Organic multilayer reference materials for depth profiling

S. J. Spencer, A. G. Shard and S. A. Smith

Nanoanalysis Group, National Physical Laboratory, Teddington, UK Email: steve.spencer@npl.co.uk http://www.npl.co.uk/nanoanalysis

Introduction
Understanding the depth distribution of organic species is of great importance for the manufacture of a number of innovative devices such as organic electronics, medical devices and polymeric films.

Fluorinated materials
*
F F O HN F F OH Fmoc

Few analytical methods can measure these depth distributions to the required levels of accuracy and sensitivity, however in recent years it has become possible using cluster ion beam sputtering combined with X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS).

O N O AI N N O N

Multilayer reference materials

Irganox 1010 Irganox 1010 Irganox 1010 50 nm 50 nm 100 nm
Irganox 1010 matrix. 1, 3 or 10nm Irganox 3114 layers (different thicknesses available on request). XPS Use nitrogen as a marker, present in Irganox 3114 not in Irganox 1010 SIMS Use negative SIMS analysis, unique Irganox 3114 secondary ions at 26 Da, 42 Da, 346 Da and 564 Da.

A material that has higher XPS sensitivity than the nitrogen in Irganox 3114 was needed. FMOCpentafluoroL-phenylalanine N C24H16F5NO4 was selected and the fluorine signal used as the marker.

*Data courtesy of W. Boxford and C. Blomfield, Kratos

Figure 4 Profiles of Irganox 1010 with 3 nm FMOC marker layers

Irganox 1010

100 nm

VAMAS Interlaboratory study

Multilayered organic reference materials have enabled rapid progress in cluster ion beam sputtering for organic depth profiling. They have provided manufacturers and practitioners with a common benchmark against which the performance of different experimental methods can be judged and experimental evidence against which theories can be tested. Reference materials based on Irganox 1010 and Irganox 3114 have been extensively used in this regard. VAMAS interlaboratory studies, completed in 2009 and 2011 using cluster ion beams as the sputtering source demonstrated the utility of these materials in assessing instrument performance, optimising experimental conditions and understanding fundamental processes. O O F F F F OHOH HN HN F F Fmoc F F Fmoc F F Alternatives are being studied, such as those materials which are of great commercial importance to the organic electronics industry, e.g.

Irganox 1010 Silicon

100 nm

Figure 1 - 3D SIMS of reference material with fluorinated marker layers

X-ray photoelectron spectroscopy

New materials in development

N N N N AI AI O O O O N N

O O

N N

N N

Alq3
(Tris(8-hydroxyquinolinato)aluminium) C27H18AlN3O3

NPB
(N,N-Di-[(1-naphthyl)-N,N-diphenyl] -1,1-biphenyl)-4,4-diamine) C44H32N2

Figure 2 Expected XPS response

Mixed composition samples

A new class of reference material based upon binary mixtures of organic compounds with known compositions will soon be available. Samples are produced by alternately depositing sub-nanometre layers of two materials. A VAMAS interlaboratory will start soon. Please contact alex.shard@npl.co.uk if you are interested in participating.
Queens Printer and Controller of HMSO, 2013. 10511/0613

For further details

Figure 3 XPS depth profile (coronene, 16 keV, 81 incidence angle), Irganox 1010 with 10 nm Irganox 3114 marker layers

www.npl.co.uk/science-technology/surface-and-nanoanalysis/ services/organic-multilayer-reference-and-test-materials-for-depthprofiling or contact steve.spencer@npl.co.uk

Acknowledgements
Kratos Analytical Ltd for collaboration with the XPS depth profiling. Rasmus Havelund (NPL) for the SIMS image and data.

www.npl.co.uk