What is Adventitious Carbon?

A thin layer of carbonaceous material is usually found on the surface of most air exposed samples, this layer is generally known as adventitious carbon. Even small exposures to atmosphere can produce these films. Adventitious carbon is generally comprised of a variety of (relatively short chain [1]) hydrocarbons species with small amounts of both singly and doubly bound oxygen functionality. The source of this carbon has been debated over the years. It does not appear to be graphitic in nature and in most modern high vacuum systems vacuum oils are not readily present (as they have been in the past) [1,2,3,4]. There may be some evidence that CO or CO2 species may play a role in the gradual appearance of carbon on pristine surfaces within the vacuum of the XPS chamber [3].

It’s presence on insulating surfaces provides for a convenient charge reference by setting the main line of the C 1s spectrum to 284.8 eV (although values ranging from 285.0 eV to 284.5 eV have been used in some cases, remember to check for this value when looking for binding energy references in the literature). The error in this value (284.8 eV) is, for most systems, on the order of +/-0.2 eV to 0.3 eV.  An in-depth look at the effectiveness of using AdC for charge correction purposes, including standardized fitting procedures, is presented in [5].
Work by Grey et al. [6] has explored the nature of adventitious carbon by XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS).  XPS D-parameter and ToF-SIMS analyses confirms that AdC is not graphitic in nature. An average C 1s spectrum for AdC (Figure 1, Table 1) was derived and shows that, on average, ~ 25 % of the carbon species in AdC is directly associated with oxygen functionality.  Similarly, ToF-SIMS analyses show that AdC is comprised of mainly short chain hydrocarbons with some oxygen functionality.

An advanced method for curve-fitting of the C 1s envelope for AdC (Table 2) was developed that included the effects of beta carbons (in this context, the alpha carbon is the carbon directly attached to the oxygen, and the beta carbon is attached to the alpha carbon) and were informed by the configurations of possible volatile organic compounds (VOC) that are the source of most AdC [6]. Using this method in combination with the dataset from [5], the average C–C/C–H AdC aliphatic peak position was shown to be 284.81 eV (+/- 0.25 eV) via verification with a secondary internal reference.

Figure 1. Average of 80 adventitious carbon C 1s XPS spectra.

Table 1. Average adventitious carbon C 1s fitting parameters from an average of 80 AdC spectra.

Table 2. Curve-fitting parameters for AdC C 1s including shifted beta peaks (*) (peaks E, F and G). Areas for peaks A, B, C, and D should be left unconstrained. # If peak-shape for peak D is well-defined the FWHM constraint can be removed.
[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] H. Piao, N.S. McIntyre, Surf. Interface Anal. 33 (2002) 591.

XPS Reference Pages

This site contains information gained from decades of X-ray photoelectron spectroscopy (XPS) analyses of an enormous variety of samples analyzed at Surface Science Western laboratories located at the University of Western Ontario. Originally this site was designed as a place for students and our clients to access valuable tips and information. It has since been opened to all those interested in the XPS technique. Summaries of literature data, relevant references and unpublished data taken of well characterized standard samples are presented. Also curve-fitting tips, instrument set-up tips (specifically for the Kratos AXIS Supra, Ultra and Nova), and CasaXPS tips pertaining to questions we normally get from our students and clients, and other odd bits of information are presented.

The fine print:
Surface Science Western and the University of Western Ontario does not warranty any of the information shown at this site. Any use of this data in scientific publications or other forms should include referencing to the originally published data referenced herein.


Table 1. S 2p3/2 binding energies compiled from the NIST database [1] and other sources.

Notes: 2p3/2 - 2p1/2 doublet separation = 1.18eV, peaks constrained to a 2:1 area ratio (2p3/2 : 2p1/2), generally one sets both peaks to an equal FWHM for ease of use although in pure samples this may not be the case.

Smart et al. [9] and Pratt et al. [10] give an excellent overview of binding energy ranges for the study of mineral surfaces. These ranges can be used with other sulphur containing systems as well. Of particular interest is the assignment for polysulphides eg. (S4)2- = 162.0-163.0 eV, (S5)2- = 161.9 - 163.2 eV, (Sx)2-) = 163.7 eV. Surface species can also play a role in XPS, especially for in-situ fractured sulphide mineral species [11].

[a] Nesbitt et al. [12] give a value of 162.2 eV for the disulphide in arsenopyrite.
[b] A more detailed look at organic sulphur species can be found here.

In a recent paper from Sarah Harmer's group at Flinders University, synchrotron XPS is used to convincingly elucidate surface 3-coordinate, bulk and surface 4-coordinate and bulk 5-coordinate sulfur in the chalcogenide (Fe,Ni)9S8.  This work shows that sulfide coordination changes can be seen by XPS [13].

A Na2S2O3.5H2O (sodium thiosulphite cooled to -130C during analysis) reference sample gave S 2p3/2 peak positions of 162.1 eV and 168.1 eV for S*SO3 and SS*O3 moieties, respectively.

There is a lot of confusion in the literature when presenting the data for sulphur. Some papers mention S 2p when they really mean S 2p3/2, these are not interchangeable! Please remember to be specific about the exact peak you are referring to.

[1] C.D. Wagner, A.V. Naumkin, A. Kraut-Vass, J.W. Allison, C.J. Powell, J.R.Jr. Rumble, NIST Standard Reference Database 20, Version 3.4 (web version) (http:/srdata.nist.gov/xps/) 2003.
[2][2] Z.E. Pettifer, J.S. Quinton, S.L. Harmer, Minerals Engineering, 184 (2022) 107666.
[3] A.N. Buckley, W.M. Skinner, S.L. Harmer, A. Pring, L-J. Fan, Geochimica et Cosmochimica Acta, 73 (2009) 4452-4467.
[4] A.N. Buckley, W.M. Skinner, S.L. Harmer, A. Pring, R.N. Lamb, L.J. Fan, Y. Yang, Canadian Journal of Chemistry, 85 (2007) 767- 781.
[5] S.L. Harmer, A.R. Pratt, H.W. Nesbitt, M.E. Fleet, Canadian Mineralogist, 43 (5) (2005) 1619-1630.
[6] M.E. Fleet, X. Liu, S.L. Harmer, H.W. Nesbitt, Surface Science, 584 (2005) 133-145.
[7] V.P. Zakaznova-Iakovleva, S.L. Harmer, H.W. Nesbitt, G.M. Bancroft, A.R. Pratt, R. Flemming, Surface Science, 600(2) (2006) 348-356.
[8] A.R. Pratt, H.W. Nesbitt, American Mineralogist, 85 (2000) 619-622.
[9] R.St.C. Smart, W.M. Skinner and A.R. Gerson, Surface and Interface Analysis, 28 (1999) 101-105.
[10] A.R. Pratt, I.J. Muir and H.W. Nesbitt, Geochimica et Cosmochimica Acta, 58 (2) (1994) 827-841.
[11] H.W. Nesbitt, M. Scaini, H. Hochst, G.M. Bancroft, A.G. Schaufuss and R. Szargan, American Mineralogist, 85 (2000) 850-857, 
[12] H.W. Nesbitt, I.J. Muir, A.R. Pratt, Geochimica et Cosmochimica Acta, 59 (9) (1995) 1773-1786,
[13] Z.E. Pettifer, J.S. Quinton, W.M. Skinner, S.L. Harmer, Applied Surface Science, 504 (2020) 144458. 

The Chemical Significance of XPS BE Shifts: A Perspective

A recent publication from Paul Bagus (University of North Texas), Connie Nelin, and Dick Brundle [1] discusses the chemical significance of XPS BE shifts. Paul, Connie and Dick have made many outstanding contributions to the field of XPS, in particular by using computational chemistry approaches to model various XPS phenomena and spectral shapes - especially of transition metal species with complex multiplet splitting and satellite structures. 

Dr. Bagus describes this perspective below. This will be a good starting point for researchers interested in applying MO theory to XPS measurements. 

An all too common interpretation of the shifts of XPS BEs, Delta BE, for a given element in different compounds and in different environments is to relate the sign of the BE shift to the change in the effective charge, Q, of the core ionized atom. Thus, a shift to lower BE from sample 1 to sample 2 is interpreted as meaning that the atom in sample 2 has a smaller positive Q or a larger negative Q than the same atom in sample 1. Similarly, a shift to a larger BE is taken to mean that the atom in sample 2 has a larger Q. This paper shows that this simple interpretation of BE shifts is incomplete and that it is likely to be misleading.

While the effective charge Q does contribute to BE shifts, it is not the only physical or chemical mechanism that can contribute to XPS BE shifts. Two other mechanisms are the environment of the ionized atom that can lead to electrostatic potential that are different at different sites in a given sample and are different for different samples. Another mechanism is the degree of hybridization of an atom again at different sites and different compounds. An important objective of this perspective is to examine the mechanisms that lead to BE shifts. The chemical and physical content of these different mechanisms is first examined for a model system. With this model system, the different mechanisms can be separated and the magnitudes of the XPS BE shifts due to the different mechanisms can be understood directly in terms of the electronic charge distribution. Then five specific examples of XPS BEs measured for real systems are discussed and the observed BEs related to the physical and chemical mechanisms which are the origin of the BE shifts. The paper also considers the initial and final state contributions to the BE shifts and identifies when it is likely that initial state effects will dominate.

An important goal of the paper is that the principles and mechanisms for BE shifts can be applied, not only to the specific systems discussed in the paper but also to the understanding of the Delta BE for systems in general. It can lead readers to make suggestions for theoretical studies to help explain specific observations of BE shifts.

[1] P.S. Bagus, C.J. Nelin, C.R. Brundle, J. Vac. Sci. Technol. A 41 068501 (2023).

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.  

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 [6] which uses this number for charge correction.

[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] G. Beamson, D. Briggs, High Resolution XPS of Organic Polymers - The Scienta ESCA300 Database Wiley Interscience, 1992.