Using Adventitious Carbon for Charge Correction (Referencing)

by M. Biesinger (UWO)

Spectra from insulating samples can then be charge corrected by shifting all peaks to the adventitious C 1s spectral component (C-C, C-H) binding energy set to 284.8 eV. The C 1s spectrum for adventitious carbon can be fit by defining a peak constrained to be shifted 1.3 eV above the tallest peak, with a FWHM equal to the main peak (C-C, C-H). This higher binding energy peak is ascribed to alcohol and/or ether functionality (C-OH, C-O-C). Further high binding energy components can be added if required. For example: C=O at approximately 2.8 eV above the main peak and O-C=O (acid or ester) at 3.8 to 4.2 eV above the main peak. One or both of these peaks may have to be constrained to the FWHM of the main peak if they are poorly resolved.

Spectra from insulating samples can then be charge corrected by shifting all peaks to the adventitious C 1s spectral component (C-C, C-H) binding energy set to 284.8 eV. There is certainly error associated with this assignment. Swift [1] lists a number of studies showing errors ranging from ±0.1eV to ±0.4 eV.  “Newer” studies (late 1970’s) range from ±0.1 to ±0.3 eV. “Older” studies (late 1960’s to early 1970’s) were in the ±0.4eV range – however, reproducibility and resolution of the spectrometers of the time may have played a role.  Barr’s [2] work from 1995 states that error in using adventitious carbon is ±0.2 eV.  Our work [3] in 2002 also suggests error in the ±0.2eV to  ±0.3eV range.  Experience with numerous conducting samples (1995 to present) and a routinely calibrated instrument have shown that the C 1s signal generally ranges from 284.7 eV to as high as 285.2 eV [4].

For organic systems, especially polymers, it is convenient to charge correct to the C-C, C-H signal set to 285.0 eV. This makes for easier comparison to the polymer handbook [5] which uses this number for charge correction.

References:
[1] T.L. Barr, S. Seal, J. Vac. Sci. Technol. A 13(3) (1995) 1239.
[2] P. Swift, Surf. Interface Anal. 4 (1982) 47.
[3] D.J. Miller, M.C. Biesinger, N.S. McIntyre, Surf. Interface Anal. 33 (2002) 299.
[4] M.C. Biesinger, unpublished results
[5] G. Beamson, D. Briggs, High Resolution XPS of Organic Polymers – The Scienta ESCA300 Database Wiley Interscience, 1992.