Charge Transfer Induced Molecular Hole Doping into Thin Film of Metal-Organic-Frameworks

TL;DR

This study demonstrates that iodine doping induces hole doping in Co3(NDC)3DMF4 MOF thin films, transforming them from insulators to p-type semiconductors, with potential applications in optoelectronic devices.

Contribution

It introduces a method to enhance MOF electrical conductivity via iodine doping, enabling their use in electronic and optoelectronic applications.

Findings

Iodine doping converts MOFs into p-type semiconductors.

Charge transfer induces hole doping in MOFs.

Enhanced interfacial charge transfer with TiO2 observed.

Abstract

Despite the highly porous nature with significantly large surface area, metal organic frameworks (MOFs) can be hardly used in electronic, and optoelectronic devices due to their extremely poor electrical conductivity. Therefore, the study of MOF thin films that require electron transport or conductivity in combination with the everlasting porosity is highly desirable. In the present work, thin films of Co3(NDC)3DMF4 MOFs with improved electronic conductivity are synthesized using layer-by-layer and doctor blade coating techniques followed by iodine doping. The as-prepared and doped films are characterized using FE-SEM, EDX, UV/Visible spectroscopy, XPS, current-voltage measurement, photoluminescence spectroscopy, cyclic voltammetry, and incident photon to current efficiency measurements. In addition, the electronic and semiconductor property of the MOF films are characterized using Hall Effect measurement, which reveals that in contrast to the insulator behavior of the as-prepared MOFs, the iodine doped MOFs behave as a p-type semiconductor. This is caused by charge transfer induced hole doping into the frameworks. The observed charge transfer induced hole doping phenomenon is also confirmed by calculating the densities of states of the as-prepared and iodine doped MOFs based on density functional theory. Photoluminescence spectroscopy demonstrate an efficient interfacial charge transfer between TiO2 and iodine doped MOFs, which can be applied to harvest solar radiations.