Periodic Reporting for period 4 - ELECNANO (Electrically Tunable Functional Lanthanide Nanoarchitectures on Surfaces)
Berichtszeitraum: 2023-03-01 bis 2024-02-29
Lanthanide metals are ubiquitous nowadays, finding use in luminescent materials, optical amplifiers and waveguides, lasers, photovoltaics, rechargeable batteries, catalysts, alloys, magnets, bio-probes, and therapeutic agents. In addition, they bear potential for high temperature superconductivity, magnetic refrigeration, molecular magnetic storage, spintronics and quantum information.
Surprisingly, the study of lanthanide physico-chemical properties on surfaces is at its infancy, particularly at the nanoscale. To address this extraordinary scientific opportunity, we have researched the foundations and prospects of lanthanide elements to design functional nanoarchitectures on surfaces and studied their inherent physico-chemical phenomena in distinct coordination environments, targeting novel approaches for sensing, nanomagnetism and electroluminescence. Importantly, our studies encompass both metal substrates and decoupling surfaces including ultra-thin film insulators and graphene. Nurturing from these studies and in parallel, we have focused on graphene voltage back-gated supports (devices), thus surpassing the seminal knowledge on electrically-inert substrates and enhancing the scope of our research to address the overarching objective of the proposal, i.e. the design of electrically tunable functional lanthanide nanomaterials.
In summary, ELECNANO has allowed the deployment of state-of-the-art instrumentation for atomic scale visualization of advanced materials. The project has addressed the feasibility of designing complex lanthanide-directed metal-organic networks on surfaces, assessing their electronic and magnetic properties, while comparing them to their 3d-based materials counterparts.
In parallel, we have expanded the knowledge of porphyrinoid nanoscience at interfaces and coordination capabilities, while exploring novel reaction pathways for on-surface covalent synthesis.
Altogether, the proposal has paved new ways for the engineering of low-dimensional functional lanthanide-based nanomaterials.
Surprisingly, the study of lanthanide physico-chemical properties on surfaces is at its infancy, particularly at the nanoscale. To address this extraordinary scientific opportunity, we have researched the foundations and prospects of lanthanide elements to design functional nanoarchitectures on surfaces and studied their inherent physico-chemical phenomena in distinct coordination environments, targeting novel approaches for sensing, nanomagnetism and electroluminescence. Importantly, our studies encompass both metal substrates and decoupling surfaces including ultra-thin film insulators and graphene. Nurturing from these studies and in parallel, we have focused on graphene voltage back-gated supports (devices), thus surpassing the seminal knowledge on electrically-inert substrates and enhancing the scope of our research to address the overarching objective of the proposal, i.e. the design of electrically tunable functional lanthanide nanomaterials.
In summary, ELECNANO has allowed the deployment of state-of-the-art instrumentation for atomic scale visualization of advanced materials. The project has addressed the feasibility of designing complex lanthanide-directed metal-organic networks on surfaces, assessing their electronic and magnetic properties, while comparing them to their 3d-based materials counterparts.
In parallel, we have expanded the knowledge of porphyrinoid nanoscience at interfaces and coordination capabilities, while exploring novel reaction pathways for on-surface covalent synthesis.
Altogether, the proposal has paved new ways for the engineering of low-dimensional functional lanthanide-based nanomaterials.
In order to study the properties and functionalities of lanthanides at the nanoscale, the project focuses on the design and study of three distinct nanomaterials embedding lanthanide elements: metal-organic networks, metalated porphyrinoids and molecular species containing rare-earths.
To this aim, we rely on a powerful instrumentation based on surface science techniques. First, we have designed and deployed a state-of-the-art low-temperature nc-AFM-STM.
Work Package 1, the core of the project, has been developed successfully with the engineering of unique lanthanide metal-organic networks both on metals and on sp2-materials (graphene). On the one hand, concerning lanthanides, we are currently growing distinct networks on graphene, which are being rationalized and prepared for publication. We have also paid attention to multinuclear systems, revealing that we can tailor the energy level alignment and magnetic anisotropy on binuclear lanthanide architectures. Furthermore, we have revealed that we can engineer lanthanide-directed metallosupramolecular single molecule magnets (metallocenes). On the other hand, regarding 3d elements to compare their behaviour to the one with lanthanides and understand complex phases of matter, we have paid a lot of attention in cobalt-directed nanoarchitectures, pioneering novel antiferromagnetic materials and displaying how to tune the magnetic anisotropy by changing the coordination number.
In Work Package 2 we have focused on porphyrin-based nanoarchitectures. We have successfully sublimated expanded porphyrins and pioneered the field. We have also discovered a way to promote on-surface formation of porphyrin tapes while trying to metallate tetrapyrroles with lanthanides, opening for the first time the fascinating topic of hybrid metal-organic/covalent nanoarchitectures, which is a new and unexpected research areas of lanthanides by itself. In addition, following our discovery about the capabilities of the =CBr2 functional group for on-surface synthesis, we have developed unique molecular wires for molecular electronics.
In Work Package 3, centered on tip-induced electroluminescence, so far no luminescence from lanthanides could be measured, thus precluding any result for such workpackage, though leading us to the use of other substrates in future years.
Finally, we have implemented a device STM , targeted to explore the properties of lanthanide nanomaterials, while gating them on devices, though such research will be explored in future research.
The dissemination of the project has been highly successful producing very high quality impact articles (>10) and presenting them in leading scientific conferences.
Regarding outreach, thanks to the project we have participated in the Nanocar Race II, being eventually crowned the winners. Subsequently, we have promoted our research through distinct initiatives including the design of a videogame for internet. Motivated by the interest of such outreach project, Quantum Fracture (the leader of Science Communication in the Spanish language) has promoted a video about the Nanocar Race II, which now has been visited by 250,000 viewers.
In summary, the project has advanced the knowledge of the chemical, electronic and magnetic properties of lanthanide-based nanomaterials, anticipating fascinating discoveries in the near and mid-term future.
To this aim, we rely on a powerful instrumentation based on surface science techniques. First, we have designed and deployed a state-of-the-art low-temperature nc-AFM-STM.
Work Package 1, the core of the project, has been developed successfully with the engineering of unique lanthanide metal-organic networks both on metals and on sp2-materials (graphene). On the one hand, concerning lanthanides, we are currently growing distinct networks on graphene, which are being rationalized and prepared for publication. We have also paid attention to multinuclear systems, revealing that we can tailor the energy level alignment and magnetic anisotropy on binuclear lanthanide architectures. Furthermore, we have revealed that we can engineer lanthanide-directed metallosupramolecular single molecule magnets (metallocenes). On the other hand, regarding 3d elements to compare their behaviour to the one with lanthanides and understand complex phases of matter, we have paid a lot of attention in cobalt-directed nanoarchitectures, pioneering novel antiferromagnetic materials and displaying how to tune the magnetic anisotropy by changing the coordination number.
In Work Package 2 we have focused on porphyrin-based nanoarchitectures. We have successfully sublimated expanded porphyrins and pioneered the field. We have also discovered a way to promote on-surface formation of porphyrin tapes while trying to metallate tetrapyrroles with lanthanides, opening for the first time the fascinating topic of hybrid metal-organic/covalent nanoarchitectures, which is a new and unexpected research areas of lanthanides by itself. In addition, following our discovery about the capabilities of the =CBr2 functional group for on-surface synthesis, we have developed unique molecular wires for molecular electronics.
In Work Package 3, centered on tip-induced electroluminescence, so far no luminescence from lanthanides could be measured, thus precluding any result for such workpackage, though leading us to the use of other substrates in future years.
Finally, we have implemented a device STM , targeted to explore the properties of lanthanide nanomaterials, while gating them on devices, though such research will be explored in future research.
The dissemination of the project has been highly successful producing very high quality impact articles (>10) and presenting them in leading scientific conferences.
Regarding outreach, thanks to the project we have participated in the Nanocar Race II, being eventually crowned the winners. Subsequently, we have promoted our research through distinct initiatives including the design of a videogame for internet. Motivated by the interest of such outreach project, Quantum Fracture (the leader of Science Communication in the Spanish language) has promoted a video about the Nanocar Race II, which now has been visited by 250,000 viewers.
In summary, the project has advanced the knowledge of the chemical, electronic and magnetic properties of lanthanide-based nanomaterials, anticipating fascinating discoveries in the near and mid-term future.
The culmination of ELECNANO project will provide strategies for:
1.-Design of functional nanomaterials on high-technological supports.
2.-Development of advanced coordination chemistry on surfaces.
3.-Rationale of the physico-chemical properties of lanthanide-coordination environments.
4.-Engineering of lanthanide nanoarchitectures for ultimate sensing, nanomagnetism and electroluminescence.
5.-Atomistic insights of electrically tunable materials and unprecedented fundamental studies of charged-molecule/metal physics on devices.
This ERC project will be in the vanguard of knowledge of physics and chemistry, and will be skippered by our expertise of complex surface characterization with scanning probe microscopies and spectroscopy. The funding of this project would consolidate us as leading pioneers in the innovative field of lanthanides at the nanoscale.
1.-Design of functional nanomaterials on high-technological supports.
2.-Development of advanced coordination chemistry on surfaces.
3.-Rationale of the physico-chemical properties of lanthanide-coordination environments.
4.-Engineering of lanthanide nanoarchitectures for ultimate sensing, nanomagnetism and electroluminescence.
5.-Atomistic insights of electrically tunable materials and unprecedented fundamental studies of charged-molecule/metal physics on devices.
This ERC project will be in the vanguard of knowledge of physics and chemistry, and will be skippered by our expertise of complex surface characterization with scanning probe microscopies and spectroscopy. The funding of this project would consolidate us as leading pioneers in the innovative field of lanthanides at the nanoscale.