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Title: Surface Morphology and Electrical Properties of Cu3BTC2 Thin Films Before and After Reaction with TCNQ

Journal Article · · ACS Applied Materials and Interfaces
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Technical Univ. Munich, Garching (Germany)
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HKUST-1 or Cu3BTC2 (BTC = 1,3,5-benzenetricarboxylate) is a prototypical metal–organic framework (MOF) that holds a privileged position among MOFs for device applications, as it can be deposited as thin films on various substrates and surfaces. Recently, new potential applications in electronics have emerged for this material when HKUST-1 was demonstrated to become electrically conductive upon infiltration with 7,7,8,8-tetracyanoquinodimethane (TCNQ). However, the factors that control the morphology and reactivity of the thin films are unknown. Here, we present a study of the thin-film growth process on indium tin oxide and amorphous Si prior to infiltration. From the unusual bimodal, non-log-normal distribution of crystal domain sizes, we conclude that the nucleation of new layers of Cu3BTC2 is greatly enhanced by surface defects and thus difficult to control. We then show that these films can react with methanolic TCNQ solutions to form dense films of the coordination polymer Cu(TCNQ). This chemical conversion is accompanied by dramatic changes in surface morphology, from a surface dominated by truncated octahedra to randomly oriented thin platelets. The change in morphology suggests that the chemical reaction occurs in the liquid phase and is independent of the starting surface morphology. The chemical transformation is accompanied by 10 orders of magnitude change in electrical conductivity, from <10–11 S/cm for the parent Cu3BTC2 material to 10–1 S/cm for the resulting Cu(TCNQ) film. In conclusion, the conversion of Cu3BTC2 films, which can be grown and patterned on a variety of (nonplanar) substrates, to Cu(TCNQ) opens the door for the facile fabrication of more complex electronic devices.

Research Organization:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1487415
Report Number(s):
SAND-2018-10298J; 668028
Journal Information:
ACS Applied Materials and Interfaces, Vol. 10, Issue 45; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

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Cited By (3)

Micro-spectroscopy of HKUST-1 metal–organic framework crystals loaded with tetracyanoquinodimethane: effects of water on host–guest chemistry and electrical conductivity journal January 2019
Coordination polymer-based conductive materials: ionic conductivity vs. electronic conductivity journal January 2019
Achieving current rectification ratios ≥ 10 5 across thin films of coordination polymer journal January 2019

Figures / Tables (9)

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36 MATERIALS SCIENCE
2D nucleation
bimodal growth
coordination polymers
electrical conductivity
MOFs
surface morphology
thin-film growth