayer graphene. Ultraviolet photoelectron spectroscopy indicated a significant work function reduction, as high as 1.5 eV, induced by all polymer zwitterions when applied as ultrathin films (<10 nm) on monolayer graphene. Of the polymers studied, the piperidinyl-substituted version, produced the largest dipole normal to the graphene sheet, thereby inducing the maximum work function reduction. Density functional theory calculations probed the influence of zwitterion composition on dipole orientation, while lithographic patterning allowed for evaluation of surface potential contrast via Kelvin probe force microscopy. Overall, this polymer zwitterist design holds promise for fine-tuning 2D materials electronics with spatial control based on the chemistry of the polymer coating and the dimensions of the lithographic patterning.

Automated summary

The engineering of work function of 2D materials with polymer coatings can significantly reduce the work function of monolayer graphene. The chemical structure of the polymer zwitterions plays a crucial role in modulating the work function, with the piperidinyl-substituted version showing the largest reduction in work function.