Semiconducting to Metallic Electronic Landscapes in Defects Controlled Two-Dimensional ?-d Conjugated Coordination Polymer Thin Films

Published

October 16, 2020

Author(s)

Cherno Jaye, Daniel A. Fischer, Jonathan Ogle, Nabajit Lahiri, Christopher Tassone, Janis Louie, Luisa Whittaker-Brooks

Abstract

Two-dimensional coordination polymers (2D CPs) are of significant interest due to their intriguing structural, optical, and electrical properties which can be tuned through the selective coordination of different metals and organic linkers. Although, 2D CPs have been predicted to exhibit very exotic properties such as superconductivity, topological insulating behavior, catalytic and sensing activity for CO2 conversion, and superior ion transport for energy applications, experimentally, these materials have fallen short to their expectation due to the lack of synthesis protocols that yield continuous, large crystallite domains, and single-crystalline thin films with controllable physical and chemical properties. In contrast to top-down exfoliation and bottom-up liquid-assisted synthesis approaches that often yield uncontrollable 2D CP morphologies, herein, we describe guidelines for the fabrication of large area, single crystalline 2D CP thin films with large crystallite domains using chemical vapor deposition (CVD) approaches. We demonstrate that defects and the packing motifs of 2D CP thin films may be controlled by adjusting the vapor-vapor and vapor-solid interactions of the metal and organic linker precursors and reactions during the CVD fabrication process. Such control allows for the fabrication of defects controlled 2D CP thin films that show either semiconducting or metallic behavior. Our findings provide the first demonstration of metallic behavior at room temperature in 2D CP thin films. As such, we determine that large area, single-crystalline 2D CP 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.

Citation

Advanced Functional Materials

Volume

31

Issue

4

Pub Type

Journals

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DOI Link

Keywords

Two-dimensional, polymers, CVD, NEXAFS, GIWAXS, XPS, AFM, HRTEM

Citation

Jaye, C. , Fischer, D. , Ogle, J. , Lahiri, N. , Tassone, C. , Louie, J. and Whittaker-Brooks, L. (2020), Semiconducting to Metallic Electronic Landscapes in Defects Controlled Two-Dimensional ?-d Conjugated Coordination Polymer Thin Films, Advanced Functional Materials, [online], https://doi.org/10.1002/adfm.202006920 (Accessed April 19, 2024)