Control of conformational effects in layered kagome MOF films and systematic access to their use in electronic applications

层状共轭金属-有机骨架具有强的面内共轭和弱的面外范德华力，已成为实现导电材料的良好平台，并在可靠的场效应晶体管、自旋电子器件等精细电子应用中显示出巨大的前景，甚至可能显示出超导电性。然而，到目前为止，这一原则承诺还没有兑现。科学界面临的关键挑战之一是，如何在原子或分子水平上合成具有高结构控制性的层状共轭MOF，以实现特定的电子性质。在这方面，只有在COORNETs SPP中的协调计划中才能取得进展，如果合成化学和凝聚态物理联合起来--就像这里提议的项目中所做的那样。该提议的雄心勃勃的目标是开发具有可控层取向和功能的无氢Kagome 2D共轭MOF(2D c-MOF)薄膜，例如，通过选择配体和层堆积动机进行调整。为此，我们的目标是控制晶格结构，如几何形状、孔尺寸和金属-金属距离，从而实现电荷和自旋分布的平面工程。为了实现MOF薄膜的面外构象工程，即层取向/堆积控制，人们将致力于各种合成方法的发展，包括Langmuir-Blodgett辅助的在水合成和软模板辅助的界面合成。另一方面，我们的目标是发展一种系统的方法，通过电荷输运实验来分析即将开发的新型MOF的电子性质。为此，我们将开发纳米级的接触方案，使用高分辨率光刻来获得直流电荷传输特性。在开发最佳接触方案和挑选最佳MOF的初始筛选阶段之后，我们将研究霍尔效应、MOF作为薄膜晶体管在灵活的电子应用中的使用、自旋传输、超导或记忆特性或将其用作气体传感器。我们将进一步使用非接触式太赫兹扫描近场显微镜来获取局部交流电导。作为关键成果，我们希望建立新的电子结构和可靠的合成策略，描绘可靠的结构与传输关系，以展示新型Kagome MOF薄膜优越的电荷传输性能。我们的工作将使Kagome MOF成为通用的电子材料。

Layered conjugated metal-organic frameworks, characterized with strong in-plane conjugation and weak out-plane van der Waals force, have emerged as promising playground for realizing of electrically conductive materials and show large promise for delicate electronic applications such as reliable field-effect transistors, spintronic devices or possibly might even show superconductivity. However, up to now this principle promise has not been put into reality. One of the key challenges faced by the scientific community is, to synthesize layered conjugated MOFs with high structural control at the atomic or molecular level to dial-in specific electronic properties. In this respect, progress can be only reached in coordinated programs as in the COORNETs SPP and if synthetic chemistry and condensed matter physics join forces – as done in the here proposed project.The ambitious goal of the proposal is to develop hydrogen-free kagome 2D conjugated MOF (2D c-MOF) films with controlled layer orientation and functionality as for example tuned by choice of ligands and layer stacking motive on the one side. To this end, we aim to control lattice structures like geometries, pore sizes and metal-metal distances thus achieving in-plane engineering of charge and spin distribution. To achieve the out-of-plane conformational engineering, i.e., the layer orientation/stacking control in MOF films, a great effort will be devoted into the development of various synthetic methodologies, including the Langmuir-Blodgett-assisted on-water synthesis and soft-template-assisted interfacial synthesis. On the other side, we aim to develop a systematic methodology to analyze the electronic properties of the to-be-developed novel MOFs via charge transport experiments. To this end, we will develop nanoscale contacting schemes using high-resolution lithography to access DC-charge transport properties. After an initial screening phase to develop the best contacting schemes and single out the best MOFs, we will investigate Hall effect, the use of MOFs as thin-film transistors in flexible electronic applications, spin transport, superconductive or memristive properties or their use as gas sensors. We will further use non-contact THz-scanning near field microscopy to access the local AC conductivity.As key achievements, we expect to establish novel electronic structures and reliable synthesis strategies, delineation of reliable structure-transport relationships to demonstrate the superior charge transport performance of novel kagome MOF films. Our work will establish kagome MOFs as versatile electronic material.