title: Charge Transfer-Induced Molecular Hole Doping into Thin Film of Metal-Organic Frameworks.
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 properties 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 demonstrates an efficient interfacial charge transfer between TiO2 and iodine doped MOFs, which can be applied to harvest solar radiations.
authors.affiliation: Department of Chemistry, Hanyang University , Seoul 133-791, Republic of Korea.
authors.forename: Deok Yeon
authors.initials: DY
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Hanyang University , Seoul 133-791, Republic of Korea.
authors.forename: Eun-Kyung
authors.initials: EK
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Hanyang University , Seoul 133-791, Republic of Korea.
authors.forename: Nabeen K
authors.initials: NK
authors.lastname: Shrestha
authors.affiliation: Department of Chemistry, Hanyang University , Seoul 133-791, Republic of Korea.
authors.forename: Danil W
authors.initials: DW
authors.lastname: Boukhvalov
authors.affiliation: Energy Storage Research Center, Korea Institute of Science and Technology , Seoul 136-791, Republic of Korea.
authors.forename: Joong Kee
authors.initials: JK
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Hanyang University , Seoul 133-791, Republic of Korea.
authors.forename: Sung-Hwan
authors.initials: SH
authors.lastname: Han
keywords: Hall Effect measurement; MOFs; charge transfer complex; molecular hole doping; thin film