ISO 19830:2015
(Main)Surface chemical analysis — Electron spectroscopies — Minimum reporting requirements for peak fitting in X-ray photoelectron spectroscopy
Surface chemical analysis — Electron spectroscopies — Minimum reporting requirements for peak fitting in X-ray photoelectron spectroscopy
ISO 19830:2015 Standard is to define how peak fitting and the results of peak fitting in X-ray photoelectron spectroscopy shall be reported. It is applicable to the fitting of a single spectrum or to a set of related spectra, as might be acquired, for example, during a depth profile measurement. This International Standard provides a list of those parameters which shall be reported if either reproducible peak fitting is to be achieved or a number of spectra are to be fitted and the fitted spectra compared. This International Standard does not provide instructions for peak fitting nor the procedures which should be adopted.
Analyse chimique des surfaces — Spectroscopie d'électrons — Exigences minimales pour le rapport d'ajustement de pic en spectroscopie de photoélectrons X
General Information
Standards Content (Sample)
INTERNATIONAL ISO
STANDARD 19830
First edition
2015-11-15
Surface chemical analysis — Electron
spectroscopies — Minimum reporting
requirements for peak fitting in X-ray
photoelectron spectroscopy
Analyse chimique des surfaces — Spectroscopie d’électrons —
Exigences minimales pour le rapport d’ajustement de pic en
spectroscopie de photoélectrons X
Reference number
ISO 19830:2015(E)
©
ISO 2015
---------------------- Page: 1 ----------------------
ISO 19830:2015(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2015, Published in Switzerland
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Ch. de Blandonnet 8 • CP 401
CH-1214 Vernier, Geneva, Switzerland
Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – All rights reserved
---------------------- Page: 2 ----------------------
ISO 19830:2015(E)
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Terms and definitions . 1
3 Symbols and abbreviated terms . 2
3.1 Abbreviated terms . 2
3.2 Symbols . 2
4 Reporting of relevant data acquisition parameters . 3
4.1 General . 3
4.2 Spectrometer . 3
4.3 Instrument resolution. 3
4.4 Detector . 3
4.5 X-ray source . 4
4.6 Element identity . 4
4.7 Energy range in the spectrum . 4
4.8 Energy step size in spectrum . 4
4.9 Charge compensation . 4
5 Reporting of single-spectrum peak-fitting parameters . 5
5.1 General . 5
5.2 Background range . 5
5.3 Background integration range . 5
5.4 Background type . 5
5.5 Application of a fitted background . 5
5.6 Setting the peak parameters . 6
5.7 Peak area and peak height . 6
5.8 Peak area and peak height ratios . 6
5.9 Full width at half maximum . 6
5.10 Peak shape . 6
5.11 Peak asymmetry parameters . 7
5.12 The peak-fitting process . 7
5.13 Residual spectrum . 7
6 Multi-spectrum peak fitting . 7
6.1 General . 7
6.2 Peak fitting methods for multi-spectrum data sets . 7
6.3 Propagation of constraints . 8
6.4 Background propagation . 8
7 Satellite subtraction . 9
8 Doublet subtraction . 9
9 Spectrum deconvolution .10
10 Fit quality and uncertainties .10
10.1 General .10
10.2 Fit quality .10
10.3 Uncertainty in the reported binding energies .10
10.4 Uncertainty in the peak areas .10
Annex A (informative) Example of reporting peak fitting .11
Annex B (informative) Reporting peak fitting for multi-level data sets .14
Annex C (informative) Template for reporting peak fitting parameters .17
Annex D (informative) Statistical methods .19
© ISO 2015 – All rights reserved iii
---------------------- Page: 3 ----------------------
ISO 19830:2015(E)
Bibliography .22
iv © ISO 2015 – All rights reserved
---------------------- Page: 4 ----------------------
ISO 19830:2015(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information.
The committee responsible for this document is ISO/TC 201, Surface chemical analysis, Subcommittee
SC 7, Electron spectroscopies.
© ISO 2015 – All rights reserved v
---------------------- Page: 5 ----------------------
ISO 19830:2015(E)
Introduction
X-ray photoelectron spectra produced from the surfaces of many materials are complex and frequently
consist of overlapping or unresolved peaks. The lack of resolution can be due to instrumental
parameters, the X-ray line width, the natural line width of the transition, or a contribution from all of
these. It is frequently necessary, therefore, to use a mathematical procedure to fit some or all of the
peaks in XPS spectra in order to establish the position and intensity of each of the component peaks
contained within each peak envelope. This is often the first step in the identification of the chemical
states which give rise to the overall peak envelope and the quantification of each chemical state present.
The analyst must therefore have confidence in both the position (to establish the chemical state) and
the peak area (to allow accurate quantification) of each peak reported following peak fitting.
The mathematical procedure applies model peak and background shapes, the defining parameters
of which are varied in order to obtain the optimum fit to the experimental data. Most commonly, the
model peak shapes are some combination of Gaussian and Lorentzian functions.
Many of the parameters that should be reported following peak fitting are those that define these
curves. Other factors are those which are selected by the analyst to ensure that the peak-fitting process
results in a chemically meaningful description of the peak envelope or to minimize the time taken for
the fitting process. These include parameters that the analyst
— chooses to fix at a constant value during the fitting process,
— defines as a range of values over which the parameter can vary during the fitting process, and
— mathematically links the value of a parameter to that of another parameter
Peak fitting is a purely mathematical process from which quantitative and qualitative results are
obtained which may be related to the chemistry of the surface being analysed. The results will depend
upon the analyst’s choice of parameters and constraints and this choice will influence the interpretive
conclusions that the analyst reaches from the peak-fitting results. For that reason, it is important that
these parameters and constraints are reported. This will allow another analyst to
— assess the reliability and validity of the conclusions drawn from the peak fitting exercise,
— repeat the peak-fitting process on the same data set and obtain the same results, and
— repeat the peak-fitting process on data which has been obtained from a similar sample and be in a
position to make a valid comparison of the data sets.
Most software packages which have been designed for use with XPS data contain a peak-fitting routine.
These routines allow the operator to select appropriate parameters and apply the desired constraints
to the fitting process. It is highly likely that the software will provide an output which reports these
and usually includes the facility to copy them for use with another spectrum. Such an output will make
reporting the appropriate parameters particularly convenient.
This International Standard is not intended to provide instructions for either fitting XPS peaks or for
linking the outcome of a peak-fitting routine to the chemistry of the surface being analysed. Indeed,
in the examples shown in this International Standard, it is not claimed that the fitting shown is the
only way fitting can be done or even that the examples show the optimum peak fitting method. The
examples serve to illustrate the purpose of this International Standard.
vi © ISO 2015 – All rights reserved
---------------------- Page: 6 ----------------------
INTERNATIONAL STANDARD ISO 19830:2015(E)
Surface chemical analysis — Electron spectroscopies —
Minimum reporting requirements for peak fitting in X-ray
photoelectron spectroscopy
1 Scope
The purpose of this International Standard is to define how peak fitting and the results of peak fitting in
X-ray photoelectron spectroscopy shall be reported. It is applicable to the fitting of a single spectrum or
to a set of related spectra, as might be acquired, for example, during a depth profile measurement. This
International Standard provides a list of those parameters which shall be reported if either reproducible
peak fitting is to be achieved or a number of spectra are to be fitted and the fitted spectra compared.
This International Standard does not provide instructions for peak fitting nor the procedures which
should be adopted.
2 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
2.1
background, inelastic
intensity distribution in the spectrum for particles originally at one energy but which are emitted at
lower energies due to one or more inelastic scattering processes
[SOURCE: ISO 18115-1, 4.50]
2.2
background, Shirley
background calculated to fit the measured spectrum at points at higher and lower kinetic energy than
the peak or peaks of interest such that the background contribution at a given kinetic energy is in a
fixed proportion to the total peak area above that background for higher kinetic energies.
[SOURCE: ISO 18115-1:2010, 4.54]
2.3
background, Tougaard
intensity distribution obtained from a model for the differential inelastic scattering cross section with
respect to energy loss and the three-dimensional distribution of the emitting atoms in the surface region
[SOURCE: ISO 18115-1:2010, 4.57]
2.4
pass energy
mean kinetic energy of the detected particles in the energy dispersive portion of the energy analyser
[SOURCE: ISO 18115-1:2010, 4.325]
2.5
peak fitting
procedure whereby a spectrum, generated by peak synthesis, is adjusted to match a measured spectrum
© ISO 2015 – All rights reserved 1
---------------------- Page: 7 ----------------------
ISO 19830:2015(E)
2.6
peak synthesis
procedure whereby a synthetic spectrum is generated using either model or experimental peak
shapes in which the number of peaks, peak shapes, peak widths, peak positions, peak intensities, and
background shape and intensity are adjusted for peak fitting
[SOURCE: ISO 18115-1:2010, 4.329]
2.7
residual spectrum
difference between the experimentally acquired spectrum and the synthesized spectrum
3 Symbols and abbreviated terms
3.1 Abbreviated terms
BE binding energy
eV electron volt
FWHM full width at half maximum
L/G ratio of the intensity of the Lorentzian component to the Gaussian component of a pseudo
Voigt peak consisting of the sum of a Gaussian and a Lorentzian function
PE pass energy
XPS X-ray photoelectron spectroscopy
3.2 Symbols
2
2
χ value of χ after the minimization process has been completed
min
2
χ chi square
σ standard deviation for the binding energy of a peak
a
c total number of counts in channel i prior to background subtraction
i
i channel number in a spectrum
M number of independently adjustable parameters used in the fitting process
N number of energy channels in the part of the spectrum being fitted
r spectrum residual in channel i (obtained from the total number of counts, not counts per sec-
i
ond)
Δa energy by which a peak position is changed (from the position which results in the minimum
chi square value) during the process of estimating the uncertainty in the peak position
Δh amount by which a peak height is changed (from the value which results in the minimum chi
square value) during the process of estimating the uncertainty in the peak intensity
Δw amount by which a peak width is changed (from the value which results in the minimum chi
square value) during the process of estimating the uncertainty in the peak width
2 © ISO 2015 – All rights reserved
---------------------- Page: 8 ----------------------
ISO 19830:2015(E)
4 Reporting of relevant data acquisition parameters
4.1 General
This Clause applies to the instrumental parameters that can affect the shape of a peak, peak envelope,
or background in a spectrum. Such parameters will therefore affect the parameters that define the
fitted spectrum and so they shall be reported.
4.2 Spectrometer
There are instrumental and acquisition parameters that influence the shape of the peaks in an XPS
spectrum. These parameters can also affect the results of any peak fitting activity and shall be reported.
In addition, the relationship between instrumental parameters and the results obtained from peak
fitting may depend upon the precise design of instrument used. An example of this is the relationship
between the pass energy used to acquire the data and the resolution of the peaks in the spectrum. It is
therefore necessary to report the manufacturer and the model of the instrumentation used. This can
either be the model name (including a version identifier, if appropriate) of the complete spectrometer or
the model names of the key components.
4.3 Instrument resolution
The parameters that can affect the results of a subsequent peak fitting shall be reported. These include
any of the following factors which can affect the resolution of the spectrometer:
— chosen pass energy;
— if the spectrometer has adjustable slits which control instrument resolution at the entrance and/or
exit of the analyser, the settings for those slits;
— if the spectrometer has a transfer lens having an adjustable angular acceptance and/or an adjustable
field of view aperture, the settings of each of these can affect the resulting resolution and shall
therefore be reported.
Clearly, the above parameters do not form part of the peak-fitting process and the relationship between
the values reported and the shape of the spectrum may be dependent upon the spectrometer used.
The value of each of these parameters shall be reported so that a meaningful comparison can be made
between peak-fitted data obtained from different spectrometers can be made.
4.4 Detector
The type of detector employed in the spectrometer can have an effect upon the shape of the acquired
spectrum. Common types of detector include multiple channel electron multipliers and channel
plate detectors. The type of detector employed shall be reported. Instruments with channel plates
or a large number of channel electron multipliers may be operated in either the “scanned mode” or
the “snapshot mode” depending upon whether the median energy of the analyser changes during the
spectrum acquisition (scanned) or whether it is constant (snapshot). The type of spectrum acquired
shall be reported.
If the quality and reliability of the fitted spectrum is to be fully assessed, then there shall be some
indication of the amplitude of the noise in the spectrum. The majority of XPS spectrometers use an
electron multiplier connected to some form of pulse counting equipment. This means that the dominant
form of noise in the spectrum is due to Poissonian statistics. Since this form of noise is purely statistical,
it is only related to the number of counts in each of the channels of the spectrum. For the purposes of
reporting peak fitting results, it is only necessary to report the number of counts in the channel that
contains the maximum number of counts. It should be noted that if the data are transformed in some
way (for example, by correcting for the transmission function of the instrument), then the data may not
conform to Poissonian statistics.
© ISO 2015 – All rights reserved 3
---------------------- Page: 9 ----------------------
ISO 19830:2015(E)
If the instrument used to acquire the spectra has multiple detectors, it is likely that the data have been
unavoidably smoothed; this reduces the noise amplitude from that expected from Poisson statistics.
The extent to which the noise amplitude is reduced depends upon the design of the spectrometer
and the conditions chosen by the analyst to acquire the spectrum (for example, the energy difference
between successive data points in relation to the energy difference between adjacent detectors). This
will reduce the relative noise amplitude in the spectrum but reporting the number of counts in the peak
maximum will provide an indication of the likely influence of noise upon the peak fitting process.
NOTE 1 It is the number of counts that is important here not the number of counts per second.
At high count rates, the output from electron multipliers will become nonlinear. This will affect the
peak shape and influence the quality of the fitted spectrum. For the purposes of reporting peak-fitting
results, it is only necessary to report the count rate in the channel that contains the maximum number
of counts. A method for checking the linearity of a detector may be found in ISO 21270.
NOTE 2 It is the number of counts per second that is important here not the number of counts.
4.5 X-ray source
The type of X-ray source used to obtain the spectra shall be reported. This includes the nature of the
anode (aluminium, magnesium, etc.) or X-ray energy and whether an X-ray monochromator was used.
The type of X-ray source used will affect not only the shapes of the peaks being fitted but also the nature
of any satellite peaks which might be present in the spectrum and which might need to be taken into
account during the fitting process. Some monochromators have the ability to focus the X-ray beam in
order to control the spot size and therefore, the analysis area. If such a monochromator is used, then the
selected spot size shall be recorded because this might have an effect upon the resolution of the peaks.
4.6 Element identity
The identity of the element (or elements) contributing to the peak envelope being fitted shall be reported.
Often, doublet peaks are included within a single envelope and are part of a single peak-fitting process.
In this case, it is not necessary to list the component doublet (e.g. reporting Si 2p would be sufficient).
In some cases when the components of a doublet are widely separated, a fit may be applied to a single
component. If this is the case, the identity of the fitted transition shall be reported.
4.7 Energy range in the spectrum
The energy window in the spectrum used for peak fitting shall be recorded.
4.8 Energy step size in spectrum
The number of data points present in the spectrum will affect the quality and reliability of the fitted
spectrum. For this reason, the energy difference between adjacent energy channels shall be reported.
This applies to both scanned and “snapshot” spectra.
4.9 Charge compensation
For the analysis of insulating samples, some form of charge compensation or static charge correction
is usually required if a reliable spectrum is to be obtained. For example, this may be accomplished
using a low-energy beam of electrons or a combination of electrons and low-energy ions. The type of
charge compensation shall be reported along with some indication of the approach used for setting the
conditions (for example, the identity of the spectral peak used and whether the settings were adjusted
to optimize peak position, peak shape, or peak width). If the charge compensation causes a shift in the
peak positions, the size of the shift shall be reported. If the spectrum has been corrected for this charge,
shift the size and direction of the shift shall be reported. The identity of any peak used as a reference for
charge compensation shall be reported along with its energy.
4 © ISO 2015 – All rights reserved
---------------------- Page: 10 ----------------------
ISO 19830:2015(E)
5 Reporting of single-spectrum peak-fitting parameters
5.1 General
This Clause applies to the type of measurement that leads to the acquisition of individual spectra. A
later Clause will apply to measurements that lead to multiple spectra, examples of which are depth
profiles, line scans, and the type of images which have a spectrum at each pixel.
The Clause describes parameters which shall be reported together with any fitting constraints or linkages.
5.2 Background range
When peak-fitting is carried out on a spectrum, it is necessary to consider the background. The chosen
background should extend beyond the peak envelope at both higher and lower binding energies.
There are circumstances under which the choice of background range can severely affect the values
calculated for the peak areas (for example, when there is an energy loss feature in the spectrum close
to the peak being fitted). For this reason, the energy of each extreme of the fitted background shall be
reported along with the type of averaging algorithm used (arithmetic average, polynomial fit, etc.) if
this is known.
5.3 Background integration range
If the background contains significant noise, it might be necessary to take an average intensity over a
range of energies at each end of the chosen background range. This defines more accurately the start
and end positions o
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.