Spatial and Bidirectional Work Function Modulation of Monolayer Graphene with Patterned Polymer "Fluorozwitterists".

Understanding the electronic properties resulting from soft-hard material interfacial contact has elevated the utility of functional polymers in advanced materials and nanoscale structures, such as in work function engineering of two-dimensional (2D) materials to produce new types of high-performance devices. In this paper, we describe the electronic impact of functional polymers, containing both zwitterionic and fluorocarbon components in their side chains, on the work function of monolayer graphene through the preparation of negative-tone photoresists, which we term "fluorozwitterists." The zwitterionic and fluorinated groups each represent dipole-containing moieties capable of producing distinct surface energies as thin films. Kelvin probe force microscopy revealed these polymers to have a p-doping effect on graphene, which contrasts the work function decrease typically associated with polymer-to-graphene contact. Copolymerization of fluorinated zwitterionic monomers with methyl methacrylate and a benzophenone-substituted methacrylate produced copolymers that were amenable to photolithographic fabrication of fluorozwitterist structures. Consequently, spatial alteration of zwitterion coverage across graphene yielded stripes that resemble a lateral p-i-n diode configuration, with local increase or decrease of work function. Overall, this polymeric fluorozwitterist design is suitable for enabling simple, solution-based surface patterning and is anticipated to be useful for spatial work function modulation of 2D materials integrated into electronic devices.

Stabilization of Three-Particle Excitations in Monolayer MoS2 by Fluorinated Methacrylate Polymers.

While extrinsic factors, such as substrates and chemical doping, are known to strongly influence visible photoemission from monolayer MoS2, key fundamental knowledge for p-type polymeric dopants is lacking. We investigated perturbations to the electronic environment of 2D MoS2 using fluorinated polymer coatings and specifically studied stabilization of three-particle states by monitoring changes in intensities and emission maxima of three-particle and two-particle emissions. We calculated changes in carrier density and trion binding energy, the latter having an additional contribution from MoS2 polarization by the polymer. Polarization is further suggested by Kelvin probe force microscopy (KPFM) measurements of large Fermi level shifts. Changes similar in magnitude, but opposite in sign, were observed in 2D MoS2 coated with an analogous nonfluorinated polymer. These findings highlight the important interplay between electron exchange and electrostatic interactions at the interface between polymers and transition metal dichalcogenides (TMDCs), which govern fundamental electronic properties relevant to next-generation devices.

Polarization-Driven Asymmetric Electronic Response of Monolayer Graphene to Polymer Zwitterions Probed from Both Sides.

We investigated the nature of graphene surface doping by zwitterionic polymers and the implications of weak in-plane and strong through-plane screening using a novel sample geometry that allows direct access to either the graphene or the polymer side of a graphene/polymer interface. Using both Kelvin probe and electrostatic force microscopies, we observed a significant upshift in the Fermi level in graphene of ∼260 meV that was dominated by a change in polarizability rather than pure charge transfer with the organic overlayer. This physical picture is supported by density functional theory (DFT) calculations, which describe a redistribution of charge in graphene in response to the dipoles of the adsorbed zwitterionic moieties, analogous to a local DC Stark effect. Strong metallic-like screening of the adsorbed dipoles was observed by employing an inverted geometry, an effect identified by DFT to arise from a strongly asymmetric redistribution of charge confined to the side of graphene proximal to the zwitterion dipoles. Transport measurements confirm n-type doping with no significant impact on carrier mobility, thus demonstrating a route to desirable electronic properties in devices that combine graphene with lithographically patterned polymers.

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.

Polymer Zwitterions for Stabilization of CsPbBr3 Perovskite Nanoparticles and Nanocomposite Films.

Functional polymers with sulfobetaine or phosphorylcholine zwitterions as pendent groups are demonstrated as both ligands and host matrices for CsPbBr3 perovskite nanoparticles (PNPs). These polymers produce nanocomposite films with excellent NP dispersion, optical transparency, and impressive resistance to NP degradation upon exposure to water. Multidentate interactions of the zwitterion-containing copolymers with the PNPs induce dispersed or weakly aggregated nanocomposite morphologies, depending on the extent of zwitterionic functionality in the polymer. Incorporating additional functionality into the polymers, such as benzophenone pendent groups, yields lithographically patternable films, while time-resolved photoluminescence measurements provide insight into the electronic impact of PNPs in zwitterionic polymer matrices.

Tuning charge transport dynamics via clustering of doping in organic semiconductor thin films.

A significant challenge in the rational design of organic thermoelectric materials is to realize simultaneously high electrical conductivity and high induced-voltage in response to a thermal gradient, which is represented by the Seebeck coefficient. Conventional wisdom posits that the polymer alone dictates thermoelectric efficiency. Herein, we show that doping - in particular, clustering of dopants within conjugated polymer films - has a profound and predictable influence on their thermoelectric properties. We correlate Seebeck coefficient and electrical conductivity of iodine-doped poly(3-hexylthiophene) and poly[2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-3,6-diyl)-alt-(2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] films with Kelvin probe force microscopy to highlight the role of the spatial distribution of dopants in determining overall charge transport. We fit the experimental data to a phonon-assisted hopping model and found that the distribution of dopants alters the distribution of the density of states and the Kang-Snyder transport parameter. These results highlight the importance of controlling dopant distribution within conjugated polymer films for thermoelectric and other electronic applications.