Engineering van der Waals heterostructures: from atomic level layer-by-layer assembly to printable innovative devices

Lead Research Organisation: University of Manchester
Department Name: Physics and Astronomy

Abstract

Modern technology demands increasingly larger number of new materials to suit the specific requirement of the particular applications. The search for new materials, or even better, for materials with tuneable properties, has dramatically intensified over the last decade. The best strategy here are the composite materials and heterostructures, which allow ultimate tuning of material parameters, combinations of otherwise unmatchable properties and can provide multiple functionalities. However, usually such materials are not readily accessible due to cost and the complex technology required for assembly/production of such structures. Here we propose a new paradigm in creating such composite materials: heterostructures based on 2D atomic crystals, which can be assembled by mass-production means. This way we will decouple the performance of particular devices from the properties of naturally available materials. The ultimate goal is to develop a new paradigm of "materials on demand" with properties precisely tailored for novel complex architectures and structures. The ground-breaking nature of our research and the development of the mass-production technique of the production of such heterostructures will have huge impact on future technology. We will also demonstrate prototypes of multifunctional devices which are based on such a technology. Examples of devices we are planning to create are temperature, humidity, light, strain and many other sensors which will be battery-free and powered by absorbing radio waves (RFID technology, also enabled by printed electronics) for remote sensing applications. Such wirelessly interconnected tuneable sensors and actuators can create a platform for the fast-growing "Internet of Things" paradigm.

2D atomic crystals are one atom thick materials. The family of such crystals is very large and includes transition metal dichalcogenides, hexagonal boron nitride, graphene among many others. Collectively, they cover a large range of properties: from conductive to insulating, from transparent to opaque, from mechanically stiff to compliant. Also, very often the properties of such 2D crystals are very different from the properties of their 3D precursors. Interestingly, many of the unique properties of the 2D crystals are preserved even when we create suspensions (2D inks) out of these materials. Such inks can be used for deposition of the 2D materials to any surfaces, creating low-cost, conformal functional coating.

Still, the most important property of materials in this family is the possibility to assemble them into 3D stacks, creating novel heterostructures. Such heterostructures have proven to have new functionalities (tunnelling transistors, LED, etc) or even combinations of several functionalities. The large selection of 2D crystals, ensures that the parameters of such heterostructures can be tuned in a wide range.

In this project we propose to develop a low-cost technique to be able to print such heterostructures from 2D inks. Several members of the consortium have already demonstrated that tunnelling diodes, tunnelling transistors and photodetectors can be printed using standard mass-production technologies. We will significantly increase the range of heterostructures produced by such methods, and will specifically concentrate on heterostructures which produce active response (thermo-power, piezoelectric, photovoltaic, etc). Such heterostructures can act as sensors in a number of applications. We will then combine this technology with already developed technique of printing RFID antenna by using graphene inks. This would allow us to create RFID sensors of different types which do not require power source. For instance, we can record temperature of a product or illumination this product has been subjected to. Multifunctional sensors can naturally be achieved with such technique (for instance temperature, strain and humidity could be recorded at the same time).

Planned Impact

This project has a broad range of ambitious objectives: from identifying new 2D materials to developing mass-production methods of producing heterostructures based on such materials. Consequently, we expect a broad impact on industrial, research and academic communities:
* Materials Library and engagement with broader academic and engineering communities: We will initiate an active intelligent search (with the help of DFT calculations) for novel 2D materials and create heterostructures based on such materials. As we expect to accumulate a significant database on such crystals we will publish a catalogue (in a form of a research paper) which will provide structured information on the properties of all known 2D materials and the way they interact when assembled in heterostructures. We expect such a catalogue to be widely used by researchers in academia and industry. We also will create a web version of the catalogue.
* Paradigm Shift: We expect the very concept of "materials on demand" will have a significant resonance in the academic and industrial community. The possibility to design the materials for any specific application is new and very attractive. We will work with various industrial partners (including those outside of the project) with the aim of demonstrating the capabilities of our platform for various applications. We expect this to create a significant impact on the manufacturing community worldwide.
* Materials supply: We will initiate the creation of a spin-off company which will supply monolayer flakes as well as inks of various materials for academic and research purposes. Having a wide variety of well-characterised 2D materials (both in flake and ink form) on offer will benefit a large spread of researchers as well as industries.
* Equipment design: We are planning to use standard printing equipment at the beginning of the project. As we develop a more mature recipe for the inks, we will inevitably implement certain modifications to the equipment. We expect that such modifications will be of interest for equipment manufacturers as 2D inks become increasingly more used in industry.
* Software design: The use of printing technology relies on a very precise tuning of the properties of the inks. We are planning to design software which will allow one to design the inks with specific properties and simulate the printing results. Such software will be of interest to a large community of researchers and engineers working in the area of printing technology.
* Business engagement: We have a number of project partners within the consortium. We are planning to transfer the technology developed within the project to those partners. In particular, Merck is interested in development of stable inks of 2D materials. BGT Materials will be most interested in the technology of printed heterostructures. Such technology transfer will contribute to job creation and technology development.
* Training of Workforce for Industry : The project will generate a large amount of know-how along with papers and patents. We expect that the postdocs involved in the project will be of high value for the commercial companies involved in materials research (both those involved in the project and those outside of the project). Thus, this project will provide training for future staff for the advanced materials industry.
* Engaging community, allowing other materials and heterostructures (developed in other groups) to enter industrial applications: The pool of researchers studying various 2D materials and their heterostructures is increasing daily. Arguably, it is the most dynamically developing direction of research in modern condensed matter physics. Our project will create a pathway for novel materials and heterostructures to be implemented in applications. We will offer to apply our expertise and the technology developed within the project to materials and heterostructures from other research groups to bring those to application.

Publications

10 25 50
 
Description first capacitors and thermocouple have been printed by ink jet printing. Such devices will be used as sensors and energy storage for future RFID devices with sensors

multiple heterostructures of 2D materials have been created and the sensitivity of their electronic properties to the misalignment angle between the layers observed and explained theoretically, opening a new field of 2D materials twistronics.
Exploitation Route the field of 2D materials twistronics, started in the course of this project, is fast growing, involving dozens research groups worldwide,
Sectors Electronics

 
Description we will use our results to produce RFID with sensors. Such devices can be used for Internet of Things applications. Our research findings have been used for formulating Good guide on characterization of graphene, GPG145 by National Physical Laboratory [gpg145_graphene.pdf (npl.co.uk)]
First Year Of Impact 2017
Sector Electronics,Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description European Graphene Flagship
Amount € 150,000,000 (EUR)
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 04/2018 
End 03/2020
 
Description Formulating and Manufacturing Low Profile Integrated Batteries for Wireless Sensing Labels
Amount £1,289,916 (GBP)
Funding ID EP/R02331X/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 05/2018 
End 04/2021
 
Description Passively Powered Non-invasive Human Body Sensing on Bio-Degradable Conformal Substrates
Amount £655,878 (GBP)
Funding ID EP/P02713X/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 05/2017 
End 05/2020
 
Description Collaboration with Barcelona Institute of Science & Technology (ICFO) 
Organisation Barcelona Institute for Science and Technology
Country Spain 
Sector Academic/University 
PI Contribution Research on 2 DM heterostructures including van der Waals heterobilayers
Collaborator Contribution Research on 2 DM heterostructures including van der Waals heterobilayers
Impact Publications in peer-reviewed journals including 5 publications in Nature group journals
Start Year 2016
 
Description Collaboration with Columbia University, USA 
Organisation Columbia University
Country United States 
Sector Academic/University 
PI Contribution Modelling of Auger recombination of dark excitons in WS2 and WSe2 monolayers, Nanoscale thermal imaging of dissipation in quantum systems, and investigating Fast Relaxation of Photo-Excited Carriers in 2-D Transition Metal Dichalcogenides
Collaborator Contribution Modelling of Auger recombination of dark excitons in WS2 and WSe2 monolayers, Nanoscale thermal imaging of dissipation in quantum systems, and investigating Fast Relaxation of Photo-Excited Carriers in 2-D Transition Metal Dichalcogenides
Impact publications in peer-reviewed journals, including a Nature publication
Start Year 2016
 
Description Collaboration with Harvard 
Organisation Harvard University
Country United States 
Sector Academic/University 
PI Contribution Research on broken mirror symmetry in excitonic response of reconstructed domains in twisted MoSe2/MoSe(2)bilayers
Collaborator Contribution Research on broken mirror symmetry in excitonic response of reconstructed domains in twisted MoSe2/MoSe(2)bilayers
Impact Publication in Nature Nanotechnology (DOI: 10.1038/s41565-020-0728-z) - see the publication list
Start Year 2019
 
Description Collaboration with Imperial College London 
Organisation Imperial College London
Country United Kingdom 
Sector Academic/University 
PI Contribution Research on the Rational Design of Aqueous Graphene Dispersants, Nanoscale Mapping and Spectroscopy of Nonradiative Hyperbolic Modes in Hexagonal Boron Nitride Nanostructures and the Scholl Coupling Reaction for the Synthesis of Graphenes and Related Systems
Collaborator Contribution Research on the Rational Design of Aqueous Graphene Dispersants, Nanoscale Mapping and Spectroscopy of Nonradiative Hyperbolic Modes in Hexagonal Boron Nitride Nanostructures and the Scholl Coupling Reaction for the Synthesis of Graphenes and Related Systems
Impact Publications in peer-reviewed journals
Start Year 2017
 
Description Collaboration with Istituto Italiano di Tecnologia (IIT) 
Organisation Italian Institute of Technology (Istituto Italiano di Tecnologia IIT)
Country Italy 
Sector Academic/University 
PI Contribution Research on 2DMs and their heterostructures
Collaborator Contribution Research on 2DMs and their heterostructures
Impact 17 papers in peer-reviewed journals, including 7 papers published in Science and Nature group journals, that attracted 500+ references to date
Start Year 2016
 
Description Collaboration with Lancaster University 
Organisation Lancaster University
Country United Kingdom 
Sector Academic/University 
PI Contribution Research on novel 2D Materials and their heterostructures
Collaborator Contribution Research on novel 2D Materials and their heterostructures
Impact Collaboration resulted in more than 14 publications in peer-reviewed journals including 3 Science and Nature group publications - see the publications list
Start Year 2016
 
Description Collaboration with Massachusetts Institute of Technology MIT and Weizmann Institute of Science 
Organisation Massachusetts Institute of Technology
Country United States 
Sector Academic/University 
PI Contribution Research on imaging resonant dissipation from individual atomic defects in graphene
Collaborator Contribution Research on Imaging resonant dissipation from individual atomic defects in graphene
Impact Publication in Science journal (DOI: 10.1126/science.aan0877) - see the list of publications
Start Year 2016
 
Description Collaboration with Massachusetts Institute of Technology MIT and Weizmann Institute of Science 
Organisation Weizmann Institute of Science
Country Israel 
Sector Academic/University 
PI Contribution Research on imaging resonant dissipation from individual atomic defects in graphene
Collaborator Contribution Research on Imaging resonant dissipation from individual atomic defects in graphene
Impact Publication in Science journal (DOI: 10.1126/science.aan0877) - see the list of publications
Start Year 2016
 
Description Collaboration with National University of Singapore 
Organisation National University of Singapore
Country Singapore 
Sector Academic/University 
PI Contribution Research and modelling of 2DMs and their heterostuctures
Collaborator Contribution Research of 2DMs and their heterostuctures
Impact 14 Publications in peer-reviewed journals including 4 Science and Nature group publications - see the publications list
Start Year 2016
 
Description Collaboration with Scuola Normale Superiore di Pisa 
Organisation Scuola Normale Superiore di Pisa
Country Italy 
Sector Academic/University 
PI Contribution Research on 2 DMs and their heterostructures
Collaborator Contribution Research on 2 DMs and their heterostructures
Impact Publications in peer-reviewed journals including one highly cited paper and 3 Nature group publications
Start Year 2016
 
Description Collaboration with Yale University, USA 
Organisation Yale University
Country United States 
Sector Academic/University 
PI Contribution investigation of Spin-valley collective modes of the electron liquid in graphene
Collaborator Contribution investigation of Spin-valley collective modes of the electron liquid in graphene
Impact Published paper in peer-reviewed journal (DOI: 10.1103/PhysRevB.103.075422) - see the publication list
Start Year 2019
 
Description Collaboration with the University of Nottingham 
Organisation University of Nottingham
Country United Kingdom 
Sector Academic/University 
PI Contribution Research on van der Waals heterostructures, graphene superlattices and twisted bilayers of transition metal dichalcogenides
Collaborator Contribution Research on van der Waals heterostructures, graphene superlattices and twisted bilayers of transition metal dichalcogenides
Impact Publications in peer-reviewed journals including 2 Nature group publications and 2 Science publications
Start Year 2016
 
Title AEROGELS 
Description The invention relates to aerogels of two-dimensional materials such as graphene. This invention particularly relates to methods of making said aerogels by room temperature freeze casting (RTFC). 
IP Reference WO2017060719 
Protection Patent granted
Year Protection Granted 2017
Licensed No
Impact licensing in progress
 
Title GRAPHENE-BASED SENSOR 
Description The present invention relates to a textile-based sensor which incorporates graphene into the fibre. The graphene is incorporated by a dyeing process in which a liquid composition containing the graphene is contacted with the fibre. The present invention thus also relates to a process for the preparation of a graphene-based yarn and the use of the resulting yarn in a variety of sensing applications. The graphene-based yarns of the invention may be derived from naturally occurring materials such as cotton or may be based on synthetic materials such as polyester, nylon, viscose, etc., or may be a blend of natural and synthetic materials. The present invention also relates to a screen-printed textile or a porous material, such as paper, printed on its surface with a 2D material such as graphene. This printed textile (fabric) has the 2D material incorporated by a screen-printing process in which a liquid or paste composition containing the 2D material is contacted with the textile or paper substrate. The present invention thus also relates to a process for the preparation of a graphene-or other 2D material-printed substrate and the use of the resulting printed substrate in a variety of applications such as wearable technology. The textiles of the invention may be derived from naturally occurring materials such as cotton or may be based on synthetic materials such as polyester, nylon, viscose, etc., or may be a blend of natural and synthetic materials. 
IP Reference WO2017220979 
Protection Patent granted
Year Protection Granted 2017
Licensed No
Impact searching for funding to create a spin-off company
 
Title HETEROSTRUCTURES AND ELECTRONIC DEVICES DERIVED THEREFROM 
Description The advent of graphene and related 2D materials has recently led to a new technology: heterostructures based on these atomically thin crystals. The paradigm proved itself extremely versatile and led to rapid demonstration of tunnelling diodes with negative differential resistance, tunnelling transistors, photovoltaic devices and so on. In the present invention, the complexity and functionality of such van der Waals heterostructures is taken to the next level by introducing quantum wells (QWs) engineered with one atomic plane precision. We describe light-emitting diodes (LEDs) made by stacking metallic graphene, insulating hexagonal boron nitride and various semiconducting monolayers into complex but carefully designed sequences. 
IP Reference WO2016203184 
Protection Patent granted
Year Protection Granted 2016
Licensed No
Impact basic technology to produce LED devices from 2D materials. Crucial for many applications
 
Title IMPROVEMENTS RELATING TO THE AUTHENTICATION OF PHYSICAL ENTITIES 
Description An authentication device (20) comprises one or more flakes of a substantially two- dimensional material (14). The one or more flakes of the substantially two- dimensional material (14) have an operative area configured to emit, by non- resonant photoluminescence, electromagnetic radiation with a property that varies with position in the operative area. 
IP Reference WO2016120608 
Protection Patent granted
Year Protection Granted 2016
Licensed No
Impact New methods to authenticate documents and high value items for various industries
 
Title LAYERED MATERIALS AND METHODS FOR THEIR PROCESSING 
Description A method for producing nanoplates derived from a layered material, includes the steps: (a) mixing particles of said layered material with a carrier liquid to form a dispersion of said particles in said carrier liquid; (b) pressurizing the dispersion to a pressure of at least 10 kpsi; and (c) forcing the dispersion along a microfluidic channel under said pressure, to apply a shear rate of at least 105 s-1 to said particles in the dispersion. Exfoliation of nanoplates from said particles is thereby caused. The nanoplates may be graphene nanoplates, for example. Steps (b) and (c) may be repeated for a number of cycles in order to promote exfoliation. The method may be carried out using a microfluidizer. 
IP Reference WO2017060497 
Protection Patent granted
Year Protection Granted 2017
Licensed Yes
Impact widely used method for the production of 2D inks
 
Title SENSOR 
Description This invention relates to sensors and, in particular radio-frequency identification (RFID) tags. The sensors comprise oxygenated graphene which is arranged to alter the electrical properties of an electrical system in response to a change in environmental conditions. A particular advantage of the present invention is that the sensor can be assembled layer by layer to fabricate a multifunctional sensor. A multi-functional sensor may comprise multiple regions of different sensing materials that can sense different environmental changes. 
IP Reference WO2017208013 
Protection Patent granted
Year Protection Granted 2017
Licensed No
Impact searching for a party to license to