User Community Science: Soft decoupling of organic molecules on metal
The illustration shows how iodine (purple) is embedded between the organic layer and the metal, thus reducing adhesion. © IFM, University of Linköping
An international team has discovered an elegant way to decouple organic nanosheets grown on metal surfaces. After iodine intercalation, measurements at the synchrotron source BESSY II of Helmholtz-Zentrum Berlin (HZB) showed that a network of organic molecules behaved almost as it was free-standing. The strong influence of the metal on the network was reduced. This opens up new ways to transfer organic nanostructures from metal surfaces onto more suitable substrates for molecular electronics. The results have been published in “Angewandte Chemie”.
Specific organic molecules – typically on reactive metallic surfaces – can interlink via chemical bond formation into extended nanostructures. Highly stable two-dimensional molecular networks can be grown in this manner. However, these networks then adhere to the metallic support, which also strongly influences their properties. To make use of these kinds of organic networks in molecular electronics, for instance, the metal would have to be laboriously removed.
Iodine vapour reduces adhesion
Now a team headed by Markus Lackinger at the Technische Universität München and the Deutsches Museum together with partners at other universities in Germany and Sweden have discovered an elegant way to reduce the adhesion between the network and the metal. They simply exposed the networks bound to the metal to iodine vapour. “After the networks had been synthesized on a silver surface, we used iodine vapour. We hoped iodine would embed between the organic layer and the metal”, explains Lackinger. To do this, they investigated a nanosheet consisting of interlinked phenyl rings (polyphenylene) on a silver surface. The iodine actually migrated beneath the interlinked phenyl rings to form an atomically thin interlayer on the metal surface. After the intercalation of the iodine, measurements at BESSY II proved that the molecular network behaved almost as if it was detached. The strong influence of the metal was reduced.
Application: New transfer techniques
These results could be advantageous for future applications. “Molecular nanosheets do not grow on any surface. For this reason, we have to develop transfer techniques. Then we could fabricate the networks on metal surfaces and subsequently transfer them over to other surfaces that are more suitable for molecular electronics. Being able to mitigate the adhesion with an iodine interlayer is possibly a first step in this direction”, explains Lackinger.
Publication: Post-Synthetic Decoupling of On-Surface Synthesized Covalent Nanostructures from Ag(111), Atena Rastgoo-Lahrood, Jonas Björk, Matthias Lischka, Johanna Eichhorn, Stephan Kloft, Massimo Fritton, Thomas Strunskus, Debabrata Samanta, Michael Schmittel, Wolfgang M. Heckl, Markus Lackinger, Angew. Chem. Int. Ed.. doi: 10.1002/anie.201600684
- BESSY II: How intrinsic oxygen shortens the lifespan of solid-state batteriesAlthough solid-state batteries (SSBs) demonstrate high performance and are intrinsically safe, their capacity currently declines rapidly. A team from the TU Wien, Humboldt-University Berlin and HZB has now analysed a TiS₂|Li₃YCl₆ solid-state half-cell in operando at BESSY II using a special sample environment that allows for non-destructive investigation under real operating conditions. Data obtained by combination of soft and hard X-ray photoelectron spectroscopy (XPS and HAXPES) revealed a new degradation mechanism that had not previously been identified in solid-state batteries. They have gained some surprising insights, particularly regarding the harmful role played by intrinsic oxygen. This study provides valuable information for improving design and handling of such batteries.
- Spintronics at BESSY II: Real-time analysis of magnetic bilayer systemsSpintronic devices enable data processing with significantly lower energy consumption. They are based on the interaction between ferromagnetic and antiferromagnetic layers. Now, a team from Freie Universität Berlin, HZB and Uppsala University has succeeded in tracking, for each layer separately, how the magnetic order changes after a short laser pulse has excited the system. They were also able to identify the main cause of the loss of antiferromagnetic order in the oxide layer: the excitation is transported from the hot electrons in the ferromagnetic metal to the spins in the antiferromagnet.
- Environmental Chemistry at BESSY II: Radicals in waterwaysHow do radicals form in aqueous solutions when exposed to UV light? This question is important for health research and environmental protection, for example with regard to the overfertilisation of water bodies by intensive agriculture. A team at BESSY II has now developed a new method of investigating hydroxyl radicals in solution. By using a clever trick, the scientists gained surprising insights into the reaction pathway.