ULISSE - Using Electrostatic Interactions to Control Supramolecular Self-Assembly at Surfaces
Lead Research Organisation:
King's College London
Department Name: Physics
Abstract
A major promise made by Nanotechnology Research to contemporary society is that next-generation molecular-scale devices will be faster, more versatile and more energy efficient than the ones based on current technology. Organic molecules are among the best candidate bricks for future nanoscale device fabrication. Their chemical structure can be easily modified, suggesting that carefully designed molecules could in principle assemble spontaneously into any desired structure, with no need of top down intervention. The optimisation by design of the chemical linkage between molecules has been, correspondently, an extensively explored concept in the molecular self-assembly field, albeit in some way limited in its scope by the short-range character of the bonding. Very recent research suggests that controlling the state of charge of organic molecules may provide a further direct handle to determine the assembly features on larger scales, through the contribution of long-range electrostatic interactions. However, this possibility is still virtually unexplored, in spite of its potential impact on nanofabrication. The electronic properties of molecular organic materials are, meanwhile, also attracting a massive, and ever growing, interest. Indeed, Organic Electronics is currently a booming field, with novel light-emission and light-energy conversion applications of strategic importance for society being investigated and early devices being produced. Once more, some crucial properties of these devices are determined by processes occurring at the nanometre scale and involve electrostatic interactions. Charge transfer between a metal surface and a layer of organic molecules deposited on it is known, e.g., to control the electric conduction properties of a metal-organic contact. However, no consensus has been reached yet on how to model such metal-organic interfaces properly, and device design is often a trial-and-error process.The present project will study charge transfer processes between organic molecules and metallic substrates, and their connection with self-assembly. Using both theory and experiment, we will investigate if these processes can be predicted and controlled by appropriate choices of molecules, substrates and coverages. The work will be useful for both understanding fundamental principles of molecular self-organisation and for unravelling the fundamental mechanisms that govern energy level alignment at metal-organic interfaces. Crucially, the whole will be much more than the sum of the parts. Namely, starting from charge transfer and pursuing the self-assembly route, we will determine if long-range forces between charged molecules can drive the spontaneous formation of novel classes of supramolecular structures. This would represent a novel tool for predicting and controlling the assembly. Conversely, starting from the observed assembly and pursuing the Organic Electronic route, we will investigate if specific molecular linkage patterns can reveal the occurrence of charge transfer. This would provide a novel route to precious information on the electronic properties of metal-organic interfaces. Electronic structure calculations, photoemission spectroscopy experiments, molecular dynamics simulations, and scanning tunnelling microscopy imaging will be used throughout the investigation. This will link two strategic fields of research which can greatly benefit from each other, namely nanofabrication by supramolecular assembly and molecular electronics, for the first time in an integrated UK-based project.
People |
ORCID iD |
Alessandro De Vita (Principal Investigator) |
Publications
Abdurakhmanova N
(2012)
Stereoselectivity and electrostatics in charge-transfer Mn- and Cs-TCNQ4 networks on Ag(100).
in Nature communications
Della Pia A
(2016)
Two-Dimensional Ketone-Driven Metal-Organic Coordination on Cu(111).
in Chemistry (Weinheim an der Bergstrasse, Germany)
Della Pia A
(2014)
Anomalous coarsening driven by reversible charge transfer at metal-organic interfaces.
in ACS nano
Della Pia A
(2016)
Two-dimensional core-shell donor-acceptor assemblies at metal-organic interfaces promoted by surface-mediated charge transfer.
in Nanoscale
Doni G
(2013)
Structural and energetic basis for hybridization limits in high-density DNA monolayers.
in Nanoscale
Feng Z
(2015)
Trapping of Charged Gold Adatoms by Dimethyl Sulfoxide on a Gold Surface.
in ACS nano
Floris A
(2013)
Fine-tuning the electrostatic properties of an alkali-linked organic adlayer on a metal substrate.
in ACS nano
Kalashnyk N
(2014)
Self-assembly of decoupled borazines on metal surfaces: the role of the peripheral groups.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Kervyn S
(2013)
"Magic" surface clustering of borazines driven by repulsive intermolecular forces.
in Angewandte Chemie (International ed. in English)
Lo Cicero M
(2017)
A long-range ordered array of copper tetrameric units embedded in an on-surface metal organic framework.
in The Journal of chemical physics
Marsden A
(2013)
Is graphene on copper doped?
in physica status solidi (RRL) - Rapid Research Letters
Moreton B
(2013)
Dissociation and hierarchical assembly of chiral esters on metallic surfaces.
in Chemical communications (Cambridge, England)
Ohmann R
(2011)
Influence of subsurface layers on the adsorption of large organic molecules on close-packed metal surfaces.
in ACS nano
Riello M
(2014)
Pressure-induced conformation transition of o-phenylene solvated in bulk hydrocarbons.
in The journal of physical chemistry. B
Vitali L
(2010)
Portrait of the potential barrier at metal-organic nanocontacts.
in Nature materials
Vulcano R
(2017)
Toward Fractioning of Isomers through Binding-Induced Acceleration of Azobenzene Switching.
in Journal of the American Chemical Society
Wilson N
(2013)
Weak mismatch epitaxy and structural Feedback in graphene growth on copper foil
in Nano Research
Description | The project addressed the investigation of the self-assembly of molecules adsorbed on atomically smooth metal surfaces, and in particular how electrostatic forces drive the assembly. The project clarified subtle aspects of the electronic structure properties of metal-organic interfaces, and particular attention paid to clarifying how charge transfer affects electronic level alignment at the interface - a key property in advanced organic electronic devices. In the course of the work we (i) obtained the first ever molecule-scale portrait of the electrostatic field associated with a single, adsorbed molecule. We also (ii) demonstrated that it is possible to use electrostatic interactions to fabricate highly specific highly symmetric complex structures, such as, e.g., decagons of pentagons of rubrene molecules. We then (iii) investigated subtle influences of the subsurface metal layers within the substrate to influence the symmetry of the assembled molecular structures. We furthermore showed that (iv) electrostatic repulsion between molecules can be engineered into the assembly unit monomer used, and used to tune the assembly outcome (e.g., into small magic clusters of predetermined shape rather than large domains). Finally (v) we took the organic molecular layer assembly fabrication route to a new complexity level by introducing the use of alkali atoms as linkers between molecules, showing that alkali atoms can be more flexible and versatile than standard transition metal atoms as active linker used for producing regular organic supramolecular domains with desired electronic properties. |
Exploitation Route | This research has both industrial interest in the organic electronic field and fundamental interest, in that it could be used to showcase to the general public the state-of-the-art in supramolecular fabrication. The project's central ideas clarified how to generate distinctively regular structures in a controlled way, and how to do so using electrostatic interactions, demonstrating the power of the self-assembly route to nanofabrication. This research provided important new insight into possible nanofabrication routes for metal organic interfaces. It could e.g., be exploited by exploring ideas such as using alkali-metal-linked or functionalised borazine-based organic interlayers while fabricating metal organic interfaces, to achieve contacts with controlled level alignment for use in organic-electronics devices. |
Sectors | Chemicals,Electronics,Energy |
Description | The project was mainly investigating the behaviour of organic molecules on metal surfaces, involving chemical reactions catalysed by the substrate, and conformational changes in organic molecules i.e., a class of reactions of primary interest for energy companies. These results were advertised on the TYC website (London Centre for Theory and Simulation of Materials, which offers industrial services). Notably, a novel collaboration ensued, fully funded by BP and tackling a number of technologically important problems, which produced original and potentially technologically useful results e.g., on the pressure-induced behaviour of advanced functional molecules immersed in bulk hydrocarbon model fuels (a subsection of these results have been published). Similarly useful results concerning the assembly of molecules at solid-liquid interfaces in hydrocarbon solutions were also produced, which are possibly relevant for product development. |
Sector | Chemicals |
Impact Types | Economic |
Description | Collaboration with BP Formulated Products Technology |
Organisation | BP (British Petroleum) |
Country | United Kingdom |
Sector | Private |
PI Contribution | My group provided know how in running molecular dynamics simulations on hydrocarbon systems |
Collaborator Contribution | They collaborated to the development of ideas and candidate systems for a common publication. |
Impact | Publication: DOI: 10.1021/jp5096272 |
Start Year | 2012 |
Description | Collaboration with TASC Padriciano AFM and Univ. of Udine |
Organisation | TASC laboratories, Padriciano (Trieste) |
Country | Italy |
Sector | Academic/University |
PI Contribution | A new and fruitful collaboration with the group of Dr. Loredana Casalis at the TASC laboratories, Trieste, Italy, and Prof. Giacinto Scoles, Udine Italy, was enabled by the ULISSE grant (cf. paper on DNA assembly properties). The role of my group in this collaboration was to provide expertise in molecular dynamics modelling. |
Collaborator Contribution | The Casalis group carries out AFM experiments on self-assembled molecular adlayers with potential use as sensors in nanomedicine. The collaboration also extended to include Prof. Giacinto Scoles, FRSC, formerly working at Princeton NJ and the ELETTRA Synchrotron and the International School for Advanced Studies (SISSA) in Trieste, Italy, and currently working at the MOlecular NAnotechnology for LIfe Science Applications (MONALISA) at university of Udine, Italy. |
Impact | Publication: DOI: 10.1039/c3nr01799k collaboration is multi-disciplinary (since nanomedical sensors are the target of the study) |
Start Year | 2012 |
Description | Collaboration with TASC Padriciano AFM and Univ. of Udine |
Organisation | University of Udine |
Country | Italy |
Sector | Academic/University |
PI Contribution | A new and fruitful collaboration with the group of Dr. Loredana Casalis at the TASC laboratories, Trieste, Italy, and Prof. Giacinto Scoles, Udine Italy, was enabled by the ULISSE grant (cf. paper on DNA assembly properties). The role of my group in this collaboration was to provide expertise in molecular dynamics modelling. |
Collaborator Contribution | The Casalis group carries out AFM experiments on self-assembled molecular adlayers with potential use as sensors in nanomedicine. The collaboration also extended to include Prof. Giacinto Scoles, FRSC, formerly working at Princeton NJ and the ELETTRA Synchrotron and the International School for Advanced Studies (SISSA) in Trieste, Italy, and currently working at the MOlecular NAnotechnology for LIfe Science Applications (MONALISA) at university of Udine, Italy. |
Impact | Publication: DOI: 10.1039/c3nr01799k collaboration is multi-disciplinary (since nanomedical sensors are the target of the study) |
Start Year | 2012 |
Description | Collaboration with TASC Padriciano STM |
Organisation | TASC laboratories, Padriciano (Trieste) |
Country | Italy |
Sector | Academic/University |
PI Contribution | We provided part of the theoretical modelling contribution to a research work investigating the adatom-promoted assembly of DMSO molecules. |
Collaborator Contribution | The TASC group of Prof. G.Comelli (including C.Dri and Z.Feng) have carried out all the Scanning Tunneling Electron Microscopy work within the collaboration. |
Impact | Publication: ACS NANO 10.1021/acsnano.5b02284 |
Start Year | 2013 |
Description | Collaboration with Univ. of Namur |
Organisation | Heriot-Watt University |
Department | Chemistry |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | A fruitful collaboration with Prof. Dr. Davide Bonifazi ( university of Namur, Belgium, and University of Trieste, Italy, recently moved to Cardiff University) has been enabled by the ULISSE grant . My team provided the theoretical modelling expertise to the ULISSE collaboration. |
Collaborator Contribution | This added considerable value to the ULISSE project, extending it to include the chemical synthesis side of supramolecular assembly at no additional cost for the project (for an example of output: see e.g., published paper on borazine assembly). |
Impact | Publications: DOI: 10.1002/chem.201402839 DOI: 10.1021/nn505063w DOI: 10.1021/jp5096272 |
Start Year | 2010 |
Description | Collaboration with Univ. of Namur |
Organisation | University of Namur |
Country | Belgium |
Sector | Academic/University |
PI Contribution | A fruitful collaboration with Prof. Dr. Davide Bonifazi ( university of Namur, Belgium, and University of Trieste, Italy, recently moved to Cardiff University) has been enabled by the ULISSE grant . My team provided the theoretical modelling expertise to the ULISSE collaboration. |
Collaborator Contribution | This added considerable value to the ULISSE project, extending it to include the chemical synthesis side of supramolecular assembly at no additional cost for the project (for an example of output: see e.g., published paper on borazine assembly). |
Impact | Publications: DOI: 10.1002/chem.201402839 DOI: 10.1021/nn505063w DOI: 10.1021/jp5096272 |
Start Year | 2010 |