Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular Limit
Lead Research Organisation:
University of Glasgow
Department Name: School of Chemistry
Abstract
Our vision is to demonstrate functional circuits using molecular metal-oxides (MMOs), connecting self-assembled MMOs into top-down, lithographically defined CMOS architectures with the ultimate aim of achieving the molecular limit in data storage and processing: i.e. realising inorganic, single molecule transistors. Our proposal is unique because: (i) it identifies a new class of inherently CMOS-compatible and functional molecules that have not previously been considered (or even patented) for 'beyond-Moore' applications; (ii) it aims to address key practicalities of scalability, interfacing, stability and reproducibility that are often omitted from schemes aiming simply to construct a single demonstrator device; and (iii) it is underpinned by a strongly-collaborative team with complementary expertise in molecular synthesis, modelling and device fabrication. This project is highly creative and adventurous, proposing that inorganic molecules could be reliably used in the fabrication of nano-electronic devices that take advantage of the intrinsic electronic properties of molecules as switchable molecular semiconductors (EPSRC success feature 1). It supports talent at all levels - from senior professors to early career researchers - in a highly supportive and collaborative context (EPSRC success feature 2). Initially, we propose to design hybrid devices combing CMOS embedded with bistable MMOs and to examine the interplay between 'bulk' and nano-molecular semiconducting units. Our approach is both innovative and practical because it embeds molecular electronics within the current the state-of-the-art, allowing us to address practical issues and develop know-how in this new field, before down-scaling to 'beyond-Moore' dimensions down to the molecular limit with collaborations that achieve a two-way flow of knowledge between the research base and industry (Building collaborations that achieve a two-way flow of knowledge between the research base and industry (EPSRC success feature 3) and at the same time this proposal encourages and supports research that crosses the borders between disciplines (EPSRC success feature 4). Theoretical studies of both single clusters and arrays will allow us to predict their behaviour and design new architectures; surface studies and device measurements will enable us to assess the electronic characteristics of devices and drive us towards viable nanoelectronics that can be mass-produced therby developing a shared vision of tomorrow's major challenges and opportunities with stakeholders: society, industry, universities and other partners (EPSRC succes feature 5). We aim to show that MMO-CMOS (herein called M-MOS) can function with 'embedded' molecular units and we plan towards the single molecule limit. This potential will be assessed and exploited within the Glasgow Nano EPSRC KTA (EP/H500138/1) allowing 'real-time' technology transfer allowing us to immediately seize any commercial development opportunities thereby building a better understanding of where we should focus our effort to benefit both UK society and the UK economy and increase its global competitiveness (ESPRC success feature 6).Finally this programme will directly train 7 PDRAs and 4 PhDs and indirectly train 8 further PhDs and 24 undergraduate / erasmus students thereby creating and sustaining research scientists and engineers in the UK so that they are recognised worldwide as leaders in their field (EPSRC success feature 7).
Planned Impact
Who will benefit from this research? The semi-conductor / microelectronics / nano-fabrication industries will be the major beneficiaries of this research at all levels from multi-nationals to SMEs and spin out companies. In addition UK HEIs, students and the general public will also be beneficiaries as well as the UK-PLC as a whole. How will they benefit from this research? Industry: The semi-conductor / microelectronics / nano-fabrication industries will benefit from the new technologies generated in this research since it will provide, in the short term, performance upgrades to CMOS-based devices, as well as building in the ability to down-scale towards the molecular limit over the coming decade or two without the problems described above in the background. These benefits will be of great interest also to SMEs and spin-outs that develop niche applications that will directly utilize and develop some of the technology in other directions developing 'niche' high value applications. The interactions between Chemists, Physicists, and Electrical Engineers proposed in this grant will also yield great potential teaching and research benefits for the students and the University. This is because undergraduate, ERASMUS, and PhD students will get the chance to take part in research that crosses the interface of this project and it may also be possible to develop a research masters based on this area that will train the next generation of researchers and engineers for nano-electronics. General Public: The general public will benefit from this research from the increase in wealth that will be developed and the public understanding and promotion of science activities planned through public lectures at Glasgow / Edinburgh Science Weeks, Caf Scientifique, via the PPE grant that the PI is involved in entitled Giants of the Infinitesimal EP/G062536/1 which aims to bring the nano-world to life. What will be done to ensure that they have the opportunity to benefit from this research? This programme grant will incorporate an technology transfer element that will allow 'real-time' technology transfer to industry including multi-nationals, SMEs, and spin-outs. This technology transfer element will interact directly with the EPSRC funded Nanotechnology Knowledge Training Account (KTA) awarded to the University of Glasgow & Glasgow University Research and Enterprise. Through the KTA we will exploit and give this work visibility, interact with end-users, and develop a forum of interested parties that will receive information and progress about the project as it proceeds. We will make some of our funding available to ensure the following technology overlaps / exploitation / collaborations are developed: (i) Part funding of a technology transfer 'researcher' who's job it is to identify new ideas and possibilities in the programme research that can be transferred to partners by seconding this individual to the partner lab. As a result of this cross departmental collaboration, new approaches to molecular and engineering nanosciences will be developed. In synergy with the project the WP leaders will develop a lecture / workshop module to address the interdisciplinary aspects; three modules are planned from a chemical, electrical engineering, and modelling perspective. It is envisaged that as the programme develops and expands that the training element could expand into a MSc. Course in molecular and engineering nanoscience. General Public: A website will be established called Nanochemistry-NOW! that will explain our project, the collaboration, the big idea, and the advances expected. In addition we will give lectures at Glasgow Science week and Caf Scientifique. One example to be given by LC is 'Molecular nanosciences: Computing with molecules .
Publications
Surman AJ
(2016)
Sizing and Discovery of Nanosized Polyoxometalate Clusters by Mass Spectrometry.
in Journal of the American Chemical Society
Steiner S
(2019)
Organic synthesis in a modular robotic system driven by a chemical programming language.
in Science (New York, N.Y.)
Song YF
(2011)
Nanoscale polyoxometalate-based inorganic/organic hybrids.
in Chemical record (New York, N.Y.)
Sharma A
(2024)
A programmable hybrid digital chemical information processor based on the Belousov-Zhabotinsky reaction
in Nature Communications
Schupp F
(2018)
Quantum interference in silicon one-dimensional junctionless nanowire field-effect transistors
in Physical Review B
Sartzi H
(2018)
Directed Self-Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Sartzi H
(2015)
Trapping the d Isomer of the Polyoxometalate-Based Keggin Cluster with a Tripodal Ligand.
in Angewandte Chemie (International ed. in English)
Sartzi H
(2015)
Trapping the d Isomer of the Polyoxometalate-Based Keggin Cluster with a Tripodal Ligand
in Angewandte Chemie
Sans V
(2014)
Non-equilibrium dynamic control of gold nanoparticle and hyper-branched nanogold assemblies
in Chemical Science
Sans V
(2016)
Towards dial-a-molecule by integrating continuous flow, analytics and self-optimisation.
in Chemical Society reviews
Sans V
(2015)
A self optimizing synthetic organic reactor system using real-time in-line NMR spectroscopy.
in Chemical science
Salley DS
(2020)
A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates.
in ACS central science
Salley D
(2023)
Robotic Modules for the Programmable Chemputation of Molecules and Materials.
in ACS central science
Salley D
(2020)
A nanomaterials discovery robot for the Darwinian evolution of shape programmable gold nanoparticles.
in Nature communications
Ruiz De La Oliva A
(2017)
Coding the Assembly of Polyoxotungstates with a Programmable Reaction System.
in Inorganic chemistry
Rosnes MH
(2012)
Mapping the synthesis of low nuclearity polyoxometalates from octamolybdates to Mn-Anderson clusters.
in Dalton transactions (Cambridge, England : 2003)
Rosnes MH
(2010)
Assembly of modular asymmetric organic-inorganic polyoxometalate hybrids into anisotropic nanostructures.
in Journal of the American Chemical Society
Rodriguez-Garcia M
(2015)
Formation of oligopeptides in high yield under simple programmable conditions.
in Nature communications
Robbins PJ
(2013)
Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.
in Chemical communications (Cambridge, England)
Richmond CJ
(2012)
A flow-system array for the discovery and scale up of inorganic clusters.
in Nature chemistry
Quesada Cabrera R
(2012)
Spectroscopic studies of sulfite-based polyoxometalates at high temperature and high pressure
in Journal of Solid State Chemistry
Purcell JW
(2017)
Tellurite-Squarate Driven Assembly of a New Family of Nanoscale Clusters Based on (Mo2 O2 S2 )2.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Purcell JW
(2018)
Spontaneous formation of a chiral (Mo2O2S2)2+-based cluster driven by dimeric {Te2O6}-based templates.
in Dalton transactions (Cambridge, England : 2003)
Prat I
(2011)
Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C-H and C=C oxidation reactions.
in Nature chemistry
Pradeep CP
(2011)
Design and synthesis of "dumb-bell" and "triangular" inorganic-organic hybrid nanopolyoxometalate clusters and their characterisation through ESI-MS analyses.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Points LJ
(2016)
An all-inorganic polyoxometalate-polyoxocation chemical garden.
in Chemical communications (Cambridge, England)
Points LJ
(2018)
Artificial intelligence exploration of unstable protocells leads to predictable properties and discovery of collective behavior.
in Proceedings of the National Academy of Sciences of the United States of America
Parrilla-Gutierrez JM
(2017)
Adaptive artificial evolution of droplet protocells in a 3D-printed fluidic chemorobotic platform with configurable environments.
in Nature communications
Parrilla-Gutierrez JM
(2020)
A programmable chemical computer with memory and pattern recognition.
in Nature communications
Nicolaou M
(2018)
Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids
in Chemistry - A European Journal
Newton GN
(2011)
Mapping the sequential self-assembly of heterometallic clusters: from a helix to a grid.
in Angewandte Chemie (International ed. in English)
Nemeth B
(2012)
Imaging the Belousov-Zhabotinsky reaction in real time using an ion sensitive array.
in Chemical communications (Cambridge, England)
Nemeth B
(2012)
Real-time ion-flux imaging in the growth of micrometer-scale structures and membranes.
in Advanced materials (Deerfield Beach, Fla.)
Nakanishi K
(2018)
Development of a Minimal Photosystem for Hydrogen Production in Inorganic Chemical Cells.
in Angewandte Chemie (International ed. in English)
Nakanishi K
(2018)
Development of a Minimal Photosystem for Hydrogen Production in Inorganic Chemical Cells
in Angewandte Chemie
Musumeci C
(2011)
Programmable Surface Architectures Derived from Hybrid Polyoxometalate-Based Clusters
in The Journal of Physical Chemistry C
Musumeci C
(2011)
Smart high-? nanodielectrics using solid supported polyoxometalate-rich nanostructures.
in ACS nano
Molina PI
(2014)
Assembly and core transformation properties of two tetrahedral clusters: [Fe(III)13P8W60O227(OH)15(H2O)2]30- and [Fe(III)13P8W60O224(OH)12(PO4)4]33-.
in Dalton transactions (Cambridge, England : 2003)
Molina PI
(2013)
Exploring the assembly of supramolecular polyoxometalate triangular morphologies with Johnson solid cores: [(Mn(II)(H2O)3)2(K?{a-GeW10Mn(II)2O38}3)]19-.
in Inorganic chemistry
Mitchell SG
(2011)
A mixed-valence manganese cubane trapped by inequivalent trilacunary polyoxometalate ligands.
in Angewandte Chemie (International ed. in English)
Mitchell SG
(2011)
Extended polyoxometalate framework solids: two Mn(II)-linked {P8W48} network arrays.
in Inorganic chemistry
Misdrahi MF
(2011)
Amphiphilic properties of dumbbell-shaped inorganic-organic-inorganic molecular hybrid materials in solution and at an interface.
in Langmuir : the ACS journal of surfaces and colloids
Mirza MM
(2017)
One dimensional transport in silicon nanowire junction-less field effect transistors.
in Scientific reports
Mirza M
(2014)
Determining the Electronic Performance Limitations in Top-Down-Fabricated Si Nanowires with Mean Widths Down to 4 nm
in Nano Letters
Miras HN
(2012)
Solution-phase monitoring of the structural evolution of a Molybdenum Blue nanoring.
in Journal of the American Chemical Society
Miras HN
(2012)
Oscillatory template exchange in polyoxometalate capsules: a ligand-triggered, redox-powered, chemically damped oscillation.
in Journal of the American Chemical Society
Miras HN
(2012)
Engineering polyoxometalates with emergent properties.
in Chemical Society reviews
Miras HN
(2014)
Polyoxometalate based open-frameworks (POM-OFs).
in Chemical Society reviews
Miras HN
(2020)
Spontaneous formation of autocatalytic sets with self-replicating inorganic metal oxide clusters.
in Proceedings of the National Academy of Sciences of the United States of America
Description | A range of new molecules synthesised (>50), mass spectrometry screening implemented; Heteroatom guest clusters discovered and characterised with unprecedented REDOX chemistry. Substrate assembly work simplified thanks to feedback from modelling results.Molecular simulations for a range of host-guest clusters as a function of heteroatom; Modelling of flash ram as a function of molecule type, density and organisation; experiments interfacing to silicon devices with Gold Standard Theory.Interfacing of molecules to electrode arrays done; Design of new devices to characterise molecules on nanowire devices rather than electrometer. Development of CMOS based ISFET sensors to image POM assembly on surfaces. |
Exploitation Route | Using some of the molecules we discovered during the programme grant we discovered a new way of controlling the growth of polyoxometalate based microtubes that could be fabricated in real time to produce microfluidic devices. We constructed an device using a laser system connected to a IPAD which allows us to control the system and 'wire-up' tubular networks on the fly in real time. In the course of our device engineering work we came up with a new approach to integrate CMOS sensors with reactor platforms to explore chemical reactions in real time. Not only can we monitor the reactions but we also devised a platform for the control and processing of chemical reactions using integrated CMOS. The result is a new platform that could allow computations to be done using hybrid electro-chemical systems and substrates. From our construction of reactors to monitor cluster formation in the mass spectrometer we found a new approach for the synthesis of molecules by coupling feedback from the sensor system to the chemical inputs. This allowed us to devised a new route for exploring array / combinatorial chemistry much faster than before by developing new chemistry, engineering, analytics as well as new algorithms for navigating the parameter space. |
Sectors | Chemicals Electronics Energy |
Description | From: http://www.wired.co.uk/news/archive/2014-11/19/molecule-flash-storage Single molecule technology could finally break Moore's law and allow gadgets to store huge amounts of data on tiny flash storage cards. Chemists behind the new molecules say the new technology could help solve the looming flash storage dilemma. Flash memory, used in nearly all of our favourite gadgets, is hampered by the physical limits of data cells, which currently use metal-oxide-semiconductor (MOS) components. These are almost impossible to manufacture at a scale below ten nanometers, setting an upper limit on the how much can be stored. Scientists have now claimed a breakthrough in the use of individual molecules as a replacement for conventional data-storage components. The benefits are massive, or rather very small, with huge amounts of data potentially being stored on tiny flash memory units. Moore's law, which states that the number of transistors in a dense integrated circuit doubles approximately every two years, could be broken if researches can put multiple bits of data on a single molecule Laia Vila Nadal, Felix Iglesias Escudero, Leroy Cronin, Cronin Group, School of Chemistry, University of Glasgow The team from the University of Glasgow and Rovira i Virgili University in Spain have successfully designed and synthesised new molecules that work in a similar way to transistors. The new metal-oxide clusters, known as polyoxometalates (POMs), are detailed in the journal Nature. Professor Lee Cronin from the University of Glasgow, who led the research team, said that the new technology had incredible potential. "The incorporation of molecules will allow us to further scale down and extend Moore's law and potentially even go beyond this with multiple bits of storage per single molecule," he told WIRED.co.uk. "One major benefit of the POMs we've created is that it's possible to fabricate them with devices which are already widely-used in industry, so they can be adopted as new forms of flash memory without requiring production lines to be expensively overhauled." Don't miss Single-atom transistor beats Moore's Law by eight years Single-atom transistor beats Moore's Law by eight years Previous attempts to develop these high-tech molecules have been hampered by significant barriers. Low thermal stability and high resistance have both limited their use in existing gadgets. Flash memory uses transistors that "remember" when they've been turned on or off, even when no longer powered. These transistors correspond to binary, allowing data to be stored. The researchers have now been able to design, synthesise and control POM molecules that can catch a charge and behave in the same way as flash RAM. The new technology could also provide a more secure way to store sensitive information. Known as "write-once-erase" the method of storage would make it impossible to recover secret data once it has been deleted, researchers claimed. Work on this is still underway. In 2019 one of the lead researcher on this program (Dr Vila Nadal) started her independent career with a view to exploiting these findings specifically. In addition Dr Chen has begun his independent career at Xiamen University in this field. Thus these key researchers are likely to make important impacts from this work in the near future once their groups are at full force. |
First Year Of Impact | 2014 |
Sector | Digital/Communication/Information Technologies (including Software),Education |
Impact Types | Cultural Societal Economic Policy & public services |
Title | One dimensional transport in silicon nanowire junction-less field effect transistors |
Description | Raw electron microscopy and electrical characterisation data underpinning the figures presented in the manuscript. |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | Unprecedented Inequivalent Metal Coordination Environments in a Mixed-Ligand Dicobalt Complex |
Description | Important collection of information for future research. |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Impact | Easy and quick access to a database of coordination complex materials for future design and synthesis |
Description | Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular Limit |
Organisation | University of Glasgow |
Department | School of Engineering Glasgow |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Our vision is to demonstrate functional circuits using molecular metal-oxides (MMOs), connecting self-assembled MMOs into top-down, lithographically defined CMOS architectures with the ultimate aim of achieving the molecular limit in data storage and processing: i.e. realising inorganic, single molecule transistors. Our proposal is unique because: (i) it identifies a new class of inherently CMOS-compatible and functional molecules that have not previously been considered (or even patented) for 'beyond-Moore' applications; (ii) it aims to address key practicalities of scalability, interfacing, stability and reproducibility that are often omitted from schemes aiming simply to construct a single demonstrator device; and (iii) it is underpinned by a strongly-collaborative team with complementary expertise in molecular synthesis, modelling and device fabrication. This project is highly creative and adventurous, proposing that inorganic molecules could be reliably used in the fabrication of nano-electronic devices that take advantage of the intrinsic electronic properties of molecules as switchable molecular semiconductors (EPSRC success feature 1). It supports talent at all levels - from senior professors to early career researchers - in a highly supportive and collaborative context (EPSRC success feature 2). Initially, we propose to design hybrid devices combing CMOS embedded with bistable MMOs and to examine the interplay between 'bulk' and nano-molecular semiconducting units. Our approach is both innovative and practical because it embeds molecular electronics within the current the state-of-the-art, allowing us to address practical issues and develop know-how in this new field, before down-scaling to 'beyond-Moore' dimensions down to the molecular limit with collaborations that achieve a two-way flow of knowledge between the research base and industry (Building collaborations that achieve a two-way flow of knowledge between the research base and industry (EPSRC success feature 3) and at the same time this proposal encourages and supports research that crosses the borders between disciplines (EPSRC success feature 4). Theoretical studies of both single clusters and arrays will allow us to predict their behaviour and design new architectures; surface studies and device measurements will enable us to assess the electronic characteristics of devices and drive us towards viable nanoelectronics that can be mass-produced therby developing a shared vision of tomorrow's major challenges and opportunities with stakeholders: society, industry, universities and other partners (EPSRC succes feature 5). We aim to show that MMO-CMOS (herein called M-MOS) can function with 'embedded' molecular units and we plan towards the single molecule limit. This potential will be assessed and exploited within the Glasgow Nano EPSRC KTA (EP/H500138/1) allowing 'real-time' technology transfer allowing us to immediately seize any commercial development opportunities thereby building a better understanding of where we should focus our effort to benefit both UK society and the UK economy and increase its global competitiveness (ESPRC success feature 6).Finally this programme will directly train 7 PDRAs and 4 PhDs and indirectly train 8 further PhDs and 24 undergraduate / erasmus students thereby creating and sustaining research scientists and engineers in the UK so that they are recognised worldwide as leaders in their field (EPSRC success feature 7). |
Collaborator Contribution | as above |
Impact | See publications on this tagged to: EP/H024107/1 |
Start Year | 2010 |
Title | Use of Polyoxometalate Mediators |
Description | The present invention provides methods for producing hydrogen using a mediator that is capable of reversibly donating and accepting four or more electrons. A method of the invention comprises the steps of reducing a mediator by four or more electrons to yield a reduced mediator, and oxidising a reduced mediator to yield a mediator, and reducing protons to yield hydrogen. |
IP Reference | US2021032762 |
Protection | Patent application published |
Year Protection Granted | 2021 |
Licensed | No |
Impact | No impact yet. Early stages. |
Description | Advisory Role |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Other audiences |
Results and Impact | City University of New York Nanotechnology Institute |
Year(s) Of Engagement Activity | 2015 |