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

Abstract

Abstract 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.

Authors:
 [1];  [1];  [2];  [3];  [2];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Utah, Salt Lake City, UT (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1769623
Alternate Identifier(s):
OSTI ID: 1804504
Grant/Contract Number:  
CBET 2016191; DMR 1824263; AC02‐76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 4; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 2D coordination polymers; electronic structure; large‐area thin films; metallic behavior; semiconductors

Citation Formats

Ogle, Jonathan, Lahiri, Nabajit, Jaye, Cherno, Tassone, Christopher J., Fischer, Daniel A., Louie, Janis, and Whittaker‐Brooks, Luisa. Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films. United States: N. p., 2020. Web. doi:10.1002/adfm.202006920.
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Ogle, Jonathan, Lahiri, Nabajit, Jaye, Cherno, Tassone, Christopher J., Fischer, Daniel A., Louie, Janis, & Whittaker‐Brooks, Luisa. Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films. United States. https://doi.org/10.1002/adfm.202006920
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Ogle, Jonathan, Lahiri, Nabajit, Jaye, Cherno, Tassone, Christopher J., Fischer, Daniel A., Louie, Janis, and Whittaker‐Brooks, Luisa. Fri . "Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films". United States. https://doi.org/10.1002/adfm.202006920. https://www.osti.gov/servlets/purl/1769623.
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@article{osti_1769623,
title = {Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films},
author = {Ogle, Jonathan and Lahiri, Nabajit and Jaye, Cherno and Tassone, Christopher J. and Fischer, Daniel A. and Louie, Janis and Whittaker‐Brooks, Luisa},
abstractNote = {Abstract 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.},
doi = {10.1002/adfm.202006920},
journal = {Advanced Functional Materials},
number = 4,
volume = 31,
place = {United States},
year = {Fri Oct 16 00:00:00 EDT 2020},
month = {Fri Oct 16 00:00:00 EDT 2020}
}
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https://doi.org/10.1002/adfm.202006920
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