Applied X-ray spectroscopy

Implementing inorganic materials in affordable, flexible biosensor platforms

Integrating inorganic materials, that show great potential for sensing application, into platforms that are suitable for the industrial production of cheap, non-invasive sensors is of great importance for their broad implementation. In our recent open access paper in Materials Research Express, we show the successful integration of copper oxide based electrodes for glucose sensing on printed circuit board (PCB) technology. Together with collaborators at the University of Bath led by Dr Despina Moschou we could show that direct oxidation on PCB compatible substrates is possible and how production parameters including annealing duration and temperature influence the surface morphology and chemistry as well as influencing the resulting electrochemical sensing properties.

The work in the paper is based predominantly on the Masters research of Shijia Liu and Ayse Ay, who did their Masters projects as part of their MSc in Advanced Materials Science and Engineering degrees in the group in the academic year 2017/18. The research also included the involvement of two UROP (Undergraduate Research Opportunities Programme) students, Qiaochu Luo and Xiangqi Hu.

Getting to the bottom of TiW

After spending a week at EMPA in Zurich, Switzerland, depositing high quality TiW thin films in February, Curran, Nathalie and Anna travelled to DESY, Hamburg, Germany, in the first week of March to collect HAXPES data on them. We were back at one of our favourite HAXPES beamlines, P22 at PETRA III, and the work was, as always, expertly supported by the local team of Dr Christoph Schlueter and Dr Andrei Hloskovsky.

In order to ensure that the samples where in the best possible condition for measurement we needed to apply quite an involved level of logistics including vacuum sealing, glove box transferring, and in-situ sputtering. This enabled us to measure the films in their truly metallic state without interference from surface oxidation and contamination. Although HAXPES enables to probe the bulk of a sample, overlying surface oxides can significantly influence and perturb the HAXPES spectral quality. We both explored the influence of Ti/W composition on the electronic structure as well as a challenging experiment to try and probe the buried interface between TiW and the underlying SiO2/Si substructure. We also had time to explore the local offerings of cake and caffeinated beverages.

Making mixed metal systems

In the second half of February Curran and Anna spent a week at EMPA, the Swiss Federal Laboratories for Materials Science and Technology, in Zurich, Switzerland, to deposit a range of TiW films for an upcoming HAXPES experiment at DESY, Hamburg, Germany. The samples will be used to increase our understanding of mixed metal barrier materials for power electronics.

This collaboration was made possible by the award of a UCL Global Engagement Fund (GEF), a funding route available to UCL academics that supports collaboration with colleagues based in other countries.

Our colleagues at EMPA, Dr Sebastian Siol and Dr Siarhei Zhuk were excellent hosts and shared their extensive knowledge on the deposition of such metal systems. In parallel, Curran was able to immediately characterise all deposited samples using a combination of X-ray fluorescence (XRF), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). This provided a solid characterisation basis to finetune deposition parameters and achieve a high level of control over film thicknesses and composition.

Although it was an intense week of work, there was still time to enjoy the finer side of life in Zurich, including sampling some local delicacies including Schnitzel (pictured below), Raclette and a very good amount of Swiss chocolate.

How to clean metals

In early February a team led by Curran, including Prajna, Yujiang and Anna, visited beamline I09 at Diamond Light Source in an attempt to collect soft and hard X-ray photoelectron spectroscopy (SXPS and HAXPES) data on the pure metals titanium and yttrium. Sounds simple, but obtaining clean metal surfaces, and more importantly maintaining clean surfaces during measurement, is a real challenge for these two. Titanium in particular finds application as a so-called getter material, where its high reactivity is used to absorb stray molecules in vacuum chambers to achieve ultra-high vacuum (UHV) conditions. Great for vacuum chambers, not ideal when you need to keep a titanium surface free of adsorbates. After some not entirely successful previous attempts, a combination of ex-situ chemical etching, in-situ argon etching, and keeping the samples at a few hundred toasty degrees during measurement proofed to be the magical combination to obtain perfect metallic spectra. Such high quality reference datasets are crucial to aid the exploration and understanding of complex systems, where convoluted spectral data can prove to be a formidable challenge. This data will support Curran’s ongoing work on metallisation schemes for power electronics (read more about some of the work here and here) and further projects on energy materials and catalysts. As always the beamtime was masterfully supported by Pardeep Kumar. This was also the first synchrotron experience for Prajna and Yujiang.


At the end of January Aysha and Anna spent a week at the Swedish synchrotron Max IV in Lund using the solid state end station of the FinEstBeAMS beamline. Together with colleague Dr Matthias Kahk from the University or Tartu, Estonia, we used polarisation-dependent soft X-ray photoelectron spectroscopy (SXPS) to explore the electronic structure of bismuth vanadate (BiVO4) and the influence of different dopants on the system. This was Aysha’s first synchrotron experience.

SPIE Photonex 2021 – Glasgow

Nathalie, Curran and Anna ventured to Glasgow this week for the group’s first in-person conference since March 2020. Nathalie and Curran presented part of their PhD work in excellent contributed talks. Curran got people excited about studying the behaviour of TiW diffusion barriers in metallisation schemes for power electronics (see a recent paper) and Nathalie clearly showcased the importance of radiation dose when comparing the effects of X-rays on samples during diffraction and spectroscopy (see a recent paper and Diamond Light Source Science Highlight). Anna presented an invited talk on the influence of polymorphism in Ga2O3 trying to convince the audience that core level spectra are sensitive to local coordination environments (read all about it here).

It was great to get back to in-person talks and be inspired by an excellent line-up of speakers in the Photoemission Spectroscopy for Materials Analysis section organised by Robert Palgrave, Rosa Arrigo and Phil King.

Work on X-ray induced changes gets a shout-out in Diamond Light Source Science Highlights

Our recent work led by Nathalie Fernando on the effects X-ray irradiation has on small molecular crystals during X-ray diffraction and X-ray photoelectron spectroscopy has been chosen as a Diamond Light Source Science Highlight.

Nathalie and Anna had a great experience talking to the Diamond comms team, who put together an awesome article for the Science Highlights series, which has showcased work conducted at the synchrotron since 2014.

Schematic of the [M(COD)Cl]2 catalysts and the different ways in which they are affected by X-ray irradiation.

X-ray induced changes in small molecular crystals

Our most recent work, led by Nathalie Fernando, focuses on a subject matter typically considered a nuisance to many experimentalists who use X-rays. That is, the X-ray induced changes to the sample being probed. X-rays feature in many characterisation techniques today but are often (incorrectly!) regarded as non-destructive. In recent years, these unwanted X-ray-matter effects have been worsened by X-ray sources, both lab and synchrotron based, with ever increasing brightness. These X-ray induced phenomena have been widely studied in macromolecular crystallography, but unfortunately, the same cannot be said for small molecular crystals.

Recently published in the Journal of Physical Chemistry A, (available also as a preprint on ChemRxiV) our paper is the culmination of a huge collaborative effort comprising of crystallographers, spectroscopists, and theorists.

Here, we explore the effects of X-ray irradiation on two industrially important catalysts [Ir(COD)Cl]2 and [Rh(COD)Cl]2, using synchrotron-based X-ray diffraction and laboratory-based X-ray photoelectron spectroscopy. Both single crystal and powder X-ray diffraction were used to obtain a detailed understanding of the changes in structure and atomic positions upon irradiation. This was only possible through the close collaboration with an amazing team of crystallographers, including Dr Andrew Cairns (Imperial College London), Dr Claire Murray (Diamond Light Source), and Dr Amber Thompson (University of Oxford). Crystallography and spectroscopy, with density functional theory calculations, led by Dr. Laura Ratcliff (Imperial College London) and with the support of Nayera Ahmed, an MSci student in the group, provide insights into the structural, chemical, and electronic changes taking place within the samples upon X-ray irradiation. Crucially, these changes are studied with respect to X-ray dose, using the RADDOSE-3D software, with the support of Dr. Joshua Dickerson and Prof. Elspeth Garman at the University of Oxford. 

This work presents an important first step towards understanding the changes in small molecular systems due to X-ray irradiation, and we hope that the combination of techniques outlined, will form the basis of many future systematic X-ray damage studies on a wide range of important small molecular materials.

How to stop diffusion (and how to peak fit tungsten core levels)

Check out our latest collaboration with colleagues from Infineon Technologies Austria and Kai, diving further into the world of power semiconductor devices. Here, we move away from the groovy science of front-end SiC/SiO2 device technologies, in favour of back-end metallisation architectures. In order to unlock the many advantages of copper metallisation schemes in power electronics, diffusion barriers are required to isolate the metallisation from the underlying silicon substructure. In recent years, the binary alloy of titanium-tungsten (TiW) has been proposed as an effective barrier but in order to have confidence in the material, extensive characterisation of its potential degradation mechanisms need to be conducted.

Using both laboratory SXPS and synchrotron HAXPES we explore the oxidation and thermal stability of TiW, providing insight into two prominent modes of degradation, from multiple depth perspectives. Additionally, we have paired experiment with theory, working with collaborators at Imperial College London and the Barcelona Supercomputing Center to aid with better understanding the observed systematic changes to the electronic structure of the alloy in response to thermal treatments.

This marks the first first author research paper of Curran’s PhD journey, so one down and hopefully many more to come. The paper can be found here in JApplPhys (the preprint is also on arxiv) and we’d love to hear your thoughts.

P.S For all the peak fitting XPS enthusiasts, be sure to check out the SI for a detailed explanation of the W 4f procedure in all its glory 🙂

HAXPES in 2020

Ever thought about wanting to do HAXPES but not sure where to start? Well hopefully now you have a useful resource to help you decide where and what you could measure with this exciting technique!

Our review on the state-of-the-art of HAXPES in 2020 is now out in the Journal of Physics: Condensed Matter and it is fully open access for your reading pleasure. This gargantuan effort was spear headed by two fantastic PhD students in the group, Curran Kalha and Nathalie Fernando, who took on a leading role in coordinating efforts and ensuring consistency throughout the paper, beyond contributing their own individual sections to the review paper. We are also particularly proud of Prajna Bhatt, who did her undergraduate literature review in the group and which has become the starting point for one of the sections of the review.

The review would not have been possible without the gargantuan effort by a large team of collaborators and friends including Fredrik Johansson, Andreas Lindblad, Håkan Rensmo, León Zendejas Medina, Rebecka Lindblad, Sebastian Siol, Lars Jeurgens, Claudia Cancellieri, Kai Rossnagel, Katerina Medjanik, Gerd Schönhense, Marc Simon, Alexander Gray, Slavomír Nemšák, Patrick Lömker, and Christoph Schlueter. Our breadth of different experiences across the HAXPES remit has hopefully enabled us to give a comprehensive and balanced overview of machines, systems and applications of HAXPES today.

We are also incredibly grateful for all the beamline scientists and instrument staff at both synchrotrons and in laboratories across the globe who have provided information on existing instrumentation through completing surveys and answering our many questions via email. We hope that the overview we were able to include in the review acts as a selection guide for users to choose the most suitable experimental setup to perform their experiments. There truly is a HAXPES system for everyone! We also hope that this review will act as a point of comparison in the future to benchmark how the technique develops and we hope we can look back in 10 years time (when we might have to write a follow up review) and marvel at all the progress we have made.