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Most samples that have been exposed to the atmosphere will have a detectable
quantity of adventitious carbon contamination. (Typically with a layer thickness of
1-2nm.)
Adventitious carbon may be removed by argon sputtering.
Use lowest energy argon beam available (e.g. 200eV or 500eV) or argon
clusters to prevent/minimize chemical damage to the underlying material.
Interpretation of XPS Spectra
C1s spectrum for contamination typically has C-C, C-O-C and O-C=O components.
The C-C component may be set to a binding energy of 284.8eV, by default.
Not always a valid charge reference value (e.g. C1s peak for adventitious
carbon on native oxide of aluminium appears at ~286eV
A few nanometers of adventitious carbon on a sample can dramatically affect the
survey spectrum of that sample.
Polymers
Experimental Information
The C1s spectrum from a sample with high concentration of sp2 carbon will have
a broad, asymmetric tail towards higher binding energy.
One or more satellite features, several eV from the main C1s peak, will
also be observed in samples with high sp2 concentration.
For high concentrations of sp3-bonded carbon, the C1s peak will have a more
symmetric shape and will also be slightly shifted to higher binding energy.
Functionalized graphene will have a complex C1s spectrum, containing sp2 and sp3
components.
Fit the sp2 component with asymmetric shape (preferably derived from a real
graphite or graphene sample), including symmetric loss peaks where necessary.
The sp3 carbon and functionalized carbon should be fitted with symmetric peak
shapes.
The sp3 carbon peak should be 1eV to the higher binding energy side of the
sp2 component.
It is generally not possible to uniquely peak fit mixed sp2/sp3 spectra.
Analysis of the X-ray induced C KLL Auger peak can help distinguish these
bonding states in a semi-quantitative manner for non-functionalized samples.
The differentiated form of the C KLL spectrum allows measurement of the D-
parameter, which gives an indication of the relative amounts of sp2 and sp3 carbon.
Measure energy separation between maxima and minima in differentiated C KLL
spectrum.
For functionalized carbon samples, caution must be exercised if using this
method.
In the presence of ruthenium, collect full Ru3d and C1s regions (270300eV),
making sure both Ru3d5/2 and Ru3d3/2 components are acquired.
Metal carbides may be inadvertently formed during argon sputtering of metal-
containing compounds, e.g., oxides, nitrides and borides.
Use lower energy Ar+ beam for depth profiling to minimize this effect.
Use Ru3d5/2, which does not overlap with C1s, as a guide for any peak fitting.
Intensity and binding energy of Ru3dp5/2 peak is set by the Ru3d3/2 peak,
according to the spin-orbit splitting and ratio.
Remainder of intensity under at Ru3d3/2 energy can then be attributed to carbon