ABSTRACT
Recent progress in synthesizing and integrating surface-supported metal-organic frameworks (SURMOFs) has highlighted their potential in developing hybrid electronic devices with exceptional mechanical flexibility, film processability, and cost-effectiveness. However, the low electrical conductivity of SURMOFs has limited their use in devices. To address this, researchers have utilized the porosity of SURMOFs to enhance electrical conductivity by incorporating conductive materials. This study introduces a method to improve the electrical conductivity of HKUST-1 templates by in situ polymerization of conductive polypyrrole (PPy) chains within the SURMOF pores (named as PPy@HKUST-1). Nanomembrane-origami technology is employed for integration, allowing a rolled-up metallic nanomembrane to contact the HKUST-1 films without causing damage. After a 24 h loading period, the electrical conductivity at room temperature reaches approximately 5.10-6 S m-1 . The nanomembrane-based contact enables reliable electrical characterization even at low temperatures. Key parameters of PPy@HKUST-1 films, such as trap barrier height, dielectric constant, and tunneling barrier height, are determined using established conduction mechanisms. These findings represent a significant advancement in real-time control of SURMOF conductivity, opening pathways for innovative electronic-optoelectronic device development. This study demonstrates the potential of SURMOFs to revolutionize hybrid electronic devices by enhancing electrical conductivity through intelligent integration strategies.
ABSTRACT
Organic diodes and molecular rectifiers are fundamental electronic devices that share one common feature: current rectification ability. Since both present distinct spatial dimensions and working principles, the rectification of organic diodes is usually achieved by interface engineering, while changes in molecular structures commonly control the molecular rectifiers' features. Here, we report on the first observation of temperature-driven inversion of the rectification direction (IRD) in ensemble molecular diodes (EMDs) prepared in a vertical stack configuration. The EMDs are composed of 20 nm thick molecular ensembles of copper phthalocyanine in close contact with one of its fluorinated derivatives. The material interface was found to be responsible for modifying the junction's conduction mechanisms from nearly activationless transport to Poole-Frenkel emission and phonon-assisted tunneling. In this context, the current rectification was found to be dependent on the interplay of such distinct charge transport mechanisms. The temperature has played a crucial role in each charge transport transition, which we have investigated via electrical measurements and band diagram analysis, thus providing the fundamentals on the IRD occurrence. Our findings represent an important step towards simple and rational control of rectification in carbon-based electronic nanodevices.
