Single-Molecule Plasmoelectronics
Lead Research Organisation:
University of Liverpool
Department Name: Chemistry
Abstract
Continuing miniaturization of electronic components in computer chips will eventually lead to component sizes on the molecular scale. Conventional semiconductor nanostructures at these length scales will suffer from increased leakage currents due to tunnelling as well as increased thermal effects due to higher power densities. The need for developing alternative approaches has created over the last two decades the field of molecular electronics, in which electronic components are realized using single molecules. Numerous examples of prototypical devices such as diodes, memory elements and transistors employing individual molecules have been demonstrated.
One of the most important functions is the control of the current through a device with an external stimulus, i.e. gating. Stimuli which have been employed include electrostatic and electrochemical potentials, temperature, and light. Light is one of the most attractive options since it potentially allows coupling single-molecular devices with future optoelectronic circuitry, holding the promise of ultimate speed and miniaturization.
Efficient coupling of light with nanoscale objects can be achieved using plasmonic nanostructures that concentrate and focus light beyond the diffraction limit. In combination with electronic devices one speaks of plasmoelectronics. Such efficient and spatially confined coupling is a pre-requisite for the tight integration of optically gate-able molecular devices on the sub-100 nm scale. The proposed research aims at realizing single-molecular plasmoelectronic devices in which the current through a single molecule coupled to a plasmonic nanostructure is gated by external illumination. The envisaged device structures will take advantage of the plasmonic properties of noble metal nanoparticles that serve as the electrodes of the single-molecule junction. This research will open new opportunities for miniaturization, integration, and control of optoelectronic devices to the single-molecule level.
The research is interdisciplinary spanning physics, chemistry, molecular electronics and plasmonics. This is reflected in the research team which brings together expertise in organic synthesis of single-molecular conductors (Beeby, Durham), single-molecule conduction measurements (Nichols, Higgins, Liverpool), and nanoplasmonics (Jaeckel, Liverpool). This broad expertise will allow for a systematic approach varying the chemical nature of the molecular conductor and matching it with the plasmonic properties of the single-molecule junction. This will allow detailed characterization of parameters such as spectral overlap and electronic coupling in the junction and their relation to the optical gating effect in the device. The single-molecule approach will eliminate both ensemble averaging effects which can mask important effects in macroscopic measurements and sample heterogeneity which makes interpretation of results more complex. The project will deliver a fundamental understanding of plasmoelectronic single-molecule junctions and formulate design rules for future devices. The results will also open new opportunities in related research areas such photovoltaics, organic electronics, and catalysis.
One of the most important functions is the control of the current through a device with an external stimulus, i.e. gating. Stimuli which have been employed include electrostatic and electrochemical potentials, temperature, and light. Light is one of the most attractive options since it potentially allows coupling single-molecular devices with future optoelectronic circuitry, holding the promise of ultimate speed and miniaturization.
Efficient coupling of light with nanoscale objects can be achieved using plasmonic nanostructures that concentrate and focus light beyond the diffraction limit. In combination with electronic devices one speaks of plasmoelectronics. Such efficient and spatially confined coupling is a pre-requisite for the tight integration of optically gate-able molecular devices on the sub-100 nm scale. The proposed research aims at realizing single-molecular plasmoelectronic devices in which the current through a single molecule coupled to a plasmonic nanostructure is gated by external illumination. The envisaged device structures will take advantage of the plasmonic properties of noble metal nanoparticles that serve as the electrodes of the single-molecule junction. This research will open new opportunities for miniaturization, integration, and control of optoelectronic devices to the single-molecule level.
The research is interdisciplinary spanning physics, chemistry, molecular electronics and plasmonics. This is reflected in the research team which brings together expertise in organic synthesis of single-molecular conductors (Beeby, Durham), single-molecule conduction measurements (Nichols, Higgins, Liverpool), and nanoplasmonics (Jaeckel, Liverpool). This broad expertise will allow for a systematic approach varying the chemical nature of the molecular conductor and matching it with the plasmonic properties of the single-molecule junction. This will allow detailed characterization of parameters such as spectral overlap and electronic coupling in the junction and their relation to the optical gating effect in the device. The single-molecule approach will eliminate both ensemble averaging effects which can mask important effects in macroscopic measurements and sample heterogeneity which makes interpretation of results more complex. The project will deliver a fundamental understanding of plasmoelectronic single-molecule junctions and formulate design rules for future devices. The results will also open new opportunities in related research areas such photovoltaics, organic electronics, and catalysis.
Planned Impact
This proposal represents early stage work in the development of "plasmoelectronics" in which plasmon mediated optical excitation of molecular electrical junctions is used to control their electrical properties. We aim to do achieve this down to the single-molecule and single-nanoparticle level, hence realizing plasmonically gate-able single-molecular junctions. This will be an interdisciplinary effort with the team having the expertise to design and synthesise the molecular and plasmonic nanostructures, to characterise and understand their photo-physical properties and to perform the optically gated scanning probe microscopy studies necessary for device characterisation under optical illumination. Through defined experiments we aim to both fundamentally understand the plasmonic gating effect and to establish design rules for efficient plasmonic gating of future molecular devices.
We expect impact of our research in the following areas:
i) Economy
By establishing design rules for future plasmonically gate-able devices and securing connected intellectual property we will lay foundations for future applications of plasmoelectronic devices. Although any future technological implementation of plasmoelectronics is unlikely to be initially at the single-molecule level, the measurements we propose at the single molecule level offer us a defined way for establishing understanding and design rules through measurements in which the molecular bridge and plasmonic nanostructure are varied. The technological impact of plasmoelectronics has recently been highlighted in the literature by Nitzan and Galperin. These will include new molecular scale devices or sensors or also spin-off applications in organic photovoltaics or organic electronics. According to the International Technology Roadmap for Semiconductors (ITRS) the anticipated timeline for developing molecular electronics is currently in a fundamental research phase (until 2018), then transitions into development (2019-2021) and then onwards to production (from 2022). Thus we expect technologically relevant impact in terms of technologies applicable in electronic devices on the 5-10 year time scale. In the long term this will strengthen the UK's position in this future technology sector.
ii) People
The project will train young researchers and provide them with necessary skills to shape and drive the future development and production phase outlined in the ITRS starting in 2019. These include specific knowledge of the realisation and characterisation of molecular electronic devices but also more generic skill such as project management and effective communication.
iii) Society
In the short term dissemination and description of our research in accessible formats will contribute to the education of the public about the opportunities and risks associated with nanotechnology. In the long term, and intimately connected to the outlined technological impact, quality of life will be improved by the introduction of new products utilizing plasmoelectronics. These may include sectors of electronics (new device structures), health care (novel sensors), or energy (more efficient photovoltaics).
iv) Knowledge
We also expect major academic impact which is outlined in more detail in the academic beneficiary section.
We expect impact of our research in the following areas:
i) Economy
By establishing design rules for future plasmonically gate-able devices and securing connected intellectual property we will lay foundations for future applications of plasmoelectronic devices. Although any future technological implementation of plasmoelectronics is unlikely to be initially at the single-molecule level, the measurements we propose at the single molecule level offer us a defined way for establishing understanding and design rules through measurements in which the molecular bridge and plasmonic nanostructure are varied. The technological impact of plasmoelectronics has recently been highlighted in the literature by Nitzan and Galperin. These will include new molecular scale devices or sensors or also spin-off applications in organic photovoltaics or organic electronics. According to the International Technology Roadmap for Semiconductors (ITRS) the anticipated timeline for developing molecular electronics is currently in a fundamental research phase (until 2018), then transitions into development (2019-2021) and then onwards to production (from 2022). Thus we expect technologically relevant impact in terms of technologies applicable in electronic devices on the 5-10 year time scale. In the long term this will strengthen the UK's position in this future technology sector.
ii) People
The project will train young researchers and provide them with necessary skills to shape and drive the future development and production phase outlined in the ITRS starting in 2019. These include specific knowledge of the realisation and characterisation of molecular electronic devices but also more generic skill such as project management and effective communication.
iii) Society
In the short term dissemination and description of our research in accessible formats will contribute to the education of the public about the opportunities and risks associated with nanotechnology. In the long term, and intimately connected to the outlined technological impact, quality of life will be improved by the introduction of new products utilizing plasmoelectronics. These may include sectors of electronics (new device structures), health care (novel sensors), or energy (more efficient photovoltaics).
iv) Knowledge
We also expect major academic impact which is outlined in more detail in the academic beneficiary section.
Organisations
- University of Liverpool (Lead Research Organisation)
- DURHAM UNIVERSITY (Collaboration)
- University of Western Australia (Collaboration)
- University of Zaragoza (Collaboration)
- University of Bristol (Collaboration)
- Autonomous University of Madrid (Collaboration)
- Technical University of Denmark (Collaboration)
Publications
Wu C
(2020)
A Chemically Soldered Polyoxometalate Single-Molecule Transistor
in Angewandte Chemie
Vezzoli A
(2020)
A Chemically Soldered Polyoxometalate Single-Molecule Transistor
Wu C
(2020)
A Chemically Soldered Polyoxometalate Single-Molecule Transistor.
in Angewandte Chemie (International ed. in English)
Xu W
(2021)
A Peierls Transition in Long Polymethine Molecular Wires: Evolution of Molecular Geometry and Single-Molecule Conductance.
in Journal of the American Chemical Society
Leary E
(2018)
Bias-Driven Conductance Increase with Length in Porphyrin Tapes.
in Journal of the American Chemical Society
Escorihuela E
(2022)
Building large-scale unimolecular scaffolding for electronic devices
in Materials Today Chemistry
Markin A
(2020)
Conductance Behavior of Tetraphenyl-Aza-BODIPYs
in The Journal of Physical Chemistry C
Davidson RJ
(2018)
Conductance of 'bare-bones' tripodal molecular wires.
in RSC advances
Alanazy A
(2019)
Cross-conjugation increases the conductance of meta-connected fluorenones.
in Nanoscale
Leary E
(2018)
Detecting Mechanochemical Atropisomerization within an STM Break Junction
in Journal of the American Chemical Society
Reddy H
(2020)
Determining plasmonic hot-carrier energy distributions via single-molecule transport measurements
in Science
Davidson R
(2016)
Effects of Electrode-Molecule Binding and Junction Geometry on the Single-Molecule Conductance of bis-2,2':6',2?-Terpyridine-based Complexes.
in Inorganic chemistry
Herrer L
(2019)
Electrically transmissive alkyne-anchored monolayers on gold.
in Nanoscale
Liang J
(2016)
Electrochemically grafted single molecule junctions exploiting a chemical protection strategy
in Electrochimica Acta
Zhou P
(2023)
Enhanced charge transport across molecule-nanoparticle-molecule sandwiches
in Physical Chemistry Chemical Physics
Al-Owaedi O
(2016)
Experimental and Computational Studies of the Single-Molecule Conductance of Ru(II) and Pt(II) trans -Bis(acetylide) Complexes
in Organometallics
Wu C
(2020)
Folding a Single-Molecule Junction.
in Nano letters
Zhang Q
(2016)
Graphene as a Promising Electrode for Low-Current Attenuation in Nonsymmetric Molecular Junctions.
in Nano letters
Ferri N
(2019)
Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics
in Angewandte Chemie
Ferri N
(2019)
Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics.
in Angewandte Chemie (International ed. in English)
Wu C
(2020)
In situ formation of H-bonding imidazole chains in break-junction experiments.
in Nanoscale
Osorio H
(2017)
Influence of surface coverage on the formation of 4,4'-bipyridinium (viologen) single molecular junctions
in Journal of Materials Chemistry C
Ferradás R
(2016)
Low variability of single-molecule conductance assisted by bulky metal-molecule contacts
in RSC Advances
Naher M
(2021)
Molecular Structure-(Thermo)electric Property Relationships in Single-Molecule Junctions and Comparisons with Single- and Multiple-Parameter Models.
in Journal of the American Chemical Society
Herrer L
(2021)
pH control of conductance in a pyrazolyl Langmuir-Blodgett monolayer
in Journal of Materials Chemistry C
Naghibi S
(2022)
Redox-Addressable Single-Molecule Junctions Incorporating a Persistent Organic Radical**
in Angewandte Chemie
Naghibi S
(2022)
Redox-Addressable Single-Molecule Junctions Incorporating a Persistent Organic Radical.
in Angewandte Chemie (International ed. in English)
Planje IJ
(2021)
Selective Anchoring Groups for Molecular Electronic Junctions with ITO Electrodes.
in ACS sensors
Herrer L
(2023)
Sheathed Molecular Junctions for Unambiguous Determination of Charge-Transport Properties
in Advanced Materials Interfaces
Ismael A
(2017)
Side-Group-Mediated Mechanical Conductance Switching in Molecular Junctions
in Angewandte Chemie
Ismael AK
(2017)
Side-Group-Mediated Mechanical Conductance Switching in Molecular Junctions.
in Angewandte Chemie (International ed. in English)
Zhang W
(2016)
Single-Molecule Conductance of Viologen-Cucurbit[8]uril Host-Guest Complexes.
in ACS nano
Qiao X
(2023)
Single-Molecule Junction Formation in Deep Eutectic Solvents with Highly Effective Gate Coupling.
in The journal of physical chemistry. C, Nanomaterials and interfaces
Nichols R
(2021)
STM studies of electron transfer through single molecules at electrode-electrolyte interfaces
in Electrochimica Acta
Naghibi S
(2019)
Synthetic Control of Quantum Interference by Regulating Charge on a Single Atom in Heteroaromatic Molecular Junctions.
in The journal of physical chemistry letters
Milan DC
(2017)
The single-molecule electrical conductance of a rotaxane-hexayne supramolecular assembly.
in Nanoscale
Martín S
(2016)
Towards a metallic top contact electrode in molecular electronic devices exhibiting a large surface coverage by photoreduction of silver cations
in Journal of Materials Chemistry C
Escorihuela E
(2020)
Towards the design of effective multipodal contacts for use in the construction of Langmuir-Blodgett films and molecular junctions
in Journal of Materials Chemistry C
Herrer IL
(2018)
Unconventional Single-Molecule Conductance Behavior for a New Heterocyclic Anchoring Group: Pyrazolyl.
in The journal of physical chemistry letters
Xu W
(2019)
Unusual Length Dependence of the Conductance in Cumulene Molecular Wires.
in Angewandte Chemie (International ed. in English)
Description | We have studied in detail a series of materials for evaluation as single molecule conductors, including multi-podal molecules synthesised by our collaborators. This has included a detailed evaluation of molecular wires which are suited for deployment with conducting transparent optical substrates for optical investigations and plasmonics. We have also studied of a series of tripodal molecules that show a systematic structure-conductance trend allowing in depth understanding of the conductance mechanism. We have developed devices with well-defined embedded plasmonic nanostructures on which molecules can be adsorbed and we have studied these under optical illumination. We have developed new molecular conductors on indium tin oxide transparent electrodes which will facilitate further investigations under optical and plasmonic excitation. Investigator Higgins has successfully collaborated with a US group (Reddy) on transport in single-molecule junctions, created by trapping single molecules between an ultrathin gold film supporting surface plasmons and a scanning probe tip. This facilitated investigations of the plasmonic hot-carrier distributions and shows how plasmonically generated hot carriers can be harnessed in molecular junctions down to the single molecule level. |
Exploitation Route | Our work will further the development of new, ultrasensitive and ultracompact sensors which combine electrical and optical detection methods. |
Sectors | Chemicals,Education,Electronics,Energy,Environment |
Description | Collaboration with Bristol University |
Organisation | University of Bristol |
Department | School of Social and Community Medicine |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Bilateral collaboration with Bristol University on molecular electronics, spintronics and single molecule electronics and measurements and electrochemistry. |
Collaborator Contribution | Bilateral collaboration with Bristol University on molecular electronics, spintronics and single molecule electronics and measurements and electrochemistry. Collaboration with group of Walther Schwarzacher. |
Impact | A series of scientific publications. |
Start Year | 2007 |
Description | Danish Technical University |
Organisation | Technical University of Denmark |
Department | Department of Photonics Engineering |
Country | Denmark |
Sector | Academic/University |
PI Contribution | Collaboration in molecular electronics (theory) with Prof. Ulstrup group. |
Collaborator Contribution | Collaboration in molecular electronics (experiment) |
Impact | Scientific publications, see publication list. |
Description | Univeristy of Zaragoza |
Organisation | University of Zaragoza |
Department | Department of Chemistry |
Country | Spain |
Sector | Academic/University |
PI Contribution | Bilateral collaboration with Zaragoza University (Spain) on molecular electronics, LB films, single molecule electronics and electrochemistry. |
Collaborator Contribution | Bilateral collaboration with Zaragoza University (Spain) on molecular electronics, LB films, single molecule electronics and electrochemistry. |
Impact | See publications attributed. |
Start Year | 2007 |
Description | University of Durham |
Organisation | Durham University |
Department | Department of Biosciences |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Molecular Electronics (synthesis) |
Collaborator Contribution | Molecular Electronics (measurements and characterisation) |
Impact | Scientific publications. |
Start Year | 2006 |
Description | University of Madrid |
Organisation | Autonomous University of Madrid |
Country | Spain |
Sector | Academic/University |
PI Contribution | Collaboration in single molecule electronics |
Collaborator Contribution | Collaboration in single molecule electronics |
Impact | Publications in preparation. |
Start Year | 2015 |
Description | University of Western Australia (UWA) |
Organisation | University of Western Australia |
Country | Australia |
Sector | Academic/University |
PI Contribution | Molecular electronics (synthesis) |
Collaborator Contribution | Molecular electronics (measurements and characterisation) |
Impact | Scientific publications (see list) |
Start Year | 2014 |
Description | Bristol-Liverpool Workshop on Single-Molecule Electron Transport |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Industry/Business |
Results and Impact | Bristol-Liverpool Workshop on Single-Molecule Electron Transport involving academic and industrial attendees and outreach. |
Year(s) Of Engagement Activity | 2018 |