ISO 19668:2017

Surface chemical analysis — X-ray photoelectron spectroscopy — Estimating and reporting detection limits for elements in homogeneous materials

ISO 19668:2017 specifies a procedure by which elemental detection limits in X-ray photoelectron spectroscopy (XPS) can be estimated from data for a particular sample in common analytical situations and reported. This document is applicable to homogeneous materials and is not applicable if the depth distribution of elements is inhomogeneous within the information depth of the technique.

Analyse chimique des surfaces — Spectroscopie de photoélectrons par rayons X — Estimation et production de rapports sur les limites de détection des éléments contenus dans les matériaux homogènes

General Information

• Status: Published
• Publication Date: 13-Aug-2017
• ICS: 71.040.40 - Chemical analysis
• Technical Committee: ISO/TC 201/SC 7 - Electron spectroscopies
• Drafting Committee: ISO/TC 201/SC 7/WG 2 - Quantification and interpretation of data in electron spectroscopy
• Current Stage: 9060 - Close of review
• Start Date: 03-Mar-2028

Relations

• Consolidated By: ISO 11074:2015/Amd 1:2020 - Soil quality — Vocabulary — Amendment 1
• Effective Date: 06-Jun-2022

Standards Content (Sample)

INTERNATIONAL ISO
STANDARD 19668
First edition
2017-08
Surface chemical analysis — X-ray
photoelectron spectroscopy —
Estimating and reporting detection
limits for elements in homogeneous
materials
Analyse chimique des surfaces — Spectroscopie de photoélectrons par
rayons X — Estimation et production de rapports sur les limites de
détection des éléments contenus dans les matériaux homogènes
Reference number
ISO 19668:2017(E)
©
ISO 2017

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ISO 19668:2017(E)

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ISO 19668:2017(E)

Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Symbols and abbreviated terms . 1
5 Calculating and reporting detection limits from XPS data . 3
5.1 General . 3
5.2 Required data . 5
5.3 XPS measurements . 5
5.3.1 General. 5
5.3.2 Composition of the sample . 5
5.3.3 Spectra for detection limit calculation . 6
5.4 Calculation of background noise . 7
5.4.1 General. 7
5.4.2 Standard deviation of intensity from counts . 7
5.4.3 Standard deviation of intensity from background fit . 8
5.5 Calculation of the elemental detection limit. 9
5.5.1 Calculation of the minimal detectable summed intensity . 9
5.5.2 Calculation of the XPS detection limit . 9
5.6 Reporting the elemental detection limit .10
Annex A (informative) Uncertainties associated with XPS detection limits .11
Annex B (informative) Definition of XPS detection limits .15
Annex C (informative) Examples .16
Annex D (informative) Detection limit conversions .22
Bibliography .24
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ISO 19668:2017(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
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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
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This document was prepared by Technical Committee ISO/TC 201, Surface chemical analysis,
Subcommittee SC 7, Electron spectroscopies.
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ISO 19668:2017(E)

Introduction
X-ray photoelectron spectroscopy (XPS) is a technique widely employed to measure the chemical
composition of material surfaces. In many applications, it is used to either confirm or deny the
presence of an elemental species at a surface. In either case, it is important to understand the minimal
concentration of the element that can be detected by XPS under the measurement conditions either
to provide an assessment of confidence in a result or to understand how the measurement conditions
should be changed to achieve the required detection limit.
This document provides a straightforward approach to calculating detection limits in X-ray
photoelectron spectroscopy from experimental data in common analytical situations. It also provides
informative annexes which allow the uncertainty in the calculated detection limit to be determined
(see Annex A) and describe how the XPS detection limit is defined (see Annex B). Example data and
calculations are provided in Annex C. Annex D contains useful conversions and references which
describe how detection limits may be estimated for an X-ray photoelectron spectrometer in the absence
of any data except that from a reference material such as clean silver.
These calculations are of critical importance because the technique is routinely used to measure
the concentration of elements, which are present in low concentrations at a material surface, and
knowledge of the limit of detection provides a statement of confidence when no element can be
detected. Furthermore, if a particular detection limit is required, it permits the analyst to calculate the
acquisition time required to achieve the specified limit of detection.
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INTERNATIONAL STANDARD ISO 19668:2017(E)
Surface chemical analysis — X-ray photoelectron
spectroscopy — Estimating and reporting detection limits
for elements in homogeneous materials
1 Scope
This document specifies a procedure by which elemental detection limits in X-ray photoelectron
spectroscopy (XPS) can be estimated from data for a particular sample in common analytical situations
and reported. This document is applicable to homogeneous materials and is not applicable if the depth
distribution of elements is inhomogeneous within the information depth of the technique.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 18115-1, Surface chemical analysis — Vocabulary — Part 1: General terms and terms used in
spectroscopy
ISO 18115-2, Surface chemical analysis — Vocabulary — Part 2: Terms used in scanning-probe microscopy
3 Terms and definitions
For the purposes of this document, the terms and definitions given in ISO 18115-1 and ISO 18115-2 and
the following apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at http:// www .iso .org/ obp
— IEC Electropedia: available at http:// www .electropedia .org/
3.1
reference element
chemical element present in the sample for which a peak area and relative composition can be measured
3.2
specified element
chemical element for which the detection limit calculation is being undertaken
4 Symbols and abbreviated terms
A summed intensity of the photoelectron line of element i, counts or cps
i
A critical level of detection for a peak in summed intensity, counts or cps
C
A minimal detectable summed intensity for a peak at the required level of confidence
D
AMRSF average matrix relative sensitivity factor
a coefficients of order m in a polynomial equation
m
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ISO 19668:2017(E)

at.% atomic percent concentration
α average emission angle of electrons relative to the surface normal of the sample
B(E) function of E describing background, counts or cps
BE binding energy
b number of data points that define the background under a peak
c number of data points from b that are used in a summed intensity measurement
cps counts per second
d diameter of the atoms of the specified element
δ relative uncertainty of peak intensity, A
A(x) x
δ relative uncertainty of the detection limit, S
S
δ relative uncertainty of the standard deviation of the background σ
σ(B) B
δ relative uncertainty of the detection limit, X
X(D) D
E numerical value of either BE or KE, eV
E numerical value of either BE or KE of the photoelectron peak used to detect element j, eV
j
eV electron volts
ε step size in spectrum, eV
F factor by which the acquisition time should be changed to achieve target detection limit
FWHM full width at half maximum
G goodness of fit
G minimized value of G
min
Γ XPS detection limit of a thin overlayer of the specified element expressed as areic density
D
I(E) function of E describing intensity in a spectrum
i element within the sample
j element for which the detection limit is to be estimated
k coverage factor
λ inelastic mean free path of electrons with kinetic energy E in the sample
j
KE kinetic energy
M number of terms, excluding the constant term, in a polynomial description of B
m index in a general polynomial equation with integer values 0 to M
N number of data points in background spectrum
n data point indicator with integer values 1 to N
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ISO 19668:2017(E)

q factor to account for data smoothing introduced by electron detectors
θ XPS detection limit of a thin overlayer of the specified element expressed in monolayers
D
R(E) function of E describing the difference between I and B, counts or cps
RSF elemental relative sensitivity factor
S RSF of the photoelectron line used to measure the concentration of element i
i
σ standard deviation of a summed intensity measurement
A
σ standard deviation of I in background region
B
T(E) factor that transforms I(E) to have units of counts
t XPS detection limit of a thin overlayer of the specified element expressed as a thickness
D
W FWHM in eV of the photoelectron line used to detect element i
i
x element used as a photoelectron intensity reference
X atomic fraction of element i expressed in units of at.%
i
X minimal detectable concentration of an element expressed in units of at.%
D
X target XPS detection limit
T
XPS X-ray photoelectron spectroscopy
y number of data points from b that solely describe the peak
5 Calculating and reporting detection limits from XPS data
5.1 General
This clause provides a step-by-step procedure for the calculation of a detection limit for a specified
element from XPS data. The data should cover the binding energy (BE) region in which a photoelectron
peak is expected from the specified element for which the detection limit is to be calculated. The
element may be below detectable levels or present at low concentrations; slightly different procedures
will be used in each case. These procedures are described in 5.3.3.2 and 5.3.3.3, respectively. Various
simplifying approximations are used in this document to enable the calculations to be performed in a
practical manner. The typical uncertainty in the calculated XPS detection limits using this procedure
is between 10 % and 25 %, which is sufficient for practical XPS analysis. A flow chart describing the
steps required for the collection of data is provided in Figure 1, and a flow chart describing the steps
required to calculate XPS detection limits is provided in Figure 2.
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ISO 19668:2017(E)

NOTE Point “A” connects to the flow chart in Figure 2.
Figure 1 — Flow chart describing steps in data collection for estimating XPS detection limits
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ISO 19668:2017(E)

Figure 2 — Flow chart describing the steps in estimating XPS detection limits
5.2 Required data
The procedure requires knowledge of the relative sensitivity factors (RSFs), S , for photoelectron peaks
i
of all elements, i, detected in the sample and the RSF, S , for the relevant photoelectron peak of the
j
specified element, j. The BE or kinetic energy (KE) for the relevant photoelectron peak of the specified
element, E , shall also be known to within 10 eV.
j
5.3 XPS measurements
5.3.1 General
The procedure requires knowledge of the chemical composition of the sample, as determined by XPS, as
well as a spectrum which spans the BE of the photoelectron peak of the element for which the detection
limit is to be calculated. If no peak for the specified element is observed, then an additional spectrum of
an element that is present may be required.
5.3.2 Composition of the sample
Acquire a survey scan and identify all detectable elements. The summed intensities, A, of these
i
elements shall be measured either from the survey scan or from individual, narrow spectra of all
detectable elements identified. The summed intensities shall be converted into a composition using the
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experimentally determined RSFs for those elements or through the use of an appropriate transmission
function correction and average matrix relative sensitivity factors (AMRSFs) to obtain X . If the element,
i
j, for which the detection limit is to be calculated is observed in the sample, it shall have a concentration,
X , less than 10 at.%, and preferably less than 1 at.%.
j
NOTE 1 Guidance for XPS analysis, peak intensity determination and the use of RSFs can be found in
References [1], [3] and [4].
NOTE 2 If no transmission function correction is used, then the RSFs for the specific operating mode of the
instrument used for measuring the composition is applied here.
5.3.3 Spectra for detection limit calculation
5.3.3.1 General
The spectrum used for the detection limit calculation shall be at, or close to, the expected BE position
of the photoelectron line for the specified element j. At least 20 data points in the background region
of the spectrum are required and shall be selected from the spectral data as specified in 5.3.3.2 and
5.3.3.3. These selected data are termed “the background data” in the following. The background data
should contain no sharp spectral features from any elements in the sample. In some situations, it is
also necessary to have a reference spectrum of an element that is present in the sample. If the specified
element is not detected in the survey scan, proceed to 5.3.3.2, otherwise proceed to 5.3.3.3.
5.3.3.2 Specified element is not detected in the sample
If the detection limits are to be calculated for the experimental conditions used for the survey scan (see
5.3.2), a reference element, x, present in the survey scan shall be selected. The reference element shall
have an intense photoelectron peak that is as close as possible in BE to the peak position of the specified
element, j. Determine the summed intensity, A , of the photoelectron peak of reference element x from
x
the survey scan. The background data shall be selected from the survey scan and extend evenly above
and below the expected position for the peak of element j.
If the detection limits are to be calculated from data acquired under different experimental conditions
to those used for the survey scan (see 5.3.2), acquire a spectrum using these conditions and extending
evenly above and below the expected position for the peak of element j. This shall be the background
data. Select a reference element, x, present in the survey scan. The reference element shall have
an intense photoelectron peak that is as close as possible in BE to the peak position of the specified
element, j. Acquire a spectrum of this peak using identical experimental conditions to the background
data. Determine the summed intensity, A , of the photoelectron peak of reference element x from this
x
spectrum.
NOTE 1 Element x is normally the most abundant element in the sample.
NOTE 2 C.1 provides two examples of this case.
5.3.3.3 Specified element is detected in the sample
If the detection limits are to be calculated for the experimental conditions used for the survey scan
(see 5.3.2), select the background data from a region of the spectrum at lower BE (higher KE) than the
peak. Determine the summed intensity, A . If the peak for element j is sufficiently intense, such that the
j
relative uncertainty in A , its summed intensity measurement, is less than 10 %, it shall be used as the
j
reference element x and A shall be equal to A . If the uncertainty is greater than 10 %, then a reference
x j
element x shall be selected. The reference element shall have an intense photoelectron peak that is as
close as possible in BE to the peak position of the specified element, j. Determine the summed intensity,
A , of the photoelectron peak of reference element x.
x
If the detection limits are to be calculated from data acquired under different experimental conditions
to those used for the survey scan, a spectrum using these conditions shall be acquired extending evenly
above and below the position for the peak of element j. The energy range shall be wide enough that
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ISO 19668:2017(E)

more than 20 data points can be selected as the background data from a region of the spectrum at
lower BE (higher KE) than the peak. Determine the summed intensity, A . If the peak for element j is
j
sufficiently intense, such that the relative uncertainty in A , its summed intensity measurement, is less
j
than 10 %, it shall be used as the reference element x and A shall be equal to A . If the uncertainty
x j
is greater than 10 %, then a reference element x shall be selected. The reference element shall have
an intense photoelectron peak that is as close as possible in BE to the peak position of the specified
element, j. Acquire a spectrum of this peak using identical experimental conditions to the background
data. Determine the summed intensity, A , of the photoelectron peak of reference element x from this
x
spectrum.
NOTE 1 A.2 provides a method for estimating the uncertainty in summed intensity measurement.
NOTE 2 C.2 provides an example of this case.
5.4 Calculation of background noise
5.4.1 General
This subclause describes a method to estimate the background noise in the spectrum from the
background data selected in 5.3.3. If the data are in counts or can be converted into counts by a known
factor or function, proceed to 5.4.2. The method described in 5.4.3 may be used in all cases.
NOTE The method in 5.4.3 requires significantly more effort and time than the method in 5.4.2.
5.4.2 Standard deviation of intensity from counts
When the data are in counts, or can be converted into counts through a known factor or function, the
standard deviation of the background intensity may be calculated by assuming Poisson statistics as the
square root of the average intensity in counts following Formula (1):
N
 
TE IE
() ()
∑ nn
 
n=1
σ = (1)
B
N 2
TE 
()
∑ n
 
n=1
where
σ is the average standard deviation of I in background region;
B
I(E ) is the intensity at E ;
n n
T(E ) is the factor or function to change I(E ) to have units of counts;
n n
E is the energy for point n in the background region;
n
N is the number of data points in background spectrum;
n is the data point indicator with integer values 1 to N.
NOTE 1 If the data are in counts, then T(E ) = 1 for all E .
n n
NOTE 2 If the data are in counts per second (cps), then T(E ) is the product of dwell time per point and number
n
of scans for all E .
n
NOTE 3 If the data I(E ) have been transformed by a transmission function, then T(E ) is the scaled
n n
transmission function which will return the data into units of counts. Transmission functions will normally
convert data into cps, so for this purpose T(E ) will normally be the product of the transmission function, the
n
dwell time per point and the number of scans.
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ISO 19668:2017(E)

5.4.3 Standard deviation of intensity from background fit
The background data shall be fitted with a polynomial, B(E). The functional form of B(E) is provided in
Formula (2):
M
m
BE =−aE()E (2)
()
∑ mj
m=0
where
a are the coefficients of order m in a polynomial equation;
m
E is the numerical value of either BE or KE, eV;
E is the expected position of the peak for element j;
j
m is the index in a general polynomial equation with integer values 0 to M;
M is the degree of the polynomial description of B(E).
The value of M should initially be set to 1 and should not exceed 4.
Initial trial values of a should be used to calculate the residual of the fit, R(E), using Formula (3) and
m
the goodness of the fit, G, using Formula (4):
RE =IE −BE (3)
() () ()
where
I(E) is the intensity in the spectrum at a given energy, E.
1 N 2
 
G= RE (4)
()
∑ n
 
n=1
NM−−1
()
where
N is the number of data points in background spectrum;
n is the data point indicator with integer values 1 to N;
E is the numerical value of either BE or KE, eV, at data point n.
n
The initial trial values of a shall be changed iteratively to minimize G. Once the fit is minimized, the
m
residuals, R(E), shall be plotted against E and inspected visually to ensure that there are no significant
systematic deviations with energy between I(E) and B(E). If there are systematic variations, either
a) the value of M shall be increased by one and the fitting procedure repeated. The value of M shall not
be greater than 4, or
b) the value of N should be decreased to N = 20, or
c) a different photoelectron peak from the specified element j shall be used.
Once a fit to the background has been found, the minimized value of G, G , shall be used to estimate
min
the standard deviation of the background, σ , using Formula (5):
B
σ =qG (5)
B min
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where
q is equal to 1 for single channel detectors and equal to 1,15 for multi-channel detectors.
NOTE The factor 1,15 for multi-channel detectors arises from the manner in which the detector channel
outputs are placed into energy bins. See A.1.1 and Reference [4].
5.5 Calculation of the elemental detection limit
5.5.1 Calculation of the minimal detectable summed intensity
Calculate the minimal detectable summed intensity, A , using Formula (6):
D
W
j
Ak=49, σ (6)
D B
ε
where
k is the coverage factor to achieve the desired level of confidence. k = 2,33 is recommended;
W is the FWHM in eV of the photoelectron line used to detect specified element j;
j
ε is the step size in spectrum, eV.
Typical values of k are 1,645, 2, 2,33 or 3. k = 2,33 is recommended here; see B.2.
NOTE 1 Formula (6) is only valid for linear background subtraction.
NOTE 2 The form of Formula (6) is adapted from Reference [6] and a justification is provided in Annex B.
If no peak for element j is observed in the spectrum, the value of W may not be known. In the absence of
j
other information, the value W of the reference element x shall be used.
x
5.5.2 Calculation of the XPS detection limit
The method used to calculate the XPS detection limit from A is referenced to a summed intensity
D
from a reference element, A , described in 5.3.3. It is important that this reference summed intensity
x
is expressed in the same units as A , i.e. either counts or cps. If the reference peak area is expressed in
D
counts.eV or cps.eV then it will be converted to summed intensity in counts or cps by dividing the value
by the step size in spectrum, ε.
The detection limit, X , of specified element j shall be calculated using Formula (7):
D
AX S
D xx
X = (7)
D
AS
xj
where
S is the RSF of the photoelectron line used to measure the concentration of element x;
x
S is the RSF of the photoelectron line used to measure the concentration of element j;
j
X is the atomic fraction of element x expressed in units of at.%.
x
If no transmission function has been applied, the RSFs for the specific operating mode of the instrument
used to acquire spectra in 5.3.3 shall be applied here.
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5.6 Reporting the elemental detection limit
The detection limits calculated from the procedure described in this document shall be reported to
one or two significant figures, depending upon the uncertainty associated with the calculation. These
uncertainties are described in Annex A.
The following information shall be reported:
a) the specified element and photoelectron peak for which the detection limit was calculated;
b) the elemental composition of the sample for which the detection limit was calculated;
c) the coverage factor, k, used for the calculation;
d) the instrument and operating conditions for which the detection limit was calculated;
e) the means of calculating the background noise, either
1) from the square root of the intensity, or
2) from the standard deviation of the background;
f) the element and photoelectron
...