Expanding the Environmental Frontiers of Operando Metrology for Advanced Device Materials Development

Lead Research Organisation: University of Cambridge
Department Name: Engineering


Lord Kelvin famously stated "when you cannot measure it, when you cannot express it in numbers, your knowledge is of a meagre and unsatisfactory kind". This holds none more true than for nanotechnology today. Emergent materials such as 2D transition metal dichalcogenide (TMD) compounds offer exciting, wide opportunities from novel (opto-) electronic devices to energy storage and catalytic energy conversion. For the latter, TMDs materials like MoS2 have shown high catalytic activity and offer large potential as earth abundant electro-catalysts to for instance convert waste CO2 into industrially relevant chemicals/fuels and to generate hydrogen sustainably, i.e. processes of utmost significance as strategies for a sustainable, clean future economy. However, TMD catalysts can undergo significant chemical and structural changes during reactions, and the mechanisms that give the high catalytic activity remain largely unknown. Our knowledge is currently equally meagre in terms of materials synthesis. There is very little understanding how TMDs actually grow and hence how the structure and properties of these materials can be scalably controlled. These challenges and lack of understanding are common to numerous emerging materials. One key reason for this is that they typically can only be resolved and adequately characterised at a "post-mortem" stage, and we are left to speculate what mechanisms actually govern growth or material functionality at industrially relevant "real-world" conditions.

This proposal aims at true operando characterisation of novel materials like TMDs under industrially relevant reactive atmospheres at elevated temperatures, to have a transformative impact on their future use by developing a fundamental understanding of their design and functionality. Our focus will be on electron microscopy and spectroscopy, in particular scanning electron microscopy and X-ray photoelectron spectroscopy, which are among the most wide-spread and versatile characterisation techniques in modern science, used across all disciplines in academia and industry. They are endowed with high (near-)surface sensitivity, making them powerful tools for analysing the structure and chemistry of surfaces and interfaces. However, low-energy electrons are also strongly scattered by gas molecules, and therefore all these techniques are conventionally performed under high vacuum or restricted environmental conditions. We propose new environmental cell approaches that can be flexibly implemented for the many electron-based techniques to overcome these restrictions, and enable direct characterisation at high spatial and/or chemical resolution across an unprecedented range of industrially relevant process conditions for temperatures as high as 1000C and in reactive gaseous or liquid environments. The proposal builds on recent strategic equipment investment at Manchester, Cambridge and the Diamond Light Source/Harwell, and together with market-leading industrial partners our vision is to pioneer versatile approaches that open up new correlative, multi-modal operando probing capability applicable to a wide range of fields including organic semiconductors, battery/energy research, catalysis and life sciences. This will also link to simulation and theory to achieve new levels of understanding and predictive power. Applied to TMD materials, this capability will allow us to directly interrogate TMD nucleation and growth at industrially relevant reactor conditions, to develop new manufacturing processes including for so far largely unexplored metallic compounds. This will further allow us for the first time to systematically study model TMD catalysts under reaction conditions. In particular, we propose to explore metallic TMDs like NbS2, as unlike to semiconducting MoS2, their catalytic activity could extend over the entire basal plane, opening new directions to design novel electro-catalysts with low overpotential and high current densities.

Planned Impact

A recent Foresight review commissioned by the UK government (tinyurl.com/yd7harx9) highlights the importance of novel materials in terms of broad industrial and societal needs, and specifically emphasises that in order to access the more valuable part of the materials supply chain, new in-situ experimentation and modelling are required, offering the potential to shorten dramatically the design-make-test cycle that currently paces the timing of new material deployment. Our project will provide such new in-situ/operando capability matched to industrial conditions, hence will have leveraged significant impact in many strategic areas incl. Energy, Quantum Technologies, Information and Communication Technologies (ICT), the Internet of Things (IoT), Healthcare, Ultra-precision manufacturing, with a return for UK plc, in innovation and exploitation. The long term impact of our project can be significant in particular as it underpins important future developments in metrology, materials and diverse applications.
Our project addresses key questions pertinent to industrial materials development for transition metal dichalcogenide (TMD) compounds, in particular low-cost, scalable, reproducible production and device integration. This will allow to develop pathways to their industrial exploitation, and to enable commercial dividends to be paid on the substantial investment that the UK has already made in 2D materials research. Our proposal covers the whole value chain and we bring together market-leading industrial partners and key stakeholder such as NPL and national user facilities like the Diamond light source, Harwell XPS and the UK CatalysisHub hence supports the whole developing market. Our partner companies will directly benefit from the research results and will be natural exploitation pathways. The new environmental cell capabilities will strengthen the market positions of Zeiss, SPECS and Silson. Industrially relevant TMD growth processes and target applications will open new opportunities and markets for Aixtron UK. We infer that the technology IP created will yield long-term economic benefits to the UK, which will accrue as capability grows. The technologies developed will provide a particularly fertile ground for the generation of spin-out companies, for instance commercialising the proposed cell technology, and help to sustain the world-leading innovation, resilience and competitiveness of UK science parks, incl. the Cambridge Cluster of Companies, the Harwell campus and Manchester corridor, that support more than hundred thousand jobs across the UK.
The long term societal impact of our project can be significant in particular through the wide range of applications of novel materials, including for TMDs particularly new form factors in life style electronics, secure and faster communication technology, mass sensing applications in healthcare, security and environmental protection, new energy generation and storage solutions, and development of technologies which will benefit the nation's health through reductions in harmful emissions over the coming decades. Our proposal targets new type of catalysts to enable sustainable, clean energy and that can mitigate CO2 emissions and convert waste CO2 into industrially relevant chemicals and fuels. These processes have significant potential to help reducing the carbon footprint of our society, open new means for energy storage from intermittent energy sources e.g. wind and solar, and assist policy-makers and government agencies in meeting internationally-agreed ambitious emissions obligations and in building a sustainable economy to tackle pressing long-term challenges such as climate change.


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Braeuninger-Weimer P (2020) Crystal Orientation Dependent Oxidation Modes at the Buried Graphene-Cu Interface. in Chemistry of materials : a publication of the American Chemical Society

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Elizabeth S. Jones (2021) Enclosed Cells for Extending Soft X-ray Spectroscopies to Atmospheric Pressures and Above in ACS Symposium Series: Ambient Pressure Spectroscopy in Complex Chemical Environments

Description The research consortium developed new operando probing approaches with high spatial (electron microscopy) and chemical resolution (electron spectroscopy), which enables key scientific questions to be addressed pertinent to industrial materials development of monolayer crystals of transition metal dichalcogenide (TMD) compounds, in particular low-cost, scalable, reproducible production and device integration. Metal organic chemical vapour deposition conditions relevant to industrial reactors could be implented on scanning electron microscopy and X-ray photoelectron spectroscopy systems, which led to new insights into the use of more environmentally benign organosulfur precursors. A new generation of environmetal cells based on graphene membranes has been developed and these are now being used to develop new insights into catalyst design.
Exploitation Route The project covers the whole value chain and brings together market-leading industrial partners and key stakeholder such as NPL and national user facilities like the Diamond light source, Harwell XPS and the UK CatalysisHub hence supports the whole developing market. The discoveries and developed new understanding will directly benefit
many academic communities, both within the UK and worldwide, for whom our proposal will open a significant range of new opportunities to address their materials and application problems. Our operando capabilities can be implemented on numerous existing lab systems, including those sold via our industrial partners.
Sectors Digital/Communication/Information Technologies (including Software),Electronics,Energy,Environment,Healthcare,Manufacturing, including Industrial Biotechology