Professor Emeritus

Background

Secondary ion mass spectrometry (SIMS) is the mass spectrometry of ionised particles that are emitted when a surface is bombarded by energetic primary particles, usually ions (for example Ar⁺, Ga⁺, Cs⁺ and more recently Au_n⁺, Bi_n⁺ and C₆₀⁺). The emitted (sputtered) secondary particles are electrons; neutrals species atoms or molecules; atomic or cluster ions. The vast majority of sputtered particles are neutrals, but it is the secondary ions that are analysed and detected by a mass spectrometer. It is this process that provides a mass spectrum of a surface to provide detailed chemical analysis of a surface or solid. The process is destructive of surface chemistry. In the late 1960s Benninghoven’s group in Münster developed the technique – static SIMS – in which the amount of surface removed is limited to less than 1%. Under these conditions each ion impact samples virgin surface and in theory the ions emitted reflect undamaged chemistry. Until our very recent developments using cluster primary ion beams this was the only way to access molecular information via SIMS.

Research Highlights

	Static SIMS spectra DO reflect surface chemical structure. In the period 1976 to 1985 using the first quadrupole and triple quadrupole MS/MS systems the group was unique in demonstrating via systematic studies into the basic surface chemistry of metals, oxides and polymers that the spectra observed reflected the detailed chemistry of the surfaces [2].
	FABMS – a crucial contribution. The group developed the fast-atom bombardment beam in 1980 that led to the invention of fast-atom-bombardment mass spectrometry with Mike Barber. For the first time FABMS enabled non-volatile compounds to be analysed easily with a mass spectrometer – a revolutionary advance.
	The first static SIMS industrial analysis service. With DTI support this service was founded in 1983 and ultimately became the UK’s largest independent surface analysis service (CSMA Ltd)
	Time-of-flight (ToF) MS technology introduced into static SIMS instruments. ToF mass spectrometers are quasi-parallel detectors and offer ~103 increase in signal compared to quadrupole MS instruments. In 1987 the group introduced the first ToF-SIMS instrument in the UK and thus contributed to its acceptance world-wide [3].
	The first database of standard SIMS spectra for analysts which developed into The Static SIMS Library. The Handbook of Static SIMS with standard spectra was published in 1989. This has developed over the years into a CD ROM of over 1000 spectra – The Static SIMS Library [4].
	The first imaging ToF-SIMS instrument interfaced to laser post-ionisation capability to enhance sensitivity and configured for biological applications. Since 1993 with Prof. Nick Winograd’s group at Penn State University and in collaboration with Kore Technology of Cambridge and Ionoptika of Southampton the group has been involved in developing a new version of ToF-SIMS instruments aimed at bio-analysis with good spatial resolution [5, 6].
	Unique studies combining ToF-SIMS and FTIR to probe atmospheric chemistry. Since 1990 in collaboration with Dr Andrew Horn’s group combining FTIR with ToF-SIMS has proved to be very successful in the study of chemistry at the surface of ice mimics of polar stratospheric clouds and sulfuric acid hydrate particles [7, 8].
	A radically new SIMS analysis paradigm results from the development of polyatomic cluster primary ion beam systems. During 1996 to 2000 in collaboration with Ionoptika Ltd, the group developed for the first time a liquid gold ion beam system capable of delivering good Au3+ cluster ion beams, and a C60 ion beam system configured for routine installation on ToF-SIMS systems. These dramatically enhanced secondary ion yields (≥ 103) of molecular systems up to m/z 3000 – a great benefit for bio-analysis. Of even greater significance, C60 bombardment produced dramatically lower chemical damage in many systems such that the static limit could be abandoned and 100% of a sample could be used during an analysis. This is revolutionising molecular SIMS analysis and will enable not only very high sensitivity 2D imaging but also for the first time 3D analysis and imaging [9].
	Hosted 15 th International Conference on Secondary Ion Mass Spectrometry (SIMSXV) at The University of Manchester.
	A new concept SIMS instrument exploiting the capabilities of C60 and similar cluster primary ions for high spatial resolution 2D and 3D analysis and imaging of bio-systems. In 2005 the group was awarded the first EPSRC Critical Mass Award in Analytical Science with Professor Webb’s group at Surrey (~£2M) to exploit the advances resulting from the use of polyatomic ion beams in molecular SIMS analysis of biological systems. To that end a new generation of ToF-SIMS instrument interfaced with the complementary technique of ATR-IR is being developed in collaboration with Ionoptika Ltd and SAI Ltd. [more details]
	First demonstration of 3D ToF-SIMS imaging of a biological cell using C60 primary ion beam – 2006 [10].

Awards and recognition

	1987 – D.Sc, University of Bristol.
	1991 SERC Achievements in Chemistry features the group’s ToF-SIMS research
	C60 ion beam developments featured in Nature News report, D.G. Castner, View from the Edge, Nature, 422, 129 – 130 (2003) and in ESI Fast-breaking paper report – http://www.esi-topics.com/fbp/2004/december04-JohnVickerman.html
	EPSRC’s Spotlight publication in Summer 2003 reports successes with the new ToF-SIMS instrument for biological systems analysis.
	Awarded 2004 Rivière Prize of the UK Surface Analysis Forum – ‘for work which has been judged outstanding in its continuing and lasting contribution to surface analysis’.
	Thomson Scientific have recently acknowledged that our article introducing C60 as a primary ion source for ToF-SIMS, published in Analytical Chemistry in 2003, is one of the most cited papers in the field of Materials Science with 106 citations. For further information see the article in ESI-Special Topicsin March.Full reference of article: A C60 Primary Ion Beam System for Time of Flight Secondary Ion Mass Spectrometry: Its Development and Secondary Ion Yield Characteristics.Weibel, Daniel; Wong, Steve; Lockyer, Nicholas; Blenkinsopp, Paul; Hill, Rowland; Vickerman, John C.Analytical Chemistry 75 (2003) 1754-1764 [go there now…]
	Awarded the prestigious Theophilus Redwood Award 2009 by the Royal Society of Chemistry.’… for his outstanding contribution to the development and application of secondary ion mass spectrometry techniques for surface analysis and 3D chemical imaging of organic and biological systems.’

Commercial Application of Research

	1983 – With DTI support founded an industrial surface analysis service based on SSIMS which subsequently became the UK’s only independent surface analysis company (CSMA Ltd).
	1997 – Co-founded SurfaceSpectra Ltd, a scientific publishing company – supplying knowledge systems for surface analysis: http://www.surfacespectra.com
	2000 to date. Commercialization of C60 ion beam systems by Ionoptika Ltd. Over 100 sold world-wide.

 Books and reference materials

	Handbook of Secondary Ion Mass Spectrometry, A. Brown, D. Briggs and J.C. Vickerman, pp 160, John Wiley & Sons, 1989
	Secondary Ion Mass Spectrometry – Principles and Applications. Eds J.C. Vickerman, A. Brown and N.M. Reed, pp 340, Oxford University Press, 1989.
	SurfaceSpectra Static SIMS Library (1997) – a library of standard spectra against which to compare their unknowns. [4].
	‘Surface Analysis – The Principal Techniques’, Ed J.C. Vickerman, John Wiley & Sons, Chichester, 1997. Over 3000 copies sold world-wide. A second edition was published in 2008.
	‘ToF-SIMS – Surface Analysis by Mass Spectrometry’; Vickerman, J.C.; Briggs, D., Eds.; SurfaceSpectra Ltd (2001) .
	CD ROM: The Static SIMS Library, Version 4. J.C. Vickerman; D. Briggs; A. Henderson. Eds.; SurfaceSpectra Ltd., 2006

References

1. J.C. Vickerman, in ToF-SIMS – Surface Analysis by Mass Spectrometry; Vickerman, J.C.; Briggs, D., Eds.; SurfaceSpectra (2001)
2. G.J. Leggett and J.C. Vickerman, An empirical model for ion formation from polymer surfaces during analysis by secondary-ion mass spectrometry. Int. J. Mass Spectrom. Ion Proc. 122 , 281-319 (1992).
3. J.A. Eccles and J.C. Vickerman, The characterization of an imaging time-of-flight secondary ion mass spectrometry instrument. J. Vac. Sci. Technol. A7, 234 (1989);
4. J.C. Vickerman, D. Briggs and A. Henderson, “The Static SIMS Library Ver. 4”, (SurfaceSpectra Ltd, Manchester), (2006).
5. Braun, Robert M.; Blenkinsopp, Paul; Mullock, Steve J.; Corlett, Clive; Willey, Kenneth F.; Vickerman, John C.; Winograd, Nicholas. Performance characteristics of a chemical imaging time-of-flight mass spectrometer. Rapid Communications in Mass Spectrometry 12 (1998) 1246-1252
6. Jones, Emrys A.; Lockyer, Nicholas P.; Vickerman, John C,. Mass spectral analysis and imaging of tissue by ToF-SIMS-The role of buckminsterfullerene, C60 +, primary ions. International Journal of Mass Spectrometry 260 (2007) 146-157
7. H.A. Donsig, D. Herridge and J.C. Vickerman, ‘Static SIMS Studies of Reactions on Mimics of Polar Stratospheric Clouds III: Mechanism of Chlorine Nitrate Decomposition and Reaction’ . J. Phys Chem. A, 1 999, 103 , 9211-9220
8. J. Fletcher, A. Henderson, A. Horn and J.C. Vickerman, ToF-SIMS studies of sulfuric acid hydrate films, J. Phys. Chem B , 2004; 108 (19); 5960-5966.
9. Weibel, D.E.; Wong, S.; Lockyer, N.P; Blenkinsopp, P.; Hill, R.; Vickerman, J.C., A C 60 Primary Ion Beam System for ToF-SIMS: its development and secondary ion yield characteristics, Anal Chem , 2003, 75, 1754-1764.; Davies, N.; Weibel, D.E.; Lockyer, N.P; Blenkinsopp, P.; Hill, R.; Vickerman, J.C., Appl. Surf. Sci. 203-204, 223 (2002);
10. John S. Fletcher, Seetharaman Vaidyanathan, Nicholas P. Lockyer, Matthew J. Baker, John C. Vickerman. ToF-SIMS 3D biomolecular imaging of Xenopus laevis oocytes using buckminsterfullerene (C 60) primary ions. Analytical Chemistry 79 (2007) 2199-2206.