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Structural and electronic switching of a single crystal 2D metal-organic framework prepared by chemical vapor deposition

F. James Claire, Marina A. Solomos, Jungkil Kim, Gaoqiang Wang, Maxime A. Siegler, Michael F. Crommie, Thomas J. Kempa

2020Nature Communications69 citationsDOIOpen Access PDF

Abstract

Abstract The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo 2 (INA) 4 . These exceptionally uniform, high quality crystals cover areas up to 8600 µm 2 and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo 2 (INA) 4 clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.

Topics & Concepts

Chemical vapor depositionMaterials scienceSingle crystalNanotechnologyMetal-organic frameworkMetalConductivityPhase (matter)Crystal (programming language)Chemical engineeringOptoelectronicsChemistryCrystallographyAdsorptionOrganic chemistryPhysical chemistryComputer scienceMetallurgyEngineeringProgramming languageMetal-Organic Frameworks: Synthesis and ApplicationsSurface Chemistry and CatalysisMachine Learning in Materials Science