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PHOSFUN Report Summary

Project ID: 670173
Funded under: H2020-EU.1.1.

Periodic Reporting for period 1 - PHOSFUN (Phosphorene functionalization: a new platform for advanced multifunctional materials)

Reporting period: 2015-07-01 to 2016-12-31

Summary of the context and overall objectives of the project

Upto few years ago, chemists were only great builders of zero- and mono-dimensional architectures, molecules and polymers. Nowadays they started to obtain some control overthree-dimensional objects like metal-organic frameworks or some supramolecular architectures built using ad hoc building blocks. The last frontier is represented by 2D materials. The latter have attracted a great interest due to their exceptional electronic and optical properties, with a plethora of potential astounding applications covering microelectronics, optoelectronics, medicine etc. Until a few years ago, this field has been monopolized by graphene for the extraordinary combination of structural and functional properties, although its usein electronics has been hampered by the lack of a bandgap. Such a drawback may be overcome using phosphorene the “graphene cousin”, which features a direct bandgap, that can be largely tuned depending by the number of stacked layers. Phosphorene is the mono-layer of layered black phosphorus, obtained by exfoliation of the latter.
PHOSFUN project is a voyage in the reactivity and functionalization of phosphorene layers with small molecules and transition metal fragments up to the final realization and implementation of devices. The project has as added value the combination of different expertise: experimental chemists, computational chemists, material scientists and physicists. A complete control of how to modulate the chemical and physical properties of the functionalized materials is crucial for the development of new devices with many applications for society, in particular, in the field of energy harvesting and conversion, catalysis, and electronics. The overall objective of the PHOSFUN project is the demonstration and build-up of a chain-of-value based on phosphorene as a platform from the synthesis to device realization and implementation. The final aim is to achieve a complete control of the reactivity of the material and the resulting properties.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

The leitmotif of the project PHOSFUN is the investigation of phosphorene as a platform to be chemically and physically functionalized for the final manufacture of devices and application in a variety of areas. The approach, used during this first reporting period (1-18 month), was a bottom-up one starting with the synthesis of large amounts of high quality black phosphorus, the basis for the next steps. The obtained material provided few-layers black-phosphorus after exfoliation, both in solution and micromechanical one. Scientific articles have already been published by the PHOSFUN team: one paper concerns the role of water in the exfoliation in DMSO solution, and the second is related to physical measurements about weak-localization observation in black phosphorus flakes The black phosphorus and the exfoliated one have been employed as starting material for the investigation of chemical functionalization or for the formation and the investigation of heterostructures, by embedding black phosphorus flakes in polymeric matrixes, such as polystyrene. A third article was already published on the latter topic. The obtained results in the field of heterostructures are particularly appealing because they open still unexplored pathways for the synthesis of new materials with innovative electronic properties. In the field of functionalization, the research has focused on the reactivity of the exfoliated material with metals and small molecules. Many results have already been obtained, and some manuscripts are ready to be published. All the experimental procedures have been substantiated by detailed computational investigations and adhoc spectroscopic experiments, such as Raman and electronic microscopy.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

We have developed a new protocol for liquid exfoliation of Black Phosphorus. A new composite material based on a phosphorene-dispersion has been obtained, and we have demonstrated the enhanced stability of the material in air and at room temperature once incorporated inside the polymer. We also correlated the anisotropic crystalline structure of black phosphorus (bP) with weak localization effects measured in a few-layer bP field-effect transistor device. We have identified non-conventional wet processing and deposition techniques towards the realization of electronic bP devices.
Chemistry is about control at molecular level. So a fine control of the structure of phosphorene and 2D material in general will open avenues in the building of new devices as sensors or new smart materials but also in catalysis as a tool for assembling of new molecules.
This project is providing a first insight into the properties and the control of 2D materials. On the other hand, nowadays we useapplications and devices in our daily life which could be only imagined fifty year ago. For the majority of people, most of commonplace electronic devices are just black boxes although they are built using molecules and materials shaped by physics and chemistry.
We are firmly convinced that in the future phosphorene-based materials developed in this project will find their use inside these black boxes.
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