†Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany.
‡Applied Physical Chemistry, University of Heidelberg, 69120 Heidelberg, Germany.
ACS Appl Mater Interfaces. 2015 May 13;7(18):9824-30. doi: 10.1021/acsami.5b01792. Epub 2015 Apr 29.
Understanding of the electric transport through surface-anchored metal-organic frameworks (SURMOFs) is important both from a fundamental perspective as well as with regards to possible future applications in electronic devices. To address this mostly unexplored subject, we integrated a series of representative SURMOF thin films, formed by copper nodes and trimesic acid and known as HKUST-1, in a mercury-drop-based tunneling junction. Although the transport properties of these SURMOFs are analogous to those of hybrid metal-organic molecular wires, manifested by a very low value of the tunneling decay constant (β ≈ 0.006 Å(-1)), they are at the same time found to be consistent with a linear increase of resistance with film thickness. Upon loading of SURMOF pores with ferrocene (Fc), a noticeable increase in transport current was observed. A transport model and ab initio electronic structure calculations were used to reveal a hopping transport mechanism and to relate the changes upon Fc loading to those of the electronic and vibrational structures of the SURMOF films.
理解通过表面锚定的金属有机骨架（SURMOF）的电子输运无论是从基础研究的角度，还是从未来电子器件的潜在应用的角度来看都非常重要。为了研究这一大部分尚未探索的课题，我们将一系列具有代表性的 SURMOF 薄膜（由铜节点和均苯三甲酸组成，称为 HKUST-1）集成到汞滴基隧道结中。尽管这些 SURMOF 的输运性质类似于混合金属有机分子线，表现为隧道衰减常数（β≈0.006 Å-1）非常低，但同时发现它们与膜厚度的电阻线性增加一致。当 SURMOF 孔中装载二茂铁（Fc）时，观察到传输电流明显增加。使用传输模型和从头算电子结构计算揭示了一个跳跃传输机制，并将 Fc 负载时的变化与 SURMOF 薄膜的电子和振动结构的变化联系起来。
