Research article

Received: 23 October 2013

Revised: 27 November 2013

Accepted: 2 January 2014

Published online in Wiley Online Library: 5 February 2014

(wileyonlinelibrary.com) DOI 10.1002/sia.5406

Detection limits in XPS for more than 6000

binary systems using Al and Mg K X-rays
Alexander G. Shard*
A simple approach to estimating the detection limits of X-ray photoelectron spectroscopy (XPS) for any element in any elemental
matrix is presented, using the intensity of the background at the expected position for the photoelectron peak to be detected.
The approach has been extended to estimate the detection limit for all elements from lithium to bismuth in a similar range of
elemental matrices. Using a number of assumptions, it is possible to obtain a reasonable estimate of the background intensity
at any electron kinetic energy in the XPS spectrum of an element. Therefore, a detection limit for an arbitrary element homogeneously distributed in that matrix can be estimated. The results show that, although most elements are detectable at about the 1
at.% to 0.1 at.% level, for heavy elements in a light element matrix, the detection limit can be better than 0.01 at.%, whereas for
light elements in a heavy element matrix, detection limits above 10 at.% are not uncommon. Two charts detailing the detection
limits for all combinations of trace and matrix elements from lithium (Z = 3) to bismuth (Z = 83) are provided for Al K and Mg K
X-ray sources using a typical hemispherical analyser instrument which provides 106 counts eV for the Ag 3d5/2 peak from pure
silver. These detection limits can be scaled to estimate the detection limits for any given instrument and operating conditions if
the intensity of the Ag 3d5/2 peak from pure silver under those conditions is known. 2014 Crown Copyright. Surface and
Interface Analysis 2014 John Wiley & Sons Ltd.
Keywords: XPS; detection limit; background; uncertainty; measurement

Introduction

Surf. Interface Anal. 2014, 46, 175185

* Correspondence to: Alex Shard, dql, npl, Hampton Road, Teddington, UK.
E-mail: alex.shard@npl.co.uk

This article is published with the permission of the Controller of HMSO and the
Queens Printer for Scotland.
National Physical Laboratory, Hampton Road, Teddington, UK

2014 Crown Copyright.

Surface and Interface Analysis 2014 John Wiley & Sons Ltd.

175

In many practical applications of X-ray photoelectron spectroscopy

(XPS), it is important to have an estimate of the detection limit for
a particular element. The absence of a detectable signal for an
element does not mean it is not present, since it could be present
at concentrations below the XPS detection limit and it is often important to be able to state this limit. Additionally, if an element is known,
or suspected, to be present at a certain concentration it is important
to be able to calculate the acquisition time required to achieve a
detection limit below that concentration. So what are the detection
limits of XPS? The general issue is well understood and the literature
provides information on how signal to noise affects the detection of
an elemental photoelectron peak.[1] However, for particular systems,
it is not at all clear what the numerical result would be. The simplest
analyses of the problem use two points, one on the peak and the
other on the background. The detection limit in this case is given
as a signal on the peak larger than that on the background by either
two or three times the background noise,[2] but this does not
account for experimental practice in which a large number of
individual intensities are measured across both the peak and the
background. Consequently peak areas, not intensities, are used
for quantitative analysis, and detection limits should be described
in a manner that is coherent with this practice. Uncertainties in
peak area measurement have been analysed in detail,[3,4] and it
should be possible to calculate detection limits in real XPS spectra
using an approach derived from this type of analysis.
XPS detection limits[5] are generally described as being in the
region of 1 at.% to 0.1 at.%, and this accords with common
experience and practice. The true answer to the question what
are the detection limits of XPS?, as most XPS analysts know, is
it depends. In fact, it depends upon so many things that the issue cannot be addressed except on a case-by-case basis. The

purpose of this paper is to provide a guide that permits XPS analysts

to calculate detection limits from their data and to estimate the detection limit of a given element in a given elemental matrix on their
instrument. The case-by-case basis is provided in a single gure.
The essential problem revolves around determining the level of
background noise and interferences in an XPS spectrum. This is
illustrated in Fig. 1, where the XPS spectra of two elemental matrices,
carbon and silver, are presented. Marked on these spectra are the
positions of the 2p3/2 peaks for a number of elements which would
usually be identied from such peaks. In the carbon matrix, the
elements fall upon a relatively constant background, with the exception of the K 2p3/2 peak which is in a strongly varying background
region associated with the C 1s peak. The detection limit calculated
in this paper for these elements, using the 2p3/2 peak in this matrix,
is approximately 0.1 at.% and improves as the average matrix sensitivity factor, S, for the 2p3/2 peak of the trace element increases. In
carbon, XPS is about 2.5 times more sensitive to manganese than
to calcium. In silver, the background is more complicated, rising to
lower kinetic energy. This affects the noise and therefore the detection limits for the elements and here the effect of the change in
sensitivity factor of the 2p3/2 peak of the trace element and the
change in background intensity act so that the detection limits for
manganese and calcium are nearly identical. Note that the Cr 2p3/2
peak is coincident with the Ag 3p3/2 peak, and other chromium
peaks would be used to detect this element in a silver matrix.

A. G. Shard

14

14

12

12

10

10

0
800

900

1000

1100

1200

0
800

900

1000

1100

1200

Figure 1. X-ray photoelectron spectra of two elemental matrices, carbon and silver acquired using monochromatic Al K radiation. The positions of the
2p3/2 peaks for a number of elements are marked. The average matrix relative sensitivity factors, S, for those peaks and the detection limit using those
peaks in that matrix are given.

Inspection of the detection limits for calcium in carbon and silver matrices illustrates an important point. In these two matrices,
the background intensities at the Ca 2p3/2 peak position are very
similar. Therefore, it may be expected that the detection limits
should be close to identical in these two matrices. If the detection
limit was expressed in terms of atoms per unit area of
submonolayer calcium on top of the matrix, this would be true.
However, the assumption in this paper is that the trace element
is homogenously distributed in the matrix, and the limit is
expressed as an atomic fraction. It is furthermore assumed that
there are no contaminant overlayers on the sample. The number
density of matrix atoms in elemental carbon is higher than that of
elemental silver, meaning that the same number density of trace
calcium atoms has a lower atomic concentration in carbon
compared to silver. The electron attenuation length in elemental
carbon is also higher than that of elemental silver, meaning that
more trace atoms contribute to the detectable signal in carbon
compared to silver. Therefore, with the same background, we expect the detection limit for an element in silver to be worse than
in carbon when expressed as an atomic fraction. Detection limits
are affected by not only the sensitivity factor of the trace element
and the background intensity of the matrix, but also the number
density of atoms and electron attenuation lengths in the matrix.
Within this paper, a large number of terms and symbols are
used. For convenience, these are collected and described in
Table 1. It should be noted that most of these are only required
if it is necessary to inspect the details of the calculations which
give rise to the detection limits summarised at the end of the
paper. To calculate or estimate detection limits using the procedures in this paper, only a few of the terms are required, and
these are summarised in Table 2.

Uncertainty in XPS peak areas

176

A useful starting point is to consider the manner in which peak

areas are determined in the analysis of XPS data. A number of
points, usually two, are chosen to dene the position of the background. The area under the data between these two points,
containing N points, is summed, and the calculated area of the
background is subtracted from this to provide an estimate of
the true peak area, as indicated in the bottom right graph in Fig. 2.

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Although there are a number of background shapes available to

the analyst, we assume that a sensible choice has been made and
that, for trace elements, the shape is indistinguishable from a linear background. A detailed analysis of uncertainties in peak area
determination and their impact on quantitative analysis in XPS
has been provided previously:[3,4] the analysis here is somewhat
simpler than that previous work, but provides essentially the
same result. In a noise-free spectrum, the intensity expressed as
the number of counts at any point, x, in the spectrum is given
by Cx = + fxA, where is the actual background intensity in
counts, A is the true area of the peak in counts and fx is the
normalised distribution of A over x. We assume that the noise
in the spectrum is dominated by Poissonian shot noise such that
the variance in intensity 2 = Cx. It is then straightforward to show
that the variance of the summed area is 1 2 = A + N.
The variance of the background area is somewhat less straightforward. The estimated background intensity at a particular point
is usually calculated as the mean of a number, w, of adjacent data
points. The variance for one of the background points is then
2 2 = /w. The estimated background area under the N points
is calculated by summing the two background points, the sum
having variance 2 2 2, and multiplying by N/2. This multiplication
linearly scales the standard deviation of the sum, and thus the
variance scales by N2/4, giving a variance in the background area
3 2 = N2/2w. The combined variance in the estimate of A using
this approach is thus given by:



N
2A 21 23 A N 1
2w

(1)

It can be easily seen that binning or smoothing the data will

not alter this variance, except insofar as smoothing may increase
the effective value of w more signicantly than that of N. A typical
spectrum with a peak of full width at half maximum (FWHM) 1 eV
and data at every 0.1 eV may be analysed with N = 60 and w = 10
(note that the peak must be fully contained within N-w points, in
this case a 5-eV range is assumed to be sufcient). The variance in
the estimate of area will be A2 = A + 240, which clearly shows
that, unless the peak is very intense, with a peak height typically
larger than 20, the major contribution to uncertainty in XPS area
determination is the background.

2014 Crown Copyright.

Surface and Interface Analysis 2014 John Wiley & Sons Ltd.

Surf. Interface Anal. 2014, 46, 175185

XPS detection limits

Table 1. Denition of symbols used in this paper
Symbol

a
f
g
i
n,l,j
s
t
w
A
B
*
B
C
E
I
IR
Ix
L
M
N
S
T
X
Z

Description

Notes

Measured background intensity (counts)

Data point spacing (eV)
0.5
Detection limit scaling factor (eV)
3
Matrix mass density (g cm )
Standard deviation
Dwell time per point (s)
Trace element
Relationship between matrix peak and background intensity
Normalised peak shape
Matrix element
Quantum numbers
Instrumental relative sensitivity factor
Equivalent overlayer thickness (nm)
Number of points used to determine average background intensity
Photoelectron peak area (counts)
Relative true background intensity (counts)
Modelled instrumental background intensity (counts)
Number of electrons detected at a single point (counts)
Electron kinetic energy (eV)
Relative photoelectron peak area (counts eV)
Reference photoelectron peak area (counts eV)
Instrumental Ag3d5/2 photoelectron peak area (counts eV)
Attenuation length of electron in matrix (nm)
Atomic mass of matrix (Da)
Number of points used to determine peak area
Average matrix relative sensitivity factor for transmission-function corrected data.
Instrumental transmission function
Atomic fraction (at.%)
Atomic number of matrix or trace element

Detection limits
To estimate detection limits, a practical route is to nd the values
of A which are signicantly larger than A. At the 95% condence
level, the requirement is, to a good approximation, A > 2A. For
small values of A, this limit, combined with Eqn (1), becomes:
s
s






N
N
ALOD 2 A 2 N 1
2 N 1
(2)
2w
2w

Surf. Interface Anal. 2014, 46, 175185

0.5

9 (eV)

used here.

B = fI

proportional to TS

raw data or estimated

function of E
proportional to TB

10 counts eV Ag3d5/2 used here

Measured by analyst from pure silver
function of E

0.5

TE

used here

for an undetectable trace element, a, may be expressed as an

atomic fraction, X, using Eqn (3). It is important to note that peak
areas may be reported in different units: e.g. counts per second
(cps), (A/); counts eV, (A); or cps eV, (A/). To use Eqn (3), these
must be converted into total counts (A) by scaling the reported
area with the dwell time per point, , and/or the data point
spacing, , as appropriate.
X LOD a

ALOD =sa

ALOD =sa Ai =si 0:5 sa =Ai =si

(3)

The evaluation of is most conveniently done using the raw

XPS data and taken as equal to the square root of the average
background intensity in counts at the energy position where
the photoelectron line of the element of interest, a, occurs. If a
transmission function or other scaling has been applied to the
data, then the value of should be calculated from the difference between the background data and a linear, or other suitable, t to the background data. The standard deviation of this
difference will provide an estimate of .

Estimated detection limits for binary systems

Detection limits within existing data are best evaluated from the
data themselves, as described above. However, it is often necessary to have some idea of the detection limit for a given element
in a particular matrix before beginning an experiment. This is

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177

Eqn (2) clearly depends upon the choices made by the analyst
and the shape of the photoelectron peak, but under reasonable
conditions, one may achieve N 5w, with the value of N
depending upon the choice of energy step size, . For a peak of
~1 eV FWHM, we may estimate N 6/, resulting in the estimate
ALOD 90.5. For = 0.1 eV, this provides ALOD 28 , and this
value accords with the by eye detection limit indicated in Fig. 2.
In the remainder of the paper, we express detection limits as
ALOD 0.5, with = 9 (eV)0.5 and = 1 eV as the default
values, to mimic detection limits in a typical survey spectrum. If
desired, the values of and may be altered in accordance with
Eqn (2) to achieve the required condence level and to account
for local practice in data analysis.
It is important to translate the detection limit into a composition. If the sensitivity factors, s, for all relevant photoelectron
peaks in that instrument are known and the peak areas in counts,
A, of all other elements, i, are measured, then the detection limit

raw data

A. G. Shard
Table 2. Values required to calculate or estimate detection limits.
Those in parenthesis may be used in some circumstances
Symbol Equation

Comments

Calculation of detection limit from existing data

3
Step size in the data (eV)

3
May be altered to suit specic cases: 9
0.5
(eV) recommended

3
Standard deviation of background at E
sa
3
Instrumental relative sensitivity factor for trace
element line at E
si
3
Instrumental relative sensitivity factor for
matrix elements
Ai
3
Peak areas of matrix elements
E
--Kinetic energy of trace element line
0.5
()
--Background intensity (counts): B =
for raw data.
(N,
2
Alternative approach to nd ALOD for Eqn (3).
w)
The factor 2 in Eqn (2) may also be
changed to accord with local denitions.
Estimation of detection limits from Figs. 5 and 6
Ix
15
Measured using the same conditions as the
intended analysis
x
15
Step size in the intended analysis
(T)
16
XPS instruments with unusual transmission
functions.
(L)
Example Conversion of detection limit to overlayer
2
thickness or coverage

Figure 2. Simulated XPS data using constant background intensity and a

Gaussian peak with full width at half maximum equal to ten points in the
data. The area of the peak, A, is given in terms of the background noise,
B, and increases from below to above the detection limit which, visually,
is between 20 B and 40 B. Gaussian noise with variance equal to the
ideal intensity has been added to each point. The meanings of N and
w are indicated in the nal graph.

178

necessary to establish whether a particular measurement is feasible or to determine the acquisition time required to ensure that a
given detection limit is safely achieved. To estimate the detection
limits for pairwise combinations of trace elements and matrices, it
is necessary to estimate the background intensity from the matrix

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at the position of the photoelectron peaks of the trace element.

This is somewhat arduous to perform with accuracy for every
combination. However, by using a number of reasonable approximations, a good estimate may be achieved. In this work, the contribution of Bremsstrahlung radiation and X-ray satellites from
non-monochromatic sources is not considered. These should
not provide a major contribution to error in the resulting detection limits, although overlaps between trace element peaks and
matrix peaks excited by X-ray satellites will extend the range over
which interference between photoelectron lines may occur.
Estimation of photoelectron and Auger electron intensities
from elemental matrices
The relative intensity of the elastic photoelectron peak associated
with principal quantum number n, angular momentum quantum
number l, and nal state total angular momentum j is estimated
using Eqn (4).


In;l;j LEn;l;j Sn;l;j = MLE n;l;j;AM

(4)

In which LE is the electron attenuation length in the element at

the kinetic energy of photoelectron peak (n, l, j) calculated using
the equation called S4 from Seah,[6] and LE,AM is the attenuation
length at the same energy in an average matrix, taken as having
atomic number ZAM = 28 Da and atomic size 0.25 nm.[6] The
number density of atoms in the elemental material is calculated
from the mass density, in g cm3, and atomic mass, M in Da, as
is the atomic size for the calculation of LE.[6] The average matrix
relative sensitivity factor, Sn,l,j, is taken from data available on
the NPL website (http://www.npl.co.uk/science-technology/surface-and-nanoanalysis/services/xps-and-aes-average-matrix-relative-sensitivity-factors) and described elsewhere.[7] These
sensitivity factors are for transmission-function corrected spectra and are distinguished from the instrumental sensitivity
factors, s, employed in Eqn (3). This distinction is of some importance in later equations. The kinetic energies, E, of each peak are
calculated from the binding energies tabulated in the X-ray Data
Booklet[8] with some adjustments to the N 1s, O 1s and F 1s binding
energies which are given there as ~10 eV higher than their
typical solid-state binding energies. Values of binding energies
and sensitivity factors which are not available (for example, for
the element technetium) are extrapolated or interpolated from
neighbouring elements.
Valence electrons which are unaccounted for in binding energy and sensitivity factor tables, varying in number from between 1 electron for the rst group elements lithium, sodium,
etc. and 17 electrons for lutetium, are each assumed to have zero
binding energy and In,l,j = 0.01 IAg, where IAg is the relative intensity of the Ag 3d5/2 peak calculated from Eqn (5) below. This is not
unreasonable given the estimated intensities from photoelectron
peaks with small binding energies and ultimately provides a reasonable match with the data shown in Fig. 3.
In order to estimate the Auger electron relative intensities, it is assumed that all core-hole states decay by the Auger process, and
therefore the intensity of Auger electrons can be calculated from
the intensity of the corresponding photoelectrons. Thus, for a series
of Auger lines nyy, the relative intensity is estimated from Eqn (5).


Inyy LE nyy In;l;j =LEn;l;j

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Surface and Interface Analysis 2014 John Wiley & Sons Ltd.

(5)

l;j

Surf. Interface Anal. 2014, 46, 175185

20

20

18

18

16

16

14

14

Counts (104)

Counts (104)

XPS detection limits

12
10
8

12
10
8

0
200

400

600

0
200

800 1000 1200 1400

400

20

20

18

18

16

16

14

14

12
10
8

10
8
6

2
200

400

600

800 1000 1200 1400

Kinetic Energy (eV)

800 1000 1200 1400

12

600

Kinetic Energy (eV)

Counts (104)

Counts (104)

Kinetic Energy (eV)

0
200

400

600

800 1000 1200 1400

Kinetic Energy (eV)

Figure 3. XPS spectra of four elemental matrices, carbon, copper, silver and gold acquired using monochromatic Al K radiation and scaled to match
0.5
6
delivering 10 counts at the Ag 3d5/2 peak (thin line). The bold
the performance of an instrument with a transmission function TE proportional to E
line represents the estimated background counts, B*, for the same element in the same instrument using the procedure described in this work.

This neglects the ne detail of Auger features and a number of

processes, the most important being the generation of Auger
electrons from secondary radiation, especially for Auger electron
features at low (less than ~500 eV) kinetic energy. In such cases,
there may be a signicant ux of photoelectrons with sufcient
energies to excite the relevant core hole.[9] Therefore, we expect
to underestimate the low kinetic energy Auger electron background for a number of elements. Fortunately, the majority of
important photoelectron lines have kinetic energies above this
range. Less signicant errors arise from the neglect of the competitive X-ray uorescence process, which amounts to less than
10% of core-hole decays where the core binding energy is lower
than ~2000 eV, and the neglect of the difference in angular emission between the photoelectrons and Auger electrons.

Estimation of the energy-dependent background intensity

for elemental matrices

Surf. Interface Anal. 2014, 46, 175185

E < E n;l;j

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Surface and Interface Analysis 2014 John Wiley & Sons Ltd.

Bn;l;j f 0 In;l;j exp

E  E n;l;j
E1


(6)

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179

The inelastic background generated by each peak is related to

the intensity of that peak by a factor f = Bn,l,j/In,l,j, in which In,l,j is
the area of the peak in counts eV, and both f and B depend upon
the electron kinetic energy with f having a common form for all

elements. Whilst Tougaards analysis[10] of the shape and intensity of the inelastic background provides some condence in
the approach, it is not straightforward to obtain functional forms
and values of the factor f from that work. More useful
relationships for this purpose can be obtained from Seahs analysis of REELS data.[11] From Seahs paper, the background, Bn,l,j,
may be modelled as an exponential decay of E1 = 714.9 eV to
lower kinetic energy. The paper also provides a number of relationships which enable the estimation of f(En,l,j  90). This may
simply be extrapolated, by a factor of exp(90/E1) = 1.134, to nd
f(En,l,j) = 1.134 f(En,l,j  90) = f0, which is assumed constant for
any given element. In this work, the inelastic background for each
photoelectron peak is calculated using Eqn (6) and is zero at
kinetic energies higher than that of the peak. An identical approach is used to estimate the inelastic background generated
by Auger electron peaks, Bnyy, from their estimated total intensities, Inyy. The energy position used for the Auger electron peaks
is the central energy of the range over which these peaks occur
for a given element, as identied in the Phi XPS Handbook.[12]

A. G. Shard
The factors, f0, are obtained from Seahs analysis of REELS
data[11] and are expressed in Eqns (711) as a function of atomic
number, Z, atomic mass, M in Da and elemental density in g
cm3 for each element.

0:5
M
3 Z 56
f 0 0:0495
 0:0029
(7)
Z
57 Z 71

72 Z83

f0


0:0483 MZ 0:5
 0:0029
107  Z


0:0207 MZ 0:5
 0:0029
f0
Z  59

(8)

(9)

The simulated background, B, in counts, for each pure element

is calculated as the sum of the background contribution, Bn,l,j,
from all detectable photoelectron peaks and the background
contribution, Bnyy, from Auger electron peaks. For display purposes, background contributions from Auger electron features
are curtailed at the low kinetic energy of their range, and a linear
drop to zero at the high kinetic energy of their range is calculated. The range is taken from the Phi Handbook of XPS. [12] This
linear drop is clearly shown in the copper background in Fig. 3,
but does not inuence any of the calculated detection limits because trace element photoelectron peaks in this highly structured
region are excluded from the analysis, as described later. The Phi
Handbook[12] does not provide details of all Auger electron peaks
and, as is evident in Fig. 3 in the copper, silver and gold spectra,
there can be weak features outside the range identied in this
reference. Therefore, the detection limits of trace elements with
major photoelectron peaks close in energy to matrix Auger electron contributions may be worse than given in this work if their
peak positions coincide with these weak features.
Finally, the background counts for the matrix element in a typical instrument,[1315] B*, is simulated by scaling B by a transmission function proportional to E0.5 and normalising to achieve a
reference Ag 3d5/2 intensity of IR counts eV for pure silver. This
is expressed in Eqn (10), in which IAg is the relative area of the
Ag 3d5/2 peak calculated from Eqn (4) and EAg is the kinetic energy of that peak. In the rest of this work, we use a default value
of IR = 106 counts eV.


0:5
B BIR E 0:5
(10)
Ag = I Ag E

180

Figure 3 shows B* using Al K X-rays for carbon, copper, silver

and gold as bold lines. XPS data for polystyrene, copper, silver
and gold are compared to these estimated backgrounds as thin
lines. In Fig. 3, the XPS data for all samples were taken under
identical conditions using monochromatic Al K radiation on a
Kratos AXIS Ultra DLD, pass energy 160 eV, hybrid lens mode
using the slot aperture (700 m 300 m), which provides a
transmission function closely proportional to E0.21. These raw
data have been scaled by E0.29 to simulate the response of the
typical hemispherical analyser modelled by B* and a constant factor to achieve an Ag 3d5/2 intensity of 106 counts eV in the silver
spectrum. The Ag 3d5/2 intensity was 6 105 ( 1 105) counts eV
in the raw data, taken as the average intensity found using either
a Tougaard or a Shirley background subtraction. The estimated
background B* provides a good match to the scaled data, easily
within a factor of 1.5 for all four materials. Because detection

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limits scale with the square root of the background intensity, this
implies that the detection limits estimated here will be within
~20% of the detection limits of the modelled instrument. We
may note from this comparison, that the value of E1 for gold
should be somewhat smaller than 714.9 eV, at least close to the
peaks, but the approximation is still more than adequate for
the purposes of this paper.
Estimation of detection limits for trace elements in an elemental matrix
For a trace element photoelectron peak, a, the value of in the
modelled instrument can be estimated as (B*)0.5 at the kinetic energy of the peak, Ea. The intensity in counts, Ai, of a matrix photoelectron peak with kinetic energy Ei for the modelled instrument can be
calculated from Ii using Eqn (11). The choice of matrix photoelectron
peak for this purpose is not important, as shown shortly.


0:5
Ai Ii IR E 0:5
(11)
Ag = IAg E i
The expressions for B and Ai can be inserted into Eqn (3) to
obtain Eqn (12), which provides the detection limits for the photoelectron peak, a, of a trace element in a matrix of element i.

h

i
0:25
0:5 0:5 0:25
X LOD a; i B0:5 = B0:5 Ii Sa I0:5
(12)
R E Ag = Si IAg E a
It is important to recognise that the instrumental sensitivity factors, s, used in Eqn (3) are proportional to the product of the average
matrix relative sensitivity factor, S, and the transmission function of a
typical instrument, taken here to be E0.5. This eliminates Ei from Eqn
(12), and, since the ratio of Ii to Si is provided by Eqn (4) in terms of
the material properties of the matrix, the detection limit is independent of the choice of the matrix photoelectron peak, i.
For a selected trace element and matrix pair, the kinetic energy
positions of all the detectable photoelectron peaks for the trace elements, Ea, are compared with the photoelectron peaks and Auger
electron peaks of the matrix. For trace elements up to magnesium
(Z = 12) the KLL Auger electron peaks are also included as an alternative means of detection in XPS. If the kinetic energy of the trace
element photoelectron or KLL peak is more than 5 eV above or 20
eV below any of the matrix photoelectron or matrix Auger electron
kinetic energy positions, it is deemed to be in a region of the background which is relatively featureless. In these cases, the limit of
detection is calculated using Eqn (12). If the separation between
a spinorbit doublet is less than 4 eV, then the doublet pair is combined. For example, the Si 2p3/2 and Si 2p1/2 peaks are treated as a
single Si 2p peak at the kinetic energy of Si 2p3/2 but with the
summed sensitivity factor of the two peaks.
After the detection limits for all photoelectron and KLL peaks
for the trace element in the matrix have been calculated, the
elemental detection limit is selected to be the same as for the
peak that has the lowest detection limit and that has no interference from the matrix. This procedure is exemplied in Fig. 1,
where the K 2p trace photoelectron peak is too close to the C
1s matrix peak for reliable detection limits to be specied and
the K 2s photoelectron peak is selected instead to determine
the detection limit for this trace element and matrix pair. A similar interference occurs for the trace Cr 2p peak in silver.
In some cases, it is not possible to provide a detection limit due
to the overlap of all trace element photoelectron peaks with matrix features. Such combinations are classied along with those

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Surf. Interface Anal. 2014, 46, 175185

XPS detection limits

that have detection limits of 30 at.%. This is highly pessimistic,
since the precise position of the photoelectron lines in those matrices are not known and the trace element peak may be identied using careful data analysis. However it is not possible to
estimate useful detection limits in such cases using the approach
in this work and the worst case is assumed as a precaution.
XPS detection limits for Al K and Mg K X-ray sources
The estimated XPS detection limits for all trace and matrix element pairs between lithium (Li, Z = 3) and bismuth (Bi, Z = 83)
have been calculated in this manner for XPS instruments operating with either Al K and Mg K X-ray sources. These calculations

use IR = 106 counts eV, = 9 (eV)0.5 and = 1 eV, as described earlier. The data from this analysis are rather cumbersome to represent as numerical data, but are relatively easy to interpret as
colour maps. In these, a colour scale is used to indicate the detection limit, with red indicating the worst detection limits and blue
the best detection limits.
In Fig. 4, a guide to the colour maps presented in Figs. 5 and 6
is provided. Detection limits are shown on a scale from 30 parts
per million (0.003 at.%) as blue, to 10 at.% as dark orange. The
colour red is reserved for trace elements with detection limits in
that matrix of 30 at.%, or for those trace elements where there
is a signicant probability of interference from matrix features
for all photoelectron peaks. It can be seen that XPS detection

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181

Figure 4. (a) A guide to the interpretation of XPS detection limits for trace elements in an elemental matrix expressed as a colour map. Features in the
matrix element XPS spectrum that interfere with the main peak used to identify the trace element are indicated by black lines. (b) Detail of a region of
the detection limit colour map for Al K source for trace elements from Z = 13 to Z = 32 for which the 2p photoelectron is generally employed for trace
detection. Matrix elements from Z = 5 to Z = 35 are covered, and a detailed description of interferences is provided.

A. G. Shard
limits span almost four orders of magnitude, but the majority of
trace element and matrix combinations lie in the range between
0.1 and 1 at.% shown by the yellowgreen to yelloworange colours. It is easier to detect trace heavy elements in a light element
matrix and more difcult to detect trace light elements in a heavy
element matrix due to the general increase in photoemission intensity from heavier elements. This explains the underlying
change from orange to blue from the lower left to the top right

of the colour maps. Vertical breaks in colour are associated with

changes in the typical photoelectron peak used to detect the
trace element. As the value of Z increases, these peaks either
become too low in kinetic energy (<200 eV) to be useful, or
change from having a doublet classied as a single peak to
being separated peaks (e.g. 3d to 3d5/2). Horizontal breaks occur
most signicantly where Auger electron peaks change from
being strong to being absent, but also weaker breaks can be

182

Figure 5. Detection limits for an XPS instrument using Al K radiation providing 10 counts eV for the Ag 3d5/2 peak in pure silver. The key to the colour
scale is given in Fig. 4a.

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Surf. Interface Anal. 2014, 46, 175185

XPS detection limits

Figure 6. Detection limits for an XPS instrument using Mg K radiation providing 10 counts eV for the Ag 3d5/2 peak in pure silver. The key to the
colour scale is given in Fig. 4a.

Surf. Interface Anal. 2014, 46, 175185

interferences between the photoelectron peak used to detect

the trace element and Auger electron peaks in the matrix. These
are marked with dashed lines in Fig. 4a and become more significant with increasing matrix atomic number because the Auger
electron intensities and kinetic energies both increase with
atomic number. To the right of these interference lines, at higher
Z for the trace element, the detection limit is worse than on the
left because the trace element peak is at a lower kinetic energy

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183

seen at the boundaries of the elemental periods where a nonmetallic matrix is adjacent to metallic matrix with some associated density changes. Diagonal breaks in colour moving down
to the right can be associated with interferences between the
typical photoelectron peak used to detect the trace element
and photoelectron peaks in the matrix. These are identied in
Fig. 4a as solid black lines with the matrix photoelectron peak
indicated. Curved breaks moving up to the right are due to

A. G. Shard
from the indicated matrix peak and is on the background associated with that matrix peak. Figure 4b shows an expanded and
more detailed view of a small region of the colour map.
Use of the estimated XPS detection limits
Figure 5 displays the detection limits for Al K sources and Fig. 6
the detection limits for Mg K sources. These may be used in a
straightforward manner to establish whether the detection of a
particular element at a particular concentration is feasible. If the
matrix contains a mixture of elements, then the detection limit
for the trace element may, conservatively, be taken to be the
same as the worst detection limit of the trace element in the
individual elements present in the matrix. A more optimistic
approach is to use the square root of a mole-fraction-weighted
quadratic sum of the limits for all elements present in the matrix.
This is based upon an assumption of a contribution of background
intensities from each element in the matrix proportional to its concentration and is reasonable, provided that the same trace element
peak has been used to dene the detection limit for all matrix elements. This is expressed in Eqn (13) where Xi is the mole fraction of
each of the individual elements, i, in the matrix, c, and XLOD(a,c) is
the detection limit in the compound matrix.
X LOD a; c2 X i X LOD a; i2

(13)

If the performance of the XPS instrument is known, then Eqn (12)

may be employed to estimate detection limits and acquisition
times. For this purpose, a useful approximation of Eqn (12) is given
in Eqn (14) in which the terms that are most directly inuenced by
the performance of the instrument and choices made by the
analyst are collected outside the square brackets. The transmission
function of the instrument only weakly affects detection limits, and
therefore the term describing it has also been enclosed in the
square brackets. The value of is of modest importance and may
be as low as 7 (eV)0.5 for peaks sharper than 1 eV in width and as
high as 11 (eV)0.5 for peaks which are broader than 1 eV in width.
This represents ~20% error, which is of no great signicance in
the context of this work. Therefore, has also been enclosed in
the square brackets but may be altered if the local denition of
the limit of detection is different from Eqn (2).
"

0:25 #
I0:5
0:5
Ea
0:5 Ag Si
X LOD a; i 0:5 B
(14)
I
S
E
IR
i
a
Ag

detection limits, i.e. by (Xx/Xy)2, either through an increase in the

number of sweeps or the dwell time.
If the instrument used has an unusual transmission function, T,
then the detection limit found from Eqn (15) may not be suitable
and the alternative expression given in Eqn (16) should be used
instead. In this equation, TAg is the transmission function at EAg,
the kinetic energy of the Ag 3d5/2 line in pure silver. Ta is the
transmission function at Ea, the kinetic energy for the line used
to detect the trace element a.
!0:5


0:5 0:5
E Ag T Ag
106
X ref
X x x
Ix
E 0:5
a Ta

(16)

Example 1
Figure 7 shows the Al K XPS spectrum of I 3d5/2 taken from a polymer which consists largely of carbon using x = 0.1 eV and under
conditions which provide IR 106 counts eV. Quantitative XPS analysis indicates that the concentration of iodine is X1 = 0.07 at.%,
which is below the conventionally accepted XPS detection limit
but clearly well above the true detection limit. From the raw data,
we can see = 12 700 counts and therefore = 113 counts.
Therefore, from ALOD = 90.5 28, we nd ALOD 3200 counts.
Using the appropriate sensitivity factors and Eqn (3), or noting that
in this spectrum the I 3d5/2 peak has A1 = 36 000 counts and that
XLOD X1(ALOD/A1), we nd XLOD(I, polymer) 0.006 at.% for iodine
in this matrix using these experimental conditions.
From Fig. 5, we note that Xref(I, C) 0.02 at.%, and using Eqn (15)
with x = 0.1 eV and Ix = 106 counts eV, we nd Xx(I, C) 0.006 at.%.
This example demonstrates that the two approaches provide
consistent results, in this case at least.
Example 2
It is necessary to conrm that a calcium hydroxide, Ca(OH)2, thin
lm of ~10 nm thickness contains less than 0.1 at.% of vanadium.
The XPS instrument uses Al K and provides 5 105 counts eV for
the Ag 3d5/2 peak in pure silver in a 5-min acquisition using x = 1
eV. From the Al K colour map, the reference detection limits are,
Xref(V, Ca) 0.4 at.% and Xref(V, O) 0.03 at.%. The detection limit
of vanadium in Ca(OH)2 can therefore be estimated using Eqn (13)
as Xref(V, Ca(OH)2) 0.23 at.% for an instrument providing 106
counts eV for the Ag 3d5/2 peak in pure silver. Using Eqn (15), we
13800

X x x

10
Ix

6 0:5

X ref

(15)

13400
13200
13000
12800
12600
12400
12200
855

860

865

870

875

880

Kinetic Energy (eV)

184

If a particular detection limit, Xy, needs to be achieved under

these experimental conditions then the acquisition time should
be scaled in proportion to the square of the ratio of the relevant

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13600

Counts

The colour maps provided in Figs. 5 and 6 have been compiled

using IR = 106 counts eV, = 9 (eV)0.5 and = 1 eV, as described previously. To account for instrument performance under a particular
mode of operation and local practice in data analysis, the detection
limit Xref obtained from the gure should be scaled using Eqn (15)
to estimate Xx, the limit of detection under those particular operating conditions. In this equation Ix is the intensity in counts eV of the
Ag 3d5/2 peak for pure silver on the instrument and settings used
and x is the spacing of data points in eV in the spectrum.

Figure 7. The I 3d5/2 peak from a polymer containing 700 ppm iodine. The
projected detection limit calculated from the raw data shown here for iodine
in this matrix using this instrument and operating conditions is 60 ppm.

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XPS detection limits

may estimate a detection limit of Xx(V, Ca(OH)2) 0.3 at.% in the
actual instrument. This is three times worse than the desired
detection limit, and therefore the acquisition time should be
increased at least nine times to 45 min or more. To avoid any
uncertainty arising from the estimates used in this work, and to
ensure that 0.1 at.% of vanadium would be unambiguously
detected, a four times longer acquisition (~3 h) should be
employed. After the analysis is complete, a better estimate of the
detection limit may be calculated from the XPS data itself using
Eqn (3) and following Example 1 above.
If it was thought that the vanadium may exist as a surface layer on
Ca(OH)2, a reasonable estimate of the minimum average thickness
that could be detected would be provided by tLOD(V, Ca(OH)
2) LEXx(V, Ca(OH)2) = 0.0045 nm, using LE(V 2p3/2, Ca(OH)2) 1.5
nm. This is clearly in the sub-monolayer regime and, using the average atomic size of 0.25 nm, represents either a vanadium fractional
coverage of ~0.02 monolayers or ~3 1013 atoms cm2.
If the XPS instrument had an energy-independent transmission function (T constant at all E) but the same Ag 3d5/2 intensity, the detection limit may be calculated from Eqn (16).
Using Ea (V 2p3/2) = 974 eV, EAg = 1118 eV, we nd that the
detection limit in this instrument varies from the modelled
instrument by a factor of (1118/974)0.25 = 1.04. This is a negligible difference, and Xx(V, Ca(OH)2) 0.3 at.% remains the
same to within the level of the approximation used here. A signicant (factor of 1.5) difference between the detection limits
for the two instruments would only occur if Ea was lower than
~220 eV (i.e. a binding energy greater than ~1260 eV).

Conclusions
This work presents a comprehensive list of XPS detection limits
using both Al K and Mg K X-ray sources for trace elements homogeneously distributed in pure elemental matrices with no contaminant overlayers. The detection limits have been estimated
for an instrument with a transmission function which scales with
E0.5 delivering 106 counts eV at the Ag 3d5/2 photoelectron
peak. The results are generally in accord with previous generic
estimates of XPS detection limits of 1 at.% to 0.1 at.%; however,
there are cases in which detection limits may be worse than 10

at.% or better than 0.01 at.% (100 ppm). Elements which are hard
to detect in particular matrices due to interferences between substrate photoelectron and Auger electron features have been
identied. The colour maps provided in this work may be used
to estimate the detection limits elements for most XPS instruments and samples, provided that the intensity of the Ag 3d5/2
photoelectron peak under the conditions used for the analysis
are known. They may also be used to estimate the time required
to achieve a given detection limit, which will be helpful in planning work and deciding whether experiments are feasible.
Acknowledgements
This work forms part of the Chemical and Biological programme
of the National Measurement System of the UK Department of
Business, Innovation and Skills and with additional funding from
the European Union through the European Metrology Research
Programme (EMRP) project SurfChem. The EMRP is jointly funded
by the EMRP participating countries within EURAMET and the
European Union. Suggestions and comments from Martin Seah,
NPL, were invaluable in undertaking this work. The XPS data
and instrument transmission function were kindly supplied by
Steve Spencer, NPL.

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