Using Adventitious Carbon for Charge Correcting


The C 1s spectrum for adventitious carbon can be fit as follows.  A single peak, ascribed to alkyl type carbon (C-C, C-H), is fit to the main peak of the C 1s spectrum.  A second peak is added that is constrained to be 1.5 eV above the main peak, of equal FWHM to the main peak (C-C, C-H). This higher binding energy peak is ascribed to alcohol and/or ester functionality (C-OH, C-O-C). Further high binding energy components can be added if required. For example: C=O at approximately 3 eV above the main peak and O-C=O at 3.8 to 4.3 eV above the main peak. One or both of these peaks may also have to be constrained to the FWHM of the main peak if they are poorly resolved.  Reference [1] and the table below outline standard starting fitting parameters for adventitious carbon. 
Adventitious carbon C 1s curve-fitting parameters [1].
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 [2] 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 [3] work from 1995 states that error in using adventitious carbon is ±0.2 eV.  Our work [4] 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 [5].  Reference [1] presents a detailed assessment of the analysis of insulating samples from a multi-user facility from over a 5-year period that showed an adventitious C 1s (C-C, C-H) binding of 284.91 eV ±0.25eV.  A similar study confirming the utility of the adventitious carbon technique with a similar multi-user facility analysis has been published by Morgan [6].

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 [7] which uses this number for charge correction.

References:
[1] M.C. Biesinger, Appl. Surf. Sci, 597 (2022) 153681.
[2] T.L. Barr, S. Seal, J. Vac. Sci. Technol. A 13(3) (1995) 1239.
[3] P. Swift, Surf. Interface Anal. 4 (1982) 47.
[4] D.J. Miller, M.C. Biesinger, N.S. McIntyre, Surf. Interface Anal. 33 (2002) 299.
[5] M.C. Biesinger, unpublished results
[6] D.J. Morgan, Surf. Interface Anal. (2024) https://doi.org/10.1002/sia.7360. 
[7] G. Beamson, D. Briggs, High Resolution XPS of Organic Polymers - The Scienta ESCA300 Database Wiley Interscience, 1992.