Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

• Published in: Advanced functional materials 2021-01, Vol.31 (4), p.n/a
• Main Authors: Ogle, Jonathan, Lahiri, Nabajit, Jaye, Cherno, Tassone, Christopher J., Fischer, Daniel A., Louie, Janis, Whittaker‐Brooks, Luisa
• Format: Article
• Language: English
• Subjects: 2D coordination polymers; Catalytic activity; Chemical properties; Chemical vapor deposition; Coordination polymers; Crystal defects; Crystallites; Domains; Electrical properties; Electronic structure; Ion transport; large‐area thin films; Materials science; metallic behavior; Polymer films; semiconductors; Stability; Superconductivity; Thick films; Thin films
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202006920

Two‐dimensional coordination polymers (2DCPs) have been predicted to exhibit exotic properties such as superconductivity, topological insulating behavior, catalytic activity, and superior ion transport for energy applications; experimentally, these materials have fallen short of their expectation due to the lack of synthesis protocols that yield continuous, large crystallite domains, and highly ordered thin films with controllable physical and chemical properties. Herein, the fabrication of large‐area, highly ordered 2DCP thin films with large crystallite domains using chemical vapor deposition (CVD) approaches is described. It is demonstrated that defects and the packing motifs of 2DCP thin films may be controlled by adjusting the vapor–vapor and vapor–solid interactions of the metal and organic linker precursors during the CVD fabrication process. Such control allows for the fabrication of defects‐controlled 2DCP thin films that show either semiconducting or metallic behavior. The findings provide the first demonstration of tuning the electrical properties of sub 100 nm‐thick continuous 2DCP thin films by controlling their electronic landscape through defect engineering. As such, it is determined that large‐area, highly ordered 2DCP thin films may undergo a semiconducting to metallic transition that is correlated to changes in morphology, crystalline domain sizes, crystallite orientation, defect interactions, and electronic structure. The emerging theme of “Materials Genome” inspires exciting opportunities for the design of large‐area, highly oriented 2D coordination polymer thin films where semiconducting and metallic behavior may be controlled at will to enable unprecedented device applications in the area of quantum electronics.