Emergence of Metallic Conductivity in Ordered One-Dimensional Coordination Polymer Thin Films upon Reductive Doping

Mikko Nisula*, Antti J. Karttunen, Eduardo Solano, Girish C. Tewari, Maarit Karppinen, Matthias Minjauw, Himanshu Sekhar Jena, Pascal Van Der Voort, Dirk Poelman, Christophe Detavernier*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

The prospect of introducing tunable electric conductivity in metal-organic coordination polymers is of high interest for nanoelectronic applications. As the electronic properties of these materials are strongly dependent on their microstructure, the assembly of coordination polymers into thin films with well-controlled growth direction and thickness is crucial for practical devices. Here, we report the deposition of one-dimensional (1D) coordination polymer thin films of N,N′-dimethyl dithiooxamidato-copper by atomic/molecular layer deposition. High out-of-plane ordering is observed in the resulting thin films suggesting the formation of a well-ordered secondary structure by the parallel alignment of the 1D polymer chains. We show that the electrical conductivity of the thin films is highly dependent on their oxidation state. The as-deposited films are nearly insulating with an electrical conductivity below 10-10 S cm-1 with semiconductor-like temperature dependency. Partial reduction with H2 at elevated temperature leads to an increase in the electrical conductivity by 8 orders of magnitude. In the high-conductance state, metallic behavior is observed over the temperature range of 2-300 K. Density functional theory calculations indicate that the metallic behavior originates from the formation of a half-filled energy band intersecting the Fermi level with the conduction pathway formed by the Cu-S-Cu interaction between neighboring polymer chains.

Original languageEnglish
Pages (from-to)10249-10256
Number of pages8
JournalACS Applied Materials and Interfaces
Volume13
Issue number8
Early online date22 Feb 2021
DOIs
Publication statusPublished - 3 Mar 2021
MoE publication typeA1 Journal article-refereed

Keywords

  • atomic layer
  • coordination polymer
  • deposition
  • molecular layer deposition
  • thin films

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