Supramolecular self-assembly of 1-10nm templates for biofunctional surfaces, quantum information processing and nanoelectronics
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Physics & Astronomy
Abstract
Nanotechnology is concerned with the control of material properties and processes on a very small scale - comparable with the size of single molecules or atoms. The development of new techniques to achieve this level of control has been an active area of research for many years and it has become clear that there are many technological benefits which will follow from these developments. Perhaps the most obvious example of these benefits is the progressive increase in speed and memory of computers which has had enormous impact on society and is a direct result of the ability to manufacture ever smaller electronic components. The traditional approach to making small, nanoscale, structures is known as 'top-down'. In this approach the starting point is to take a large object and use various technologies to process it into smaller objects. For example one might start with a silicon surface and form features on the surface which have very small dimensions - in fact this is how a silicon microprocessor which controls a computer is manufactured. In our application we propose a revolutionary technology which may be classified as a 'bottom-up' nanotechnology. Here the approach is almost the opposite to the 'top-down' approach in that an object is built out of components which are smaller than the resulting structure. An everyday example would be a house which is built of smaller building blocks - bricks! The building blocks in our case would be single molecules, but, unlike the everyday example, our molecular bricks may be designed or programmed to interact with each other so that they spontaneously form structures of interest. This process is known as 'self-assembly' and is achieved by incorporating in the molecule some special groups which promote interactions to control the alignment and position of neighbouring molecules. In our work we use hydrogen bonding interactions - the forces which hold together many of the molecules of life such as proteins and DNA.The 'self-assembled' structures we have made so far have been relatively simple - honeycomb networks of molecules sitting on a surface. In these networks one molecule forms the honeycomb edge and another the vertex. Most importantly the spacing of the voids of the honeycomb is very small - about 3.5 nanometres, equivalent to a few tens of atoms or alternatively about 3 large molecules such as buckyballs - and can be controlled through the choice of edge molecules. Remarkably, we have found that the holes of the honeycomb network can be filled up in a controlled manner with other materials and they therefore offer a way of achieving the central goal of nanotechnology introduced above - control of materials down to the scale of single molecules. We are now proposing to develop this discovery into a technological approach to forming a whole range of new nanoscale networks using the same approach and using these structures as templates to control the properties of new materials for biotechnology, electronics and a new form of computing / quantum information processing - which is based on the controllable mixing of quantum wave functions. The work will bring together chemists who will make the specialised molecules which are required and physicists who will study the way in which these molecules combine in the self assembly process. These scientists will be joined by others who have interests in electronic materials, biology and quantum computing - these groups will use the networks for scientific and technological demonstrator applications. By the end of the project we aim to have developed the means of perfecting networks with different dimensions, strengths, and chemical properties and hope to make this templating technology available to a much wider community of scientists and engineers in academia and industry.
Publications
Swarbrick JC
(2006)
Hydrogen-bonded PTCDA-melamine networks and mixed phases.
in The journal of physical chemistry. B
Taylor JB
(2006)
Kinetic instabilities in the growth of one dimensional molecular nanostructures.
in Physical review letters
Perdigão L
(2006)
Experimental and theoretical identification of adenine monolayers on Ag-terminated Si(111)
in Physical Review B
Perdigão LM
(2006)
Surface self-assembly of the cyanuric acid-melamine hydrogen bonded network.
in Chemical communications (Cambridge, England)
Staniec P
(2006)
Honeycomb Networks and Chiral Superstructures Formed by Cyanuric Acid and Melamine on Au(111)
in The Journal of Physical Chemistry C
Perdigão LM
(2006)
Bimolecular networks and supramolecular traps on Au(111).
in The journal of physical chemistry. B
Ma J
(2006)
Dianhydride-amine hydrogen bonded perylene tetracarboxylic dianhydride and tetraaminobenzene rows.
in The journal of physical chemistry. B
Staniec PA
(2007)
Hierarchical organisation on a two-dimensional supramolecular network.
in Chemphyschem : a European journal of chemical physics and physical chemistry
Silly F
(2007)
Pairs and heptamers of C70 molecules ordered via PTCDI-melamine supramolecular networks
in Applied Physics Letters
Saywell A
(2008)
Electrospray Deposition of C 60 on a Hydrogen-Bonded Supramolecular Network
in The Journal of Physical Chemistry C
Hamblin J
(2008)
Hydrogen-bonding tectons for the construction of bimolecular framework materials
in CrystEngComm
Jensen S
(2008)
Formation of PTCDI-Based Metal Organic Structures on a Au(111) Surface Modified by 2-D Ni Clusters
in The Journal of Physical Chemistry C
Perdigão LM
(2008)
Functionalized supramolecular nanoporous arrays for surface templating.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Blunt MO
(2008)
Random tiling and topological defects in a two-dimensional molecular network.
in Science (New York, N.Y.)
Silly F
(2008)
Deriving molecular bonding from macromolecular self-assembly
Silly F
(2008)
Grating of single Lu@C(82) molecules using supramolecular network.
in Chemical communications (Cambridge, England)
Weber UK
(2008)
Role of interaction anisotropy in the formation and stability of molecular templates.
in Physical review letters
Goretzki G
(2008)
Bis-morpholine-substituted perylene bisimides: impact of isomeric arrangement on electrochemical and spectroelectrochemical properties.
in The Journal of organic chemistry
Blunt M
(2008)
Directing two-dimensional molecular crystallization using guest templates.
in Chemical communications (Cambridge, England)
Madueno R
(2008)
Functionalizing hydrogen-bonded surface networks with self-assembled monolayers.
in Nature
Perdigão LM
(2009)
Entrapment of decanethiol in a hydrogen-bonded bimolecular template.
in Langmuir : the ACS journal of surfaces and colloids
Silien C
(2009)
Self-assembly of a pyridine-terminated thiol monolayer on Au(111).
in Langmuir : the ACS journal of surfaces and colloids
Goretzki G
(2009)
Building multistate redox-active architectures using metal-complex functionalized perylene bis-imides.
in Inorganic chemistry
Mura M
(2009)
H-Bonding Supramolecular Assemblies of PTCDI Molecules on the Au(111) Surface
in The Journal of Physical Chemistry C
O'Shea J
(2009)
Adsorption of PTCDI on Au(111): Photoemission and scanning tunnelling microscopy
in Surface Science
Garrahan JP
(2009)
Molecular random tilings as glasses.
in Proceedings of the National Academy of Sciences of the United States of America
Gardener J
(2010)
Intricate Hydrogen-Bonded Networks: Binary and Ternary Combinations of Uracil, PTCDI, and Melamine
in The Journal of Physical Chemistry C
Saywell A
(2010)
Conformation and packing of porphyrin polymer chains deposited using electrospray on a gold surface.
in Angewandte Chemie (International ed. in English)
Stannard A
(2010)
Entropically-stabilised growth of a two-dimensional random tiling
Saywell A
(2010)
Self-assembled aggregates formed by single-molecule magnets on a gold surface.
in Nature communications
Phillips AG
(2010)
Tailoring pores for guest entrapment in a unimolecular surface self-assembled hydrogen bonded network.
in Chemical communications (Cambridge, England)
Stiufiuc R
(2010)
Above-barrier surface electron resonances induced by a molecular network
in Physical Review B
Russell JC
(2010)
Solubilized derivatives of perylenetetracarboxylic dianhydride (PTCDA) adsorbed on highly oriented pyrolytic graphite.
in Langmuir : the ACS journal of surfaces and colloids
Stannard A
(2010)
Entropically stabilized growth of a two-dimensional random tiling.
in Physical review. E, Statistical, nonlinear, and soft matter physics
Korolkov V
(2010)
Subsecond Self-Assembled Monolayer Formation
in The Journal of Physical Chemistry C
Jensen S
(2011)
STM Investigation on the Formation of Oligoamides on Au{111} by Surface-Confined Reactions of Melamine with Trimesoyl Chloride
in The Journal of Physical Chemistry C
Blunt MO
(2011)
Guest-induced growth of a surface-based supramolecular bilayer.
in Nature chemistry
Russell JC
(2011)
Dimerization of tri(4-bromophenyl)benzene by aryl-aryl coupling from solution on a gold surface.
in Journal of the American Chemical Society
Chamberlain TW
(2011)
Multi-electron-acceptor dyad and triad systems based on perylene bisimides and fullerenes.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Saywell A
(2011)
Single molecule magnets on a gold surface: in situ electrospray deposition, x-ray absorption and photoemission.
in Nanotechnology
Korolkov V
(2011)
High-Temperature Adsorption of p -Terphenylthiol on Au(111) Surfaces
in The Journal of Physical Chemistry C
Taleb N
(2011)
A mixed valence manganese triangle in a trigonal lattice: structure and magnetism.
in Dalton transactions (Cambridge, England : 2003)
Perdigão LM
(2011)
Haptic-STM: a human-in-the-loop interface to a scanning tunneling microscope.
in The Review of scientific instruments
Mura M
(2012)
Formation mechanism for a hybrid supramolecular network involving cooperative interactions.
in Physical review letters
Korolkov VV
(2012)
The structure and formation of hydrogen-bonded molecular networks on Au(111) surfaces revealed by scanning tunnelling and torsional-tapping atomic force microscopy.
in Physical chemistry chemical physics : PCCP
Shen C
(2012)
Structure of isophthalic acid based monolayers and its relation to the initial stages of growth of metal-organic coordination layers
in Chemical Science
Greenwood J
(2012)
Ordered Growth of Upright Melamine Species on Ni{111}: A Study with Scanning Tunnelling Microscopy and Reflection Absorption Infrared Spectroscopy
in The Journal of Physical Chemistry C
She Z
(2013)
Accommodation of Lattice Mismatch in a Thiol Self-Assembled Monolayer
in The Journal of Physical Chemistry C
Cebula I
(2013)
Monolayers of trimesic and isophthalic acid on Cu and Ag: the influence of coordination strength on adsorption geometry
in Chemical Science
Shen C
(2014)
Nanoscale patterning of a self-assembled monolayer by modification of the molecule-substrate bond.
in Beilstein journal of nanotechnology
Description | This was a multi-site project which was focussed on the formation of self-assembled templates which could be used to control the adsorption and positioning of molecules on a surface. The project grew from earlier work in which it had been demonstrated that small nano pores with a diameter of approximately 2.5 nm could be formed on a silicon surface under vacuum conditions. The consortium involved in this project aimed to form these networks on other surfaces, such as metals and graphite, which could be prepared and would be stable under atmospheric conditions as well as exploring other molecular systems which also exhibit this type of self-assembly, including the use of molecules which introduce specific molecular functionality into the pores. Within the consortium there also groups focussed on trying to exploit the networks for scientific applications in the area of pharmaceutical science and quantum engineering. The project was extremely successful in advancing the technical capability in the formation of the networks and extending fundamental understanding of the self-assembly process. In particular the deposition of similar networks from solution was demonstrated and is now used extensively int follow-up studies including the extension to insulating surfaces. In addition we were able to demonstrate a similar tempting mechanism using covalently linked networks which are much more robust. |
Exploitation Route | The use of templates has been adopted by leading researchers in the US and Europe to control molecular organisation on graphene surfaces. Further investigations of the networks have also been re-energised by the observation that they can be formed on insulating surfaces allowing the combined investigation of the organisational properties within these materials with optical and electronic properties. |
Sectors | Chemicals Electronics Energy Pharmaceuticals and Medical Biotechnology |
Description | The impact of the research has been mainly in the academic sector so far. There have been several discussions with companies who are interested in the possibilities afforded by this type of organisation of molecules but a limiting factor in their application has been the ease of producing large area layers from solution on technologically relevant surfaces. Since the end of the grant there has been ongoing progress towards this objective building on work in the project related tot he deposition of the networks on gold surfaces and using solution rather than vacuum deposition. Large area networks on insulating and metallic surfaces are now available. |
First Year Of Impact | 2006 |
Sector | Education,Other |
Impact Types | Societal |
Description | EPSRC |
Amount | £3,870,000 (GBP) |
Funding ID | EP/I012060/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |
Description | EPSRC |
Amount | £945,423 (GBP) |
Funding ID | EP/H010432/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |
Description | EPSRC |
Amount | £945,423 (GBP) |
Funding ID | EP/H010432/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |
Description | EPSRC |
Amount | £3,870,000 (GBP) |
Funding ID | EP/I012060/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |