Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432

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Journal of Electron Spectroscopy and

Related Phenomena
journal homepage: www.elsevier.com/locate/elspec

XPS analysis of nanostructured materials and biological surfaces

D.R. Baer ∗ , M.H. Engelhard
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Box 999, Richland, WA 99352, USA

a r t i c l e i n f o a b s t r a c t

Article history: This paper examines the types of information that XPS can provide about a variety of nanostructured
Available online 22 September 2009 materials. Although it is sometimes not considered a “nanoscale analysis method,” XPS can provide a
great deal of information about elemental distributions, layer or coating structure and thicknesses, sur-
Keywords: face functionality, and even particles sizes on the 1–20 nm scale for sample types that may not be readily
Nanomaterial analyzed by other methods. This information is important for both synthetic nanostructured or nanosized
Nanoparticle
materials and a variety of natural materials with nanostructure. Although the links between nanostruc-
XPS
ture materials and biological systems may not at first be obvious, many biological molecules and some
Biosurfaces
Catalysis
organisms are the sizes of nanoparticles. The nanostructure of cells and microbes plays a significant
Particle size role in how they interact with their environment. The interaction of biomolecules with nanoparticles
is important for medical and toxicity studies. The interaction of biomolecules is important for sensor
function and many nanomaterials are now the active elements in sensors. This paper first discusses how
nanostructures influences XPS data as a part of understanding how simple models of sample structure
and data analysis can be used to extract information about the physical and chemical structures of the
materials being analyzed. Equally important, aspects of sample and analysis limitations and challenges
associated with understanding nanostructured materials are indicated. Examples of the application of
XPS to nanostructured and biological systems and materials are provided.
© 2009 Published by Elsevier B.V.

1. Introduction sample features impact XPS data. In a web-based presentation Yang

X-ray photoelectron spectroscopy (XPS) has become an increas-
ingly available and powerful tool for understanding the nature of
many different types of surfaces. Although advances in existing
and newly developing tools with high spatial resolution receive a
good deal of press if they improve the analysis quality of individual
nanosized features of materials, XPS is an important, established
and frequently essential tool for understanding several important
aspects of nanostructured natural and synthetic materials that can-
not easily be obtained using other techniques. In addition, it is
finding increasing applications for analysis of the surfaces of biolog-
ical systems as well as a more traditional role in the characterization
of synthetic materials (biomaterials) designed to be used in biologi-
cal environments. Microbe and cell surfaces might be appropriately
considered as very complex nanostructured systems.
Characterization of nanostructures using XPS is not new. From
the earliest days, XPS or ESCA (electron spectroscopy for chemical
analysis) was widely used to study many aspects of nanosized cat-
alyst particles [1–3]. Over the past 30 years many researchers have
explored important aspects of how particle size or other nanosized
∗ Corresponding author.
E-mail address: don.baer@pnl.gov (D.R. Baer).
and Sacher describe many different aspects of XPS measurements
associated with nanoparticles, including references from their own
work and some of historical importance [4].
The increasing importance of XPS for many types of analysis
arises for several reasons. First, XPS can provide information
about the actual composition and chemical state of surfaces and
interfaces that dominate properties of nanostructured materials.
Surfaces are equally important for the function of biological
organisms and to the performance of synthetic biomaterials.
Second, although it is frequently not considered to be a tool with
“nano” resolution, because the electrons associated with XPS
only travel distances measured in nanometers these electrons
can be used to provide a good deal of information about the
structure of nanometer-sized features of a sample near a surface
region, as described below. Although the possibilities for obtaining
nanometer-scale information from samples with flat surfaces
may be more apparent to many researchers, information from
XPS spectra can be used to determine the size of nanoparticles
(sometimes in circumstances for which other types of high spatial
resolution measurements cannot be applied) as well as provide
information about coatings and layers on particles.
A wide variety of challenges are associated with the characteri-
zation of nanostructured materials [5,6], some specific to XPS and
others applicable to many types of measurements on nanostruc-

0368-2048/$ – see front matter © 2009 Published by Elsevier B.V.

doi:10.1016/j.elspec.2009.09.003
416 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
tured materials and nanoparticles in particular. Similar issues apply
to the study of biological surfaces and they certainly apply to the
intersection of materials science, biology and nanotechnology that
is sometimes called nanobiomaterials. These issues include sample
handling and preparation, the impacts of time and the environ-
ment on samples, problems associated with sample damage, and
fundamental issues associated with understanding and possibly
defining the structure of nanosized objects. Grainger and Castner
[7] make three recommendations related to analysis of nanobio-
materials (paraphrased below) that echo concerns and suggestions
of other reports in the literature:
(1) Existing tools are underused. It is necessary to perform com-
plete physical and chemical characterization of nanoparticles
used in research (and for most applications). There are sev-
eral indications that we are not fully using the tools currently
available to adequately characterize nanoparticles and other
nanostructured materials. A report from a nanobiotech com-
mercialization meeting noted the opinion of several researchers
that important physical and chemical properties of nanoparti-
cles used in research were unreported and apparently unmea-
sured [8]. A Working Party on Manufactured Nanomaterials of
the Organization for Economic Co-operation and Development
(OECD) has established a list of physical–chemical properties
and material characterization needs for nanostructured mate-
rials [9]. Several surface properties are listed among the needed
parameters, but in many circumstances the importance of the
surface chemistry of nanoparticles, especially as applied to
toxicity, has been under-emphasized [10]. The importance of
surface information about these materials is one reason that
XPS measurements are being increasingly applied to them.
However, it has usually been found necessary to systematically
apply a variety of tools to adequately understand the proper-
ties of nanoparticles [5,6,11]. A similar need applies to studies
of biologically related surfaces [12–14].
(2) Nanomaterials and biological surfaces exaggerate analysis chal-
lenges. Because of the high sensitivity of nanoparticles to their
environment, because they often change with time and are
easily damaged (altered during measurement), and because
surface contamination can have dramatic impacts on material
properties as well as what is measured [5], it is essential
to establish reliable measurement, sample preparation and
handling, and storage protocols. The importance of carefully
assessing the interactions of these with their environment
raises several analytical objectives, needs, and challenges.
Sample handling and preparation guides have been prepared
by ISO and ASTM committees [15,16]. Sample lifetime or
time-dependent effects influence analysis needs but may
also have significant impact on shelf and product lifetime for
useful applications. It is equally important to understand the
strengths, limitations, and impacts of the variety of analysis
methods that can be applied to these materials [7,17]. Because
they can significantly impact analysis, some of the fundamen-
tal limitations of both routine and more advanced XPS data
analysis will be introduced in this paper.
(3) New tools and techniques are needed. Scientific and technological
advances associated with nanostructured materials, biological
systems, and nanobiomaterials require detailed information
about the composition, physical and chemical structure and the
presence of contaminants or impurities of complex systems,
frequently while they remain in their natural or operating envi-
ronments [7]. In some circumstances the information needed is
beyond the reach of current analysis tools. It has been observed,
for example, that there are no robust methods for extracting the
needed structural information about nanostructured materials
[18], an issue the authors called the nanostructure problem.
Therefore, new analysis techniques and new methodologies
for extracting information from data need to be developed
[6]. Their development will require close linking of modeling
efforts and multiple types of data. Some sophisticated efforts
to model XPS data (including SESSA [19] and QUASES [20])
highlight some of the progress and possibilities in this area.
This paper is not a comprehensive review but an introduction to
different ways that XPS can be applied to obtain information about
nanostructured materials, including nanostructures that are either
biological in nature or connect materials to biological systems.
Specialized instruments such as synchrotron based XPS, including
unique high pressure XPS capability [21] of importance to catalysis
and biological materials [22], are not specifically addressed. Some
of the topics introduced in this paper will have been described in
greater detail in other contributions to this special issue of JESRP.
Only aspects related to nanostructured or biological surface anal-
ysis are discussed here. The next section of the paper outlines
how nanostructure influences XPS signals; it discusses issues raised
generally and specifically for XPS analysis of nanostructured mate-
rials. Section 3 considers some of the limitations for applying XPS
to nanostructured materials. Section 4 provides examples of the
application of XPS to nanostructured materials (with examples of
nanolayers and nanoparticles) and biological systems (with exam-
ples of microbe surfaces and biomaterials).
2. How nanostructure influences XPS signals
The short distances that electrons can travel within a material
without losing energy (inelastic mean free path [IMFP]) provide
the physical reason that XPS is sensitive to the surface composi-
tion of materials. Differences in IMFPs and distribution of electrons
that have lost energy can be used to extract information about the
nanostructures of many materials. Calculated versions of IMFPs for
several materials [23] are shown in Fig. 1. These curves show that
the average distances that electrons can travel without energy loss
due to inelastic scattering depend on the kinetic energy of the elec-
trons and the material within which they are traveling. These IMFPs
relate to the information depth from which XPS electrons arise.
The contribution to the detected signal from a depth z into the
material will be attenuated by material covering the layer closer
to the surface. Although the equation is only approximately valid
[24], this relationship is often expressed as follows:
 −z

dIz ≈ I1 exp dz (1)
( cos )
Fig. 1. IMFPs calculated for polymethylmethacrylate (PMMA), silicon dioxide, Si,
Cu, and W. (From [23]).
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 2. Schematic drawing of possible distributions of different elements or com-
pounds within the volume analyzed by XPS. Most routine XPS analysis assumes
that there is a uniform distribution (top example), while in many circumstances
the distribution is non-uniform. It is often possible to extract information about the
nanostructure with careful analysis of the data.
where dIz is the intensity of the detected signal at depth z, I1 is
the intensity that would have been produced if the layer were at
z = 0 (the outer surface),  is the IMFP,  is the angle of the detected
electron relative to the surface normal (see Fig. 3a), and dz is the
thickness of the layer. Because  depends on energy (Fig. 1), Eq. (1)
demonstrates both the energy and angle dependence of the sig-
nal intensity from depth z. The information depths from which
detectable signal intensities can be extracted are typically in the
range of 1–20 nm. XPS does not collect information about regions
deeper into the material than the information depth, unless these
depths are exposed for analysis using methods such as sputter
depth profiling.
As XPS data analysis is most commonly applied, information
that could be used to extract information about the structure of
nanomaterials is often ignored. Five of many possible distributions
of two elements (light and dark) within the information depth of
a flat film are schematically shown in Fig. 2. In many cases, XPS
data are analyzed assuming that all elements measured are uni-
formly distributed throughout the layer analyzed (the top image in
Fig. 2). However, in most circumstances it is likely that the elements
detected during XPS measurement are not uniformly distributed
(such as layers, clusters, or buried clusters). For both research
and technological applications it is often of importance to actu-
Fig. 3. (a) Drawing showing differences in information depth as the angle between sample surface normal and the path toward electron analyzer varies. The information
depth also changes with the energy of the electron detected. (b) Schematic drawing indicating how differences in information depth (due to photoelectron energy or angle)
influence the amount of a multilayer film structure detected. Comparison of data from small and larger information depths provides information about the sample layering.
417
ally determine as much as possible about the actual distribution
of elements. The influences of specimen structure appear in XPS
data in several different ways. By understanding how nanostruc-
tures impact XPS data and by combining this knowledge with other
knowledge about the nature of a specimen it is often possible to
obtain important structural or elemental distribution information
that can be difficult or impossible to obtain in other ways.
The nanostructure of a specimen influences XPS data in several
different ways including the following:
• Peak intensities and relative peak intensities of
o peaks for different elements
o different peaks for the same element
o variation as a function of emission angle
• Peak energies
o binding energies of peaks
o value of the Auger parameter
• Background signals from electrons that have lost energy.
Depending on what is known about the specimen and the anal-
ysis objective, each of these influences can be used to extract useful
information about nanostructured samples.
2.1. Relationships between nanostructure and relative peak
intensities
In addition to determining the “average” composition of a sur-
face, relative signal intensities can be highly useful in obtaining
information about layered structures of samples and sometimes the
sizes of particles. Because the information depths will vary with the
energy of the photoelectron (or Auger-electron) analyzed as well
as the angle at which they are collected, peak ratios can be used
to learn about compositional layering, enrichment, and segrega-
tion of elements toward or away from the surface of a specimen.
The examples provided in this section focus on flat samples for
which the concepts are most easily understood, but the same con-
cepts extend to other types of nanostructured materials including
nanoparticles, nanotubes and complex catalysts.
The impact of angle and energy on the information depth are
schematically shown in Fig. 3. For low kinetic energies (high pho-
toelectron binding energies) or high angles of emission (emission
normal to the surface is defined as  = 0), the information depth is
less than for normal emission or higher kinetic energy peaks. When
the information depth is shallow the relative signal intensities from
the elements located nearest the surface are enhanced. Therefore,
by measuring peak intensities as a function of emission angle, the
variation of elemental peak ratios provides layering information
[25]. The use of angle-resolved XPS (ARXPS) can be applied in dif-
418 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 4. XPS survey spectra of an oxidized Ni foil with carbon overlayer contami-
nation. The relative peak ratios of different Ni peaks are influenced by the carbon
overlayer.
ferent ways to get information about elemental enrichment (or
depletion) at the surface or to construct more detailed near-surface
depth profiles.
2.1.1. Layer thickness and structure
The relative intensities of photoelectron peaks from a layer are
impacted by the layer thickness and the thickness of any layers that
may cover it. For the oxidized Ni sample in Fig. 4, the intensities of
the Ni peaks are impacted by the oxide layer thickness and by a
contamination layer of carbon on top of the oxide. The ratio of the
Ni 3p/Ni2p3 photoelectron peak intensities (obtained using peak
integration and Shirley background subtraction) for a thick, sputter
cleaned Ni specimen (for typical analysis conditions applied in our
Phi Quantum 2000) is 0.29. Because the kinetic energy of the Ni
3p photoelectron peak is significantly higher than that for the Ni
2p3, the ratio can provide information about surface enrichment
or depletion. If the ratio is less than 0.29, there is relatively more
Ni 2p signal than for a uniform sample, suggesting, for example,
Ni enrichment near the outer surface of the sample. If the Ni 3p/Ni
2p3 peak ratios are >0.29, it would suggest that there is less Ni near
the surface. If, as a different example, only a thin film of Ni were
present, the Ni 3p/Ni 2p3 ratio could provide information about the
thickness of the film (if it were thinner than the information depth
of the Ni 3p electrons). Castle is among the researchers who have
used this approach to understand the structure of corrosion films
for transition metal alloys [26].
It is also important to recognize that layers on top of the ele-
ments of interest will usually alter the peak ratios from elements
within a buried film. The impact of these coating layers can provide
useful information but requires that some care to be applied to the
analysis to avoid confusion. For the oxidized Ni sample in Fig. 4,
the measured Ni 3p/Ni 2p3 peak ratio is 0.35, possibly indicating
Ni depletion from the surface. Such depletion is real in this case,
but the depletion is only due to a significant presence of carbon on
the surface. The depletion does not provide us with any informa-
tion about Ni distribution in the Ni film itself and is not likely to be
information of any value. Several approaches could be used to con-
sider the impact of the carbon on the other elemental peaks. Using
the carbon correction applied by Castle [26], the carbon overlayer
can be estimated to be approximately 8 Å thick and the impact on
the other (not carbon) peak amplitudes can be estimated and a cor-
rection made. Without carbon correction, the Ni3p/Ni2p3 ratio is
0.35, as noted above, while the ratio with the intensity correction
is 0.30, which is very close to that of pure Ni (0.29), suggesting no
enrichment or depletion of Ni in the oxide layer under the carbon
contamination layer. Similar effects would occur for different layers
of multi-layered surface structures.
When a specimen is known to have two layers and XPS photo-
electron peaks unique to each layer are present, the thickness of the
layers can be estimated using several different analysis approaches
usually based on equations similar to Eq. (1). Cumpson has pre-
sented a graphical approach to calculating the thickness of the layer
[27] using peak intensity ratios, instrumental sensitivity factors,
and the energy ratio for the photoelectrons involved. The involve-
ment of the energy ratio provides a method for accounting for the
different attenuation length or electron free paths for photoelec-
trons of different energies.
Peak amplitudes can be used in a variety of ways to extract lay-
ering information, both for flat films and other structures as noted
below. Mohai [28] has developed a free computer program that
uses peak amplitudes to analyze layer structures using only XPS
signal amplitudes. XPS MultiQuant is described as a “quantitative
evaluation program for X-ray Photoelectron Spectroscopy, serving
as a practical and universal tool for the surface analyst. It applies
the ‘classic’ methods of the quantitative calculations using the inte-
grated intensity of the measured XPS lines.” As one example, XPS
MultiQuant has been used to characterize and confirm the structure
and quality of a Langmuir Blodgett film on glass [29].
A spreadsheet (ARCtick) for assisting layer structure determi-
nation from ARXPS measurements is provided by the National
Physical Laboratory [30,31]. ARCtick allows comparison of a variety
of methods that can be used to extract thickness, elemental dis-
tribution and elemental layering and provides some suggestions
when different approaches may be most useful (e.g. regularization
[32] may be the best method when concentration gradients may
be important not just discrete layers). As described below XPS data
simulation or analysis programs (e.g. QUASES [33] or SESSA [34])
may be useful for understanding layer thickness and structure.
2.1.2. Molecular orientation
A variety of methods can be used to determine the orienta-
tion of molecules attached to a surface including near-edge X-ray
adsorption fine structure (NEXAFS) [35] and optical methods, such
as surface enhanced Raman spectroscopy [36]. Although XPS can be
insensitive to molecular orientation in some circumstances [37],
for ordered molecular assemblies [38] and larger molecules with
asymmetric elemental distribution [39], XPS can be used to deter-
mine some information about molecular orientation. For ordered
molecular assembles, there can be shifts in the binding energies
associated with molecular orientation [38]. For the larger molecules
the primary impact is that related to signal strength due to depth
or layering effects as discussed above. Alessandrini et al. [39], for
example, have used XPS to show differences in protein orientation
on surfaces by comparing the magnitudes of N 1s photoelectron
peak amplitudes. Frequently, XPS is used in combination with
other methods to understand the overall composition, uniformity
and molecular orientation [40]. XPS is often applied to determine
molecular orientation of the relatively large molecules associated
with adhesion [41].
2.1.3. Coatings on particles
In nanotechnology and many related areas, it is useful to under-
stand the nature of coatings on particles, and there are increasing
numbers of applications of what are often called core-shell par-
ticles. Although there are some added complexities, many of the
approaches to determining layer thickness for thin films can be
applied to particles of different shapes [42], and over the years a
number of people have considered quantitative analysis of contam-
inants on particles [43]. A schematic drawing [44] (Fig. 5) shows the
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 5. Schematic drawing showing a coating on a thin film and on a nanoparticle.
Note the different distances that electrons from the substrate need to travel to be
detected by the analyzer (effective coating thickness). For the films, the distance is
defined by the emission angle. For an isolated particle, the distance varies depending
on the location on the particle (but is independent from the emission angle). Because
of the effects of the direction of electron emission, the ratio of signals from the
coating and the thin film or nanoparticle will generally differ. However, it is possible
to model these effects. The results of one model calculation are shown in Figs. 6
and 7.
differences in effective film thicknesses measured by XPS for a coat-
ing on a flat film and on a cylinder or sphere. The differences in the
ratio of intensities from coating to substrate at normal emission
( = 0) for coatings of the same thickness on a flat film, on a cylin-
der, and on spheres are shown in Fig. 6. In these cases, the radius of
the cylinders or spheres is assumed to be significantly larger than
the electron attenuation length. As the radius of a sphere (or cylin-
der) approaches the size of the electron path length, XPS begins to
sense the whole particle and the influence of the coating is further
enhanced (Fig. 7). Although the shape of curves for different ele-
ments and film thickness may be similar to Fig. 7, the actual values
will change as a function of the materials involved and the energies
of the photoelectron peaks detected [45].
As shown by the significant changes in the signal ratio shown
in Fig. 7, as particle size approaches the size of the IMFP (d ∼ ) dif-
ferent analysis approaches are required. Although coatings on both
larger and smaller nanoparticles was of interest and importance,
the approach for determining coating thickness for smaller parti-
cles with d ∼  will be more complex than for larger particles where
d ≫  [46]. The condition when d ∼  has been widely considered
and applied to supported metal catalysts and is described later in
this section. For the condition d ≫ , the determination of coating
thickness might be considered that of either a specific shape (as
Fig. 6. Diagram showing the relative intensities of surface and substrate signals
for a coating on a thin film (at normal emission,  = 0), a cylindrical particle, and a
spherical particle. The nominal coating thickness is 0.5 nm and the calculations were
performed using an IMFP of ≈1.65 nm.
419
Fig. 7. Normalized signal from the surface layer to the substrate for a film (lower line
and  = 0) and nanoparticle (darker line with data points). For larger sized particles
the shape effects are relatively insensitive to curvature. As particles get smaller
and approach the electron escape length, the amount of signal from surface layer
increases. (After [44]).
described below) or possibly that from a rough surface that has
also been considered in some detail.
Shard et al. [45] have systematically examined some of the
effects of geometry on coating thickness measurements and have
derived a correction factor (topofactor) for the thickogram [27] that
adjusts for known particle shapes. Using values of particle (sphere
or cylinder) radius and electron attenuation lengths, it is possible to
calculate the overlayer thickness. Although these topofactors can
vary with layer thickness and particle radius, for many conditions
(when particles are smaller than the X-ray penetration distances
[usually microns] but larger than electron escape depths) the topo-
factors are relatively constant with values of 0.67 for spheres and
0.79 for cylinders. The topofactors confirm the understanding con-
veyed in Fig. 5. If a measurement is made at normal emission angles
( = 0) for the general sample surface, but the surface is actually
made up of spheres, a simple flat layer calculation would over-
estimate the layer thickness. In particular, the calculation made
assuming the flat surface needs to be reduced by about one-third
(multiplied by 0.67). The amount of correction needed increases
when the particles become smaller than the distances of electron
escape. Shard et al. also have considered the analysis of shadowed
spheres (a pile of spheres), which may be a relatively common con-
dition for analysis of a collection of larger nanoparticles, as opposed
to a distribution of smaller supported nanoparticles, which occur
in catalysis applications.
It is relevant to mention the concept of a “magic angle” for XPS
data collection. A magic angle is an angle of XPS data collection
for which surface roughness effects are averaged or minimized
allowing approximately “correct” values of coating thickness to be
determined [47,48]. A limited understanding of this may be pro-
vided by considering a surface made up of spheres. The collection
angle for electrons emitted from a sphere (without any support-
ing substrate effects) would be independent of the collection angle.
However, if the calculated coverage were made assuming a flat sur-
face with  = 0◦ the calculated thickness of the coverage would be
larger than the true value. However, if this “flat surface” calcula-
tion for the spheres were made assuming  = 45◦ rather than the
experimental situation of  = 0◦ , the cos () impact on the cos()
term in Eq. (1) would be to go from 1 to 0.71. In effect we are using
an “effective” tilt angle for this spherical surface. Chatelier et al.
[49] developed a method to determine the effective or averaged
tilt angle for arbitrary rough surfaces using atomic force microscopy
(AFM) data. In the spherical case, the  = 45◦ correction to the escape
depth produced a correction value that happened to be between
the corrections for spheres (0.67) and cylinders (0.79) calculated
by Shard et al.
The proposed application of magic angle data collection is to
actually collect the data at the magic angle and to analyze the data
using magic angle in a version of Eq. (1). Although circumstances
exist where this method is useful, two limitations need to be con-
420 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
sidered. First, there is no true magic angle; detailed calculations
of the magic angle for different rough surfaces suggest that the
magic angle can vary from 30◦ to 55◦ [45]. Second, analyzing a
rough surface (depending on the scale of roughness) may introduce
shadowing of some photoelectrons and cause an unknown selec-
tive collection of the photoelectrons. These issues can be avoided
if a sample with known surface roughness (or a collection of par-
ticles with well-defined geometry) is present and the geometry is
ordered enough to use a Shard et al. [45] correction. Note that even
in the most ideal circumstance a magic angle approach would not
include impacts of small particles with d ∼ .
2.1.4. Particle size
Research teams have developed different methods for extract-
ing particle size information from XPS spectra. This has been
particularly important for catalysis research when small metal par-
ticles are present on various types of support material. Often the
nature of the support and the size of the particles make direct
observation of particles by microscopy (such as transmission elec-
tron microscopy (TEM)) on actual catalysis difficult, particularly
for particles less than ∼1–2 nm in diameter. Obtaining particle size
information from XPS requires modeling of the signals. One of the
early approaches looked at ratios of signals from particles to that
of the support with a model structure [50] and appeared to be very
successful for many applications [3]. A second approach uses the
signal intensity ratio of photoelectron or Auger-electron peaks of
different kinetic energies arising from the particles [51]. Yang and
Sacher [52] have used this type of method to examine Cu clusters
deposited on Dow Cytlotene 3022. They have shown that there is
excellent agreement among TEM measurements of many clusters,
XPS determination of the average cluster size, and AFM measure-
ments of cluster size (after a tip shape correction). The equation
used by Yang and Sacher involves measuring a peak intensity ratio
and applying the following equation:
I 0 [1 − exp(−d/1 )]
R = 10
I [1 − exp(−d/2 )]
2
where I10 and I20 are the intensities of the two peaks that would be
obtained from very thick layers (d ≫ ). This ratio would be equal
to the ratio of appropriately determined sensitivity factors; d is the
average cluster diameter and the two s are the appropriate IMFPs
for the kinetic energies of the two measured transitions.
In both methods of determining particle size, the calculation
relates to supported clusters or nanoparticles for which the par-
ticles are at least somewhat separated from each other. These
approaches apply only to particle sizes for which signals are within
the information depth of XPS. If d is significantly greater than  for
both s, R = 1 and no information can be extracted [3]. The methods
are particularly useful for relatively low density of substrate sup-
ported particles and would apply to aggregates for which electrons
generated in adjacent particles might travel through a particle and
reach the detector.
Venezia [3] notes that contamination, which alters peak ratios as
described above, limits the accuracy of the above methods of par-
ticle size estimation. To the extent possible care should be taken
to minimize contamination. It may be possible to use a carbon
overlayer correction with the assumption that coatings are uniform
[53].
2.2. Nanostructures and peak energies
For the past 30 years, it has been established that metal clus-
ters and nanoparticles, particularly when the clusters are supported
on nonmetal supports, have XPS binding energies that differ from
those of bulk materials of between 0.05 eV and 0.6 eV [54]. Tao et
al. [55] note that because of a high catalytic activity, metal clus-
ters grown on oxide substrates have been the subject of increasing
research interest and understanding the origin of these shifts is of
increased importance. In many cases, the binding energy (BE) shifts
vary with sufficient regularity such that Gonzalez-Elipe et al. [56]
proposed that BE peak position could be a useful way to determine
particle size, possibly better than some approaches involving peak
intensity described above. One important process of changing BE
for isolated particles (including those supported on insulating sub-
strates) is a Coulomb attraction between ejected electrons and the
remaining charged particle [57]. A simplified analytical expression
of the Coulomb effect would suggest that the BE of a nanoparti-
cle would increase as the inverse of the particle diameter, which is
observed in many cases [52]. Several other sources of the BE shifts
have been identified and likely apply to varying degrees in different
circumstances. They include changes in the particle energy levels
due to size, lattice strain, charge shifting to a substrate interaction,
and final state relaxation effects. The detailed understanding of the
mechanisms causing the shift is subject to ongoing research.
These BE shifts have been of fundamental interest and when
the photoelectron peak shifts are combined with Auger line shifts
to determine an Auger parameter there can be a strong correlation
among the Auger parameter variation and BE shifts with particle
size and catalysis turnover frequency (TOF). In other words, these
shifts in the electronic behavior of nanoparticles correlate with cat-
alytic activity and can be used to relate catalytic activity to the
electronic charge on the particles [3,58]. These BE shifts are also
of interest to those designing sensors [59]. Differences between
Auger parameter shifts and BE shifts can be used to determine dif-
ferences between initial state (energy levels including substrate
interactions) and final state (relaxation) effects [55,60].
An example of the BE shifts for Au is provided below within the
context of developing materials for chemical sensing and catalysis.
2.3. Nanostructure from background signals
(2)
In addition to altering the relative intensity of peaks, layer-
ing and atomic distribution alters the presence of electrons not
readily identifiable as part of photoelectron peaks because they
have lost energy due to inelastic scattering and no longer have
the energy characteristic of the photoelectron peak. These energy-
loss electrons have been considered by many researchers, but
Tougaard [20,61] has developed a systematic approach to using
this background signal to obtain information about the elemen-
tal distribution in the outer 20 nm of a sample. He correctly calls
this “a tool for the analysis of surface nanostructures by electron
spectroscopy.”
Some relationships between nanostructure and background sig-
nal are schematically shown in Fig. 8. Four different elemental
distributions of Cu are shown, all of which produce the same
intensity for the Cu 2p photoelectron peaks. However, significant
alterations exist in the distribution of electrons at lower kinetic
energy (higher binding energy). This background signal from Cu
photoelectrons that have lost energy before they escaped the sam-
ple actually contains information about the depth distribution of
Cu in the volume of material analyzed by XPS. When combined
with high-lateral resolution methods, the Tougaard background-
analysis approach can be used to obtain a three-dimensional image
of the composition of the near-surface region of a complex film
or material [20,61]. Tougaard has developed a computer model-
ing program, QUASES [62], that can be used to create a model of
the elemental distribution near the surface of a material and to
calculate the spectrum background that would be caused by that
distribution. By iterating between the model and experimental data
it is possible to establish with reasonable confidence the likely
elemental distribution in the sample. QUASES is used to fit the
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 8. Diagrams and spectra showing the relationships between elemental distri-
bution and background signal for different distributions of Cu in the near-surface of
a sample. The four different elemental distributions of Cu produce the same inten-
sity for the Cu 2p photoelectron peaks. However, there are significant alterations in
the distribution of electrons at lower kinetic energy (higher binding energy). (After
[20,62]).
background for individual peaks. Several developments and adap-
tations of QUASES have been and are being made. Hajati et al. [63]
have combined QUASES-generated models to determine the size
and diffusion of Au clusters formed on a polystyrene surface, and
QUASES has been used as part of the development of a software tool
for the generation of survey spectra in XPS to simulate wide spectra
with a range of 200–1500 eV for nanostructured surfaces [64].
A new National Institute for Standards and Technology (NIST)
database called Simulation of Electron Spectra for Surface Analysis
(SESSA) has been developed for quantitative Auger-electron spec-
troscopy (AES) and XPS [19]. The database contains extensive sets
of physical data important for AES and XPS. SESSA can simulate AES
and XPS spectra for a multi-layered thin-film sample designed by a
user for measurement conditions relevant to the user. This database
and simulation program combines the current understanding of the
physical processes of electron spectroscopy and a large amount of
data to simulate the full spectra that would be expected for the sam-
ple designed by the user. Comparison between experimental data
and the SESSA calculation enable information about the elemen-
tal distribution to be extracted. SESSA does not include chemically
induced alterations in peak shape but calculates the full spectra
including the background signals. Although there are not yet as
many applications of SESSA as QUASES, it has potential for great
use and value.
QUASES, SESSA, and related modeling programs make use of the
most up-to-date understanding of the processes associated with
electron spectroscopy and can be used to extract much more infor-
mation about the nanoscale distribution than processes that simply
use peak amplitudes.
3. Barriers and limitations to obtaining information about
nano- and bio-structures
Several challenges may need to be overcome to obtain the infor-
mation desired from a nanostructured material [5,7]. Among these
challenges are the impact of surface contamination on data col-
421
lection and analysis, the possibility of environmentally induced
changes in samples, specimen alterations and contamination
derived from mounting methods, susceptibility of nanoparticles
to damage during analysis, and limitations about what is initially
known about the about the system being analyzed.
3.1. Contamination
Because nanostructured materials inherently involve many
atoms associated with surfaces or interfaces, the presence of unex-
pected surface species is common and can sometimes significantly
impact the analysis. As noted above, the very common layers of
adventitious carbon can alter peak ratios and even mask impor-
tant signals. Sometimes impurities have been introduced to sample
surfaces during “cleaning” processes. The minimization of contam-
ination is an important issue for specimen preparation, handling,
and mounting. In addition to carbon being introduced during
sample handling, chemical impurities can be introduced during
synthesis or processing. Both extreme care and consistency checks
are needed to assure that what is measured is characteristic of the
sample and not contamination or some other artifact.
3.2. Environmentally induced changes
XPS is inherently a vacuum-based method (although differen-
tially pumped synchrotron based systems allowing samples to be
maintained at higher pressures have been developed [21]). Some
samples are altered by placing them in a vacuum and the possible
impact of the vacuum should be considered. In many circumstances
these effects are less than expected, but a variety of approaches can
be used to minimize such effects as needed. Approaches include
cooling samples and collecting data as a function of time to deter-
mine if there are vacuum-induced changes. Equally important,
exposure of some samples to air before analysis can alter them. In
some of our research, we need to examine iron metal-core oxide-
shell nanoparticles. We have found, as shown in Fig. 9, that we can
remove a specimen from solution in a N2 environment and see both
the metal-core and the oxide-shell. However, exposure of the same
particles to air induced additional oxidation and the signal from
the core was significantly diminished. Therefore, in our research
with reactive metal nanoparticles, we usually handle, mount, and
analyze particles without exposing them to air [65].
Fig. 9. Fe 2p photoelectron spectra from iron metal-core oxide-shell nanoparticles
showing the effect of different handling methods. The first spectrum was measured
after removal from storage in a glovebox and transferred to an XPS system without
exposure to air. The second blue spectrum shows the reduction of metallic iron
(∼707 eV) after a few minutes of exposure to air [11]. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of
the article.).
422 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 10. Schematic drawing of different collections of nanoparticles and how they
may be grouped for analysis. In some circumstances the collections of nanoparticles
will have properties that differ from individual particles. Particle–particle separation
distances and substrate interaction can alter particle binding energies in XPS and the
proximity of neighboring particles can alter the electronic, magnetic, and chemical
properties of the particles.
It seems useful to note that because of the high surface areas,
environmental effects [66] can have a larger than expected influ-
ence on a variety of properties of nanosized objects, including
surface structure, phase transformations, chemical stability, poly-
mer structure, and chemical state. One aspect of environmental
effects is that some properties can vary as a function of time [67].
Thus, from the view of analysis, storage, and functional properties, it
can be important to recognize that the properties of nanostructured
materials are NOT usually constant in time. Environmental and time
stability are important properties that may impact technological
uses of nanosized objects.
3.3. Sample preparation and mounting
The method by which nanosized objects are mounted can sig-
nificantly impact some types of particle properties (Fig. 10). In
Fig. 11. Schematic drawing of steps associated with preparation of microorganisms for XPS analysis using the freeze drying procedure (After [68]).
addition to the possible introduction of contamination during
mounting or methods of attaching specimens to a sample holder,
some properties of nano-objects can be influenced by the proxim-
ity of other particles or by interactions with the substrate. Although
many additional effects are likely, those reported include the fol-
lowing [5]:
• the buildup of charge during XPS measurements of metal clusters
supported on insulating substrates
• coupling of plasmon modes in metal nanoparticles depending on
particle separation
• coupling of quantum states
• alterations of magnetic and electronic properties
• substrate-induced charge transfer.
Shard et al. have noted that when  ∼ d, the use of XPS to deter-
mine the thickness of a layer on a specimen will be significantly
impacted if the objects are not distributed in a single layer [45].
The importance of different types of mounting will depend on the
nature of the analysis questions. If the presence or absence of a
functional group, the cleanliness of a sample or the simple pres-
ence of a coating is the analysis objective, single-layer mounting
may not be important. However, if the thickness of a coating on
smaller nanoparticles (d < 6 nm) is desired, single-layer mounting
will likely be important.
Sample preparation is one of the major issues or challenges for
analysis of microbe and other biological surfaces using XPS [22,68].
Issues associated with analyzing microbes and other biological
materials with vacuum-based techniques have received a good deal
of discussion and are one reason that XPS data are often correlated
with other types of data and checked for self-consistency. A review
paper by van der Mei et al. [68] discusses at some length sam-
ple preparation methods. Most research has been conducted on
freeze-dried microbes as outlined in Fig. 11. The process involves
culturing the microbes, washing them, freeze drying and mounting
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432 423

for inserting into the spectrometer. Duplicate and reference sam-

ples are generally required to assure that consistent, meaningful
and reproducible results are obtained.
Although much successful work has been completed using the
freeze drying process, researchers continue to search for methods
to allow biological specimens to remain and relevant physiological
environments (e.g. the presence of water). This search has included
application of differential pumped high pressure XPS systems at
synchrotrons [22]. In a different approach, Leone et al. [69] have
successfully used a fast-freezing procedure to prepare samples to
study deprotonation reactions on Bacullus subtilis as a function of
pH. The ratio of protonated-to-deprotonated N 1s photoelectron
Fig. 13. Schematic drawing of electron pathways toward an electron detector with
peak intensity as a function of pH is shown in Fig. 12. (a) no scattering, (b) inelastic scattering (for which the electron loses energy and
changes direction), and (c) elastic scattering (for which the electron changes direc-
3.4. Damage tion, but does not lose energy).

Some properties of nanoparticles, such as melting temperature,

are dependent on particle size [5]. Therefore, the susceptibility of to determine the particle size. When particles are being analyzed,
particles to X-ray and electron damage may be greater than for knowledge of the particle size can be used to assist determining the
larger-scale versions of the same materials. We have found that thickness of coating layers. Third, it is often highly informative to
for ceria nanoparticles the nature of X-ray-induced changes of the correlate information from a variety of methods that provide sim-
observed cerium chemistry depends on the processing history of ilar information. When a self-consistent understanding involving
the sample [5] and the presence of water or organic layers on the several types of data can be established, confidence in the resulting
surface. Polymers and many organic layers are easily damaged by understanding of the material is significantly increased.
X-rays.
3.5.2. Things we know we do not know
3.5. Pre-knowledge
Much of the discussion regarding peak ratio and film thickness
above was based on IMFPs and the validity of Eq. (1) or similar
3.5.1. Using what can be known
equations. However, it is now well established that Eq. (1) is an
The more that is known about a system that is being analyzed,
approximation that is not valid in all circumstances [70]. One of
the more precise and detailed the information that can be collected.
the challenges is that Eq. (1) assumes that electrons are either not
There are three useful aspects of this. First, if nothing is known (or
scattered (Fig. 13a) or are inelastically scattered (Fig. 13b) (they lose
acknowledged) about the structure of a sample, it can be very chal-
energy, change direction, and are not detected as part of the inten-
lenging to obtain all of the information that might be possible or
sity of a photoelectron peak). However, a variety of experimental
needed. For example, if the sample is known to be layered, any
and theoretical studies show that elastic scattering of electrons can
known or expected information about the layered structure can
be significant, particularly for higher angles of emission (Fig. 13c).
be tested using XPS data and calculating realistic models of the
For example, consider the experimental data from Seah and White
structures. Without the initial knowledge, learning the same infor-
[71] for a thin silicon dioxide layer on a silicon wafer shown in
mation may be possible, but it may take considerably longer to get
Fig. 14. The ratio of the Si 2p photoelectron intensities for Si in the
the information, including a need to collect additional data. Second,
film and the substrate for different angles are plotted based upon a
information provided by other methods can assist in understand-
ing XPS data and might influence the types of analysis done. If, for
example, TEM or XRD data indicate the presence of small nanoparti-
cles (in contrast to a uniform film) it may be possible to use XPS data

Fig. 12. Ratio of protonated-to-deprotonated N 1s photoelectron peak intensity for
Bacullus subtilis as a function of pH. (From [69]).
Fig. 14. Summary plot showing the effects of elastic scattering as a function of angle.
The plot of the ln (1 + Rexp ()/R0 ) vs 1/cos  for XPS measurement using Al K␣ X-rays
is for a film of SiO2 on Si. The solid circles are experimental data of Seah and White
[71]. The solid curve is a SESSA calculation allowing elastic scattering and the dashed
line has elastic scattering turned off. (After [73]).
424 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
common equation for film thickness [72]:
 
Rexp () d • Functional group termination and the coverage of self-assembled
ln 1+ = (3)
R0 L cos 
where L is the electron attenuation length, d is the film thickness,
Rexp is the experimental ratio of the Si 2p photoelectron peak inten-
sities for Si in the oxide layer and Si substrate (Iox /Im ), and R0 is the
ratio for these peaks for bulk materials. If this relationship were
accurate for all angles, a plot of ln (1 + Rexp ()/R0 ) vs 1/cos  would
produce a straight line. However, as shown by Powell et al. [73]
and in Fig. 14, the experimental data do not fit a straight line for
 > 65◦ . The SESSA modeling program described earlier can be setup
to include only inelastic scattering or to allow elastic scattering.
When only inelastic scattering is included in the model, a straight
line is predicted. However, when elastic scattering is included, devi-
ations from the linear behavior are predicted consistent with the
experimental data.
Note that in Eq. (1) the electron mean free path, , was used
while in Eq. (3) the electron attenuation length (EAL), L, was used.
The EALs differ from the corresponding inelastic mean free paths
because of the elastic scattering of the signal electrons. NIST has
databases for both of these parameters [34] and comparison of val-
ues for a few different circumstances are discussed by Powell et
al. [73]. Many of the commonly applied expressions using L or 
assume that elastic scattering can be neglected. However, modi-
fied expressions taking these into account have been developed
[74,75].
One impact of elastic scattering, which is demonstrated in
Fig. 14, is that elastic scattering is important for glancing angles of
electron emission. A corollary to this observation is that for flat sur-
faces the experimental geometry can be arranged such that elastic
scattering effects are not significant. For thin-film measurements,
the effect of elastic scattering has been included in modeling stud-
ies of ARXPS for thin films [76], the use of multiple spectral lines
to calculate film thickness [77], and, as already suggested, can be
modeled by SESSA [19]. However, as implied in Fig. 5, for nanoparti-
cles, electrons effectively leave the particles at a variety of emission
angles. To our knowledge, the role of elastic scattering on measure-
ments of particle size or coating thickness for nanoparticles has not
been examined in detail.
In addition to any complications to applying  or L due to issues
related to elastic scattering, it must be recognized that in some
cases nanostructured materials are polymorphs of larger sized
versions of these same materials [78]. Nanoparticles may have dif-
ferent structures and lattice parameters [79,80] than bulk materials
and the impact of these changes on electron path lengths has not
been explored.
Although these unknowns will impact the overall accuracy of
our ability to extract information about nanostructures from XPS
data, they do not alter the overall relationships, nor do they change
the nature of how nanostructure influences the XPS data.
4. Examples of application of XPS to nanostructured
materials and biological systems
Many different research teams have used XPS to characterize
a wide variety of nanostructured materials. Many of them have
focused on surface films or nanolayers, while others have focused
on nanoparticles of various types. Typical examples in each area are
listed below.
Surface film or nanolayer examples:
• Heating-induced segregation on metal alloys [19]
• Structure and thickness of Langmuir Blodget films on glass [29]
• Dispersion of components in a nanocomposite film for proton-
exchange membrane fuel cells [81]
monolayers on surfaces [82,83]
• Properties of thin corrosion films [26]
• Stability polymer light-emitting diodes [84]
• Thin polymer and block polymer films [85].
Nanoparticle examples:
• Presence or removal of contamination layers [86]
• Oxidation of nanoparticles [87]
• Nanoparticle size determination [63,88]
• Electrical character of core-shell nanoparticles [89]
• Confirmation of the functionalization or measurement of the
electronic structure of carbon nanotubes [90–92].
Although less familiar to some researchers, surface analysis
tools of various types are increasingly being applied to study the
surfaces of biologically related systems [14], including the surface
chemistry of microbes [68], the formation of biofilms [69,93], the
creation of biocompatible materials [94,95], drug elution on med-
ical devices [96,97], and pharmaceutical materials [7]. The surface
chemistry of microbes is important because they can attach to sur-
face and to form biofilms both on artificial surfaces (medical devices
such as stents) and on natural surfaces, such as arteries [98]. The
design of body-compatible biomaterials for medical application is
also a frequent area of study.
To a significant degree many surface tools are applied to biolog-
ically related surfaces to answer the same types of questions that
are asked for other nanostructured materials and in other areas.
These questions include what elements are on the surface, what
is their chemical state, what is their distribution and how do they
change as the environment or substrate changes? In other words,
XPS is applied to biologically relevant materials for the same rea-
sons it is applied to other materials. Because of the complexity
of biological surfaces and the roles of different analysis tools in
providing complementary information, XPS is commonly used in
combination with a wide variety of other methods [12]. As already
noted, issues associated with sample preparation, sample damage
and understanding the implications of the collected data are impor-
tant challenges and care must be taken. In comparison to general
application of XPS to materials, the application to many biologi-
cal organisms is relatively less developed and certainly much less
widely applied.
A few examples provide an initial perspective of the types of sys-
tems where XPS is being applied. In most cases, the integration of
XPS with other methods and sometimes tests of biological function
are essential components of the research.
Examples involving microbes or other natural biological mate-
rial:
• Oxidation state of chromium on Shewanella oneidensis in relations
to contaminate interaction [99]
• Relationship between surface functional groups and physico-
chemical properties of Esherichia coli [100]
• XPS analysis of chemical functions at the surface of Bacillus subtilis
[101]
• Surface properties of the human fungal pathogen Aspergillus fumi-
gatus [12]
• Characterization of the cell surface and cell wall chemistry of
drinking water bacteria [102]
• Review of XPS study of microbial cell surfaces, including a
database and discussion of sample preparation [68]
• Impact of herbal extract on the growth of urinary calculi [103]
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
• XPS characterization of flea digestion and iron chemsitry related
to Y. pestis transmission by fleas [104].
Examples involving biocompatibility, synthetic biomaterials or
functionalized surfaces:
• Attachment and delivery of bisphosphonate from metal stent sur-
faces [96,97]
• Surface functionalization of drug-eluting stent with diamond-like
carbon nanocoating [95]
• Protein attachment to polystyrene surfaces (relevant to biomed-
ical devices and sensors) [94]
• Immobilization of proteins on nitrilotriacetic acid-terminated
self-assembled monolayers [105]
• Analysis of DNA molecules on patterned surfaces (microarrays)
[13]
• Design of a surface for selective release of DNA [106]
• Study of competitive protein adsorption related to the develop-
ment of materials that have improved compatibility with blood
[107].
Several specific examples (4.7 and 4.8) highlight application of XPS
to measure the surface chemistry of microbes and creation of func-
tionalized surfaces for biological studies.
4.1. Verification of surface functionalization and product
formation
Perhaps the most common uses of XPS for characterization
of nanostructure materials involve confirmation of the reactions
expected to occur during synthesis or the presence of functional
groups on a surface. These types of experiments take advantage
of the surface sensitivity and chemical state information available
from XPS. The types of detailed analysis methods described ear-
lier are not needed to confirm the presence or absence of certain
elements or functional groups. These are sometimes highly impor-
tant experiments that involve relatively straightforward use of XPS
measurements.
As a first example, in a set of clever experiments by Lim et al.
[108], d and l cysteines were attached to the surfaces of Au nanopar-
ticles and used to regulate interparticle chiral recognition. For these
studies, XPS was used to confirm the presence of the cysteines
and to demonstrate the consistent nature of the surface coverage
and binding of the different types of cysteines to the nanoparti-
cle surfaces. An import role of XPS for these measurements was to
confirm that the surface coverage did not significantly change as
different cysteines were used and that they were actually attached
to the surfaces of the Au nanoparticles. As a second example, a
novel approach was used to create core-shell nanoparticles with
apoferritin shells and LuPO4 cores [109] as shown schematically in
Fig. 15a. In this study, Lu+3 is diffused into apoferritin nanoshells
and then PO4 3− is added. They combine to form an insoluble com-
pound in the core. TEM showed the presence of the core after the
synthesis process and XPS was used to confirm the presence of the
Lu and PO4 , as shown in Fig. 15b. An important function of XPS in
these experiments was to actually verify that the compounds antic-
ipated were actually formed and remained within the nanoparticle
shells.
4.2. Nanostructured carbon (carbon nanotubes (CNTs) and
graphene)
A wide range of tools are being applied to characterize and
understand various forms of carbon nanotubes (CNTs), including
single wall carbon nanotubes (SWCNTs or SWNTs) and multi-
walled CNTs (MWCNTs), and single-layer sheets of carbon atoms
425
(graphene) as they are synthesized, functionalized and applied.
XPS is frequently used to examine the functionalization, doping
and changes in electronic structure of these nano-forms of car-
bon. For many applications XPS is applied along with a combination
of complementary tools to characterize the range of properties of
interest.
Many research groups are working to take advantage of novel
electronic and structural properties of CNTs for a variety of appli-
cations and fundamental research. It is frequently useful to attach
molecules to the CNT surface or to actually enclose molecules
within CNTs. It is often important to understand the extent of sur-
face functionalizaton [110] as well as any changes that have taken
place in molecules sorbed to the CNT surface or the extent to which
the properties of the CNTs are altered. For example, the combina-
tion of XPS and GC-MS thermal analysis was used to examine the
CNTs functionalized by solvent-free and aqueous-based arenedi-
azonium. Both methods suggested that only the arcne group was
retained on the CNTs [90]. In another study XPS and TEM were
combined to provide information about the noncovalent bonding
and distribution of proteins (1-pyrenebutanoic acid, succinimidyl
ester) to SWNTs [111].
By using both binding energy data and overall composition data
XPS can provide several types of information about the CNTs being
examined. The combination of TEM and XPS was used to study
the growth of Au nanoclusters on CNTs functionalized by oxygen
plasma. Core-level and valence band measurements showed little
charge transfer between the Au clusters and MWCNTs, However,
the authors noted that the cleanliness of the surface, the presence of
amorphous phases and agglomeration of as grown CNTs appear to
be constraints to CNT applications [91]. As another example, Core-
level and valence band XPS in combination with near-edge-X-ray
adsorption fine structure spectroscopy have been used to study the
impact of TCNQ on the electronic structure and bonding of SWCNTs
[92].
In addition to functionalization, XPS is useful for observing the
thickness of graphene layers [112] and their purity [113].
4.3. Ultra thin SiO2 layers
The oxide layers on Si are of high importance to the electronic
industry and have been widely subject to detailed examination.
Seah and co-workers around the world have conducted an exten-
sive set of studies on how to precisely and accurately determine
the thickness of oxides within the thickness range of 0.3–8 nm
[71,114–120]. In a series of studies of at least seven papers Seah
and various co-workers have demonstrated several different points
that are worthy of being highlighted here.
Based on the development of a set of oxides of very well-defined
thicknesses and the use of different measurement angles, Seah and
others have identified critical values of R0 and L for use in Eq. (3)
[71], they have examined the various equations proposed to deter-
mine film thickness and have identified those that produce accurate
and reproducible values for SiO2 [117], and they have shown that
ARXPS can be used to map the variations in oxide thickness over a
wafer [71].
Two observations deserve particular attention because they
highlight some of the challenges in achieving accurate measure-
ments of properties at the nanometer size. A simplified drawing
of an oxide film on a Si substrate (Fig. 16a) shows that there are
four regions: a contamination coating, the main oxide, an interface
region with suboxides, and the substrate. Accurate determination
of the thickness for the series of standard films involved subtrac-
tion of satellite peaks, spin-orbit splitting removal, and inclusion
of the suboxide peaks that occur between the Si0 and SiO2 main
peaks (as shown in Fig. 16b). Using their best approach, including
the suboxide peaks with the optimum geometry, they could achieve
426 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432

Fig. 15. (a) Drawing of the approach used to create core-shell nanoparticles with apoferritin shells and LuPO4 . Lu+3 is diffused into apoferritin nanoshells and then PO4 3− is
added. They combine to form an insoluble compound in the core. TEM showed the presence of the core after the synthesis process and XPS confirmed the presence of the Lu
and PO4 as shown in (b) valence band region showing Lu 4f and Cl 3s and 3p peaks, and (c) P 2p region, respectively. (After [109]).

repeatability of 0.025 nm when using Mg X-rays. Thus, a first obser-
vation is that the oxygen at the interface (the suboxides) between
the oxide film and Si substrate contributes to the thickness and,
if included in the measurements, gives high reproducible results
that are linear with oxide thickness. Ignoring the suboxides at the
interface decreased accuracy and reproducibility.
The second observation of significance involves comparison of
a wide variety of measurements of oxide thickness using differ-
ent methods, including TEM and X-ray reflectivity [120]. When
examined with some care for the well-defined oxides of varying
thickness, it was observed that most of the methods were linear
with increases in the oxide thickness, but there was an offset at zero
(Fig. 17). Although each of the methods applied was highly precise,
the impact of effects such as undefined contamination layers or
water sorption, provided an offset to the measurements as a func-
tion of thickness that can produce an increasingly larger percent
error in measurements as thinner films are analyzed. Since these
offsets are often between 0.2 nm and 1 nm, they can contribute con-
siderable uncertainly to nanometer film thickness determination.
When done with care, the elemental specificity of XPS allows this
offset to be avoided or minimized.
The measurements of the silicon oxide layers for thin films
on wafers have become quite sophisticated and accurate. Because
nanoparticles may have different oxidation behaviors, it is of inter-
est to compare the oxidation rates for planar and nanoparticle Si.
Using the types of analysis discussed above for core-shell particles,
Yang et al. [87] have used XPS to examine the oxidation rates for
both flat Si and Si nanoparticles as shown in Fig. 18. Both the oxi-
dation rate and the activation energies appear to be significantly
different. These measurements would be subject to the electron
path length uncertainties noted earlier, but appear to be quite sig-
nificant regardless.

Fig. 16. (a) Simplified model of an oxide film on a Si substrate showing four regions: contamination coating, main oxide, interface region with suboxides, and substrate. (b)
Si 2p photopeaks from a SiO2 layer on a Si wafer after subtraction of satellite peaks and spin-orbit splitting removal. The inclusion of the suboxide peaks that occur between
the Si0 and SiO2 main peaks are needed to accurately determine thickness. (After [116]).
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 17. Offset values (extrapolation to zero thickness) for several measurement
methods used to determine the thickness of a series of well-defined oxides. Each
method showed linear variation in measured thickness for the range of oxides, but
there were varying values of offset. Although each of the methods applied was highly
precise, measurement uncertainties due the impact of undefined contamination
layers, water sorption, or other minor measurements perturbations provide an offset
to the measurements leading to measurement uncertainties that can be a significant
fraction of a nanometer. (After [120]).
4.4. Surface segregation on bimetallic catalyst particles
Because bimetallic catalyst particles sometimes have improved
catalyst performance in terms of activity, selectivity, and lifetime,
it is of interest and possible importance to understand the nature
of the active catalyst particles. Although X-ray diffraction (XRD)
might be able to provide information about particle size, it cannot
provide information about composition gradients in these metal
particles. The different escape depth information used above to help
determine particle size can also be used to examine elemental seg-
regation within particles of known sizes. This has been applied by
Venezia et al. to examine segregation in Pt/Pd catalysts [121]. In this
case the measured peak ratio for one element in a particle of known
size is normalized by Eq. (2). It was found that for this application
that Pd was depleted in the surface.
A detailed examination of the structures and phase thicknesses
for a Co-Rh/Nb2 O5 catalysis system was examined carefully by
Frydman et al. [122]. XPS, BET surface area measurements, and tem-
perature programmed desorption were combined with detailed
modeling of XPS signal strengths to determine the nature of this
bimetallic catalyst for which about 3.6% of the 60-nm-diameter
Fig. 18. Measurements of oxide thickness as a function of time for Si nanoparticles and two different flat surfaces. The apparent rates of oxidation are significantly different
for the nanoparticles in comparison to the wafers. (From [87]).
427
Nb2 O5 support particles (d ≫ ) were covered by Co3 O4 islands
with thickness >2.5 nm, which were covered by a Rh2 O3 layer that
was a couple of nanometers thick. The remaining 96.4% of the sup-
port surface was covered by a Co+2 surface phase. Although this
model involves a fair amount of additional complexity [46] in com-
parison to that applied for the Pt/Pd catalysts above, it is included
to suggest the types of detailed information that can be extracted
with careful data collection and detailed analysis.
4.5. Thickness of oxide layers on iron metal-core oxide-shell
particles
The Fe 2p spectra shown in Fig. 9 are from iron metal-core
oxide-shell nanoparticles for which we are studying their reactiv-
ity with environmental contaminants such as carbon tetrachloride
[11]. We have examined particles from a variety of sources and after
different processing and aging conditions by a variety of analysis
methods that include TEM, XPS, BET and XRD. A major focus of the
XPS measurements in these studies is to determine the presence
of surface contamination [11] and to examine differences in the
oxidation state of surface iron (which can change as a function of
time and depends on the environmental conditions [67]). TEM mea-
surements have shown that in many different circumstances the
oxide-shell is between 2 nm and about 3 nm thick. Because of dif-
ferences in particle history, we do not often see metal peaks as large
as those shown for the sample not exposed to air in Fig. 9. Because
these particular particles have particle diameters of approximately
50 nm, we have used TEM to gauge shell thickness and have found
that XRD measurements indicate an iron metal to iron oxide com-
position ratio quite consistent with 2–3 nm shell thickness. Because
XRD is an indirect measurement based on assuming that most of
the oxide is included as oxide-shell and we have observed oxide-
shell growth in the TEM [123], it can be informative to also analyze
film thickness using XPS.
Here we use Eq. (3) to obtain another measure of oxide-shell
thickness. The parameters needed to determine the thickness
include Rexp (the ratio of the experimental signal intensities for
Fe in the oxide-shell divided by the signal form the Fe0 in the par-
ticle core), R0 (the Fe signal ratios from bulk forms of the oxide
and metal), the electron attenuation length (L), and the angle ()
effective angle of emission. Because of a variety of uncertainties
the overall accuracy of the result is limited. Nonetheless, the values
of particle thickness obtained are generally consistent with other
measurements.
428 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 19. Fe 2p photoelectron peak for an Fe nanoparticle shown in Fig. 9. separated
into Fe metal and Fe oxide peaks as described in the text.
Because of the complexity of the Fe 2p photoelectron peaks,
determining the peak ratio from iron in metallic and oxide forms
is more complex than for Si and SiO2 [71] or Al and Al2 O3 [124].
The ratio of the experimental signal for iron in the oxide and metal
forms was determined by use of a reference spectrum for metallic
iron. After a Shirley background subtraction a reference spectrum
for metallic iron collected for the same conditions as the nanopar-
ticles was scaled to fit the largest metallic peak in nanoparticle
spectrum as shown in Fig. 19. The peak remaining after subtraction
of the scaled metal peak is similar to that for several iron oxides
and is identified as the oxide peak from the nanoparticle. The areas
of the scaled metal peak and the difference oxide peak are used
to obtain an oxide and metal peak ratio. For the particle before air
exposure Rexp is approximately 1.5.
The bulk signal ratios (R0 ) can be determined either theoretically
or experimentally. Seah and Spencer discuss both the methods and
results from different approaches [116] for SiO2 on Si. Because some
elastic scattering parameters (Q) do not appear to have a significant
effect for the current iron particles, we can use a simplified version
of Eq. (4) in ref [116] which reduces to the equation used by Markus
et al. [72] where R0 = Dox ox /Dm m . Dox is the density of Fe in the
oxide and Dm is the density of Fe in the metal and m and ox are the
IMFP for Fe photoelectrons the oxide and metal respectively. Val-
ues we determined were Dm = 0.14 mole/cc and Dox = 0.066 mole
(Fe)/cc. The IMFP values were determined using TPP-2 M as imple-
mented in QUASES [33] as m = 1.36 nm and ox 1.65 nm. For the
electron attenuation length we assume that L/ox = 0.85 based on
equations in [75]. Therefore we use L = 1.4 nm. The only remaining
term in Eq. (3) to apply is cos . Although the nanoparticles in ques-
tion are only nominally spherical, we note that for data collected at
normal emission the Shard et al. correction is 0.67 (applicable for
 = 0◦ ) and the cos  value for  = 45◦ is 0.71. As our data was col-
lected at 45◦ we use the 0.71 factor and the thickness of the oxide
coating is calculated to be ≈1.3 nm.
For the sample in Fig. 9 not exposed to air we expect a thick-
ness a little less than 2 nm. Thus the 1.3 nm calculated thickness is
a little smaller that the thickness expected but not far off. Among
other complications, it must be noted that we considered the oxide
to be fully dense and in recent work we have shown that the
oxides on these nanoparticles are highly defected. A high density
of defects would likely impact the attenuation length and indicate
that the actual physical thickness film may be greater than 1.3 nm.
Fig. 20. The ratio of the photoelectron peak intensities for iron in oxide and metal
forms (Rexp = Iox /Im ) and the thickness of the oxide coating on the iron metal-core
oxide-shell nanoparticle.
As already noted, there are several possible areas of uncertainty
in the calculation the method can be made more accurate (as the
case for SiO2 ) with appropriate standards and determination of the
critical parameters.
This calculation shows both the reasonableness of the calcu-
lated results and some of the areas of uncertainty. To show the
sensitivity of the coating thickness determination based on the iron
oxide to iron metal ratio, the parameters provided above have been
used to calculate a plot of oxide thickness (d) as a function of Rexp
(Fig. 20). This graph highlights the nonlinear relationship between
the experimentally observed peak ratios and the coating thickness.
For the iron particle, if a metallic peak can be identified the overall
oxide layer thickness is likely to be ∼4 nm or less.
4.6. Au nanoparticle-polyaniline composites
Au nanoparticles of certain sizes have been shown to have chem-
ical behaviors that make them of potential interest for chemical
sensing and catalytic applications. Among the issues for application
of Au nanoparticles is the need to prevent nanoparticle aggregation.
Smith et al. [57] have applied electrochemical synthetic methods to
create composites where the electronically conducting polyaniline
(PANI) polymer serves as a framework to suspend Au nanopar-
ticles. The intimate contact of the Au particles with the polymer
both stabilizes the particles and provides an electrical contact that
is potentially useful for sensing applications.
One of the questions investigated in their research was the
charge transfer between the Au and PANI. Because of the high
atomic number of the Au it was possible to use TEM to examine the
size of the gold particles contained within the lighter PANI matrix
to determine particles size (which worked for particles larger than
1 nm). XPS was used to measure the BEs of the Au particles. Unlike
the studies of metal particles on insulating substrates, these tests
involved the suspension of the particles in the conducting polymer
matrix.
The measured Au 4f photoelectron BEs for several size particles
are plotted as a function of particle size in Fig. 21. The solid line
is Coulomb interaction energy. Although there is a shift from the
Coulomb interaction line, the measured BEs generally follow the
shape of the Coulomb interaction curve. Although these changes
in BE are relatively small, they are reproducible and are consistent
with changes in BE for particles as a function of size for a variety
of different materials. The shift in Au nanoparticle BE is attributed
to the electronic contact potential formed at the PANI/Au interface.
Because the contact potential can influence properties of the matrix
the ability to control the particle size becomes a method to engineer
properties of the composite material.
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 21. Plot of the Au 4f binding energies for Au nanoparticles of different sizes
grown in a PANI film. The solid line is the Coulomb interaction energy that is used
to indicate the expected BE variation of free Au nanoparticles as a function of size.
The insert shows the 4f spectra for the various particles. (After [57]).
4.7. Surface chemistry of microbes
One of the most common uses of XPS for the study of microbes
is in the determination of the relative amounts of different surface
functional groups for differing microbes or as the environment is
altered. As discussed by van der Mei et al. [68], a basis for much of
the work is a correlation between biological (or other properties) of
the microbes and the changes in relative peak intensities observed
by XPS analysis of the microbe surface.
As one example, in a paper using XPS to analyze the functional
groups on nine strains of B. subtilis, Ahimou et al. [101] examined
the different components of C 1s, N 1s, and O 1s photoelectron peaks
Fig. 22. Representative O 1s, N 1s, and C 1s XPS photoelectron peaks from three strains for Bacillus subtilis. The data analysis involves finding the areas of the peaks associated
with different functional groups as indicated in the figure. (After [101]).
429
as shown in Fig. 22. The different peaks are typically analyzed by
fitting for the components (or grouped components) shown in the
figure and the data are analyzed by looking at total peak ratios (e.g.
O/C, N/C, P/C, etc.) and identifying the relative intensity of different
functionalities as a ratio to total carbon (C & (C, H) [284.8 eV], C O
and O–C–O [287.9 eV], protonated N [401.3 eV], etc.). In the work by
Ahimou et al., each set of measurements for one strain of microbe
was reproduced on a totally independent culture.
This type of information is analyzed in different ways depend-
ing on the questions being asked and also to verify self-consistency.
In work by Dague et al. [12], AFM, XPS, and secondary ion mass
spectroscopy (SIMS) measurements showed that the surface pro-
teins, polysaccharide, and amino acid composition of three mutant
strains of A. fumigatus were markedly different from a wild version
of the microbe. The combined information from the three meth-
ods can provide a good deal of information about the nature of cell
surface.
4.8. Creating functionalized substrates for biological studies
Designing material substrates to minimize interaction with bio-
logical molecules, control the release of molecules (often drugs),
or enhance specific types of binding (for sensors and other appli-
cations) are common objectives of biomaterials design. In these
studies, surface analysis methods are widely used to characterize
the substrates as synthesized or modified and to then characterize
the nature of their interactions with the biological environment.
XPS is used, along with a number of surface-sensitive methods, to
assess the uniformity and extent of surface coverage and to help
identify the functional groups present and the chemical state of
the surface.
The objective of research by Robinson et al. [125] was to
create a surface gradient (variation in concentration over some
distance) of functional heparin to enable the study of biological
processes related to blood clotting, tissue structuring and organi-
zation, immunology, reproductive biology, or disease progression.
The intention was to create a substrate that allowed the fundamen-
tals of the processes involved to be examined in vitro. Although
430 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
Fig. 23. (a) Plot of the N/C ratio of N 1s and C 1s photoelectron peaks () showing a gradient (change in amount as a function of position along the surface) in a plasma-
polymerized allyl amine that had been deposited on a glass substrate. (b) Comparison of the amount of heparin bound to the substrate as a function of position (represented
by the % S in determined by XPS 䊉) and the extent of biological function (♦) as measured by a Link TSG6 binding assay. (From [125]).
there are other methods of creating such a gradient, the specific
object of this work was to develop a simple process of creating a
chemical gradient to which heparin would bind and which would
allow the heparin to retain biological function.
A chemical (concentration) gradient of plasma-polymerized
allyl amine was deposited on a glass cover slip. The gradient in poly-
merized allyl amine on the cover slip was verified by using XPS to
measure the N/C ratio across the sample as shown in Fig. 23a. Hav-
ing established the existence of the gradient, the next experiments
explored heparin binding to the surface and the biological func-
tion of the heparin (Fig. 23b). The presence and amount of heparin
were determined by XPS using the S 2p signal (from sulfates in the
heparin) and measuring the change in relative intensity across the
sample. The biological functionality of the surface-bound heparin
was examined by specific binding of biotinylated Link TSG6 using
a colorimetric assay [125].
As suggested from the list of examples above, there are many
different variations of the need to prepare materials with desired
functionality, confirm the success of the preparation, and verify the
nature of the interactions of the prepared materials with biologi-
cal or other environments. XPS, along with other surface analysis
methods, plays a major role in understanding the processes and
verifying the process steps.
5. Summary
XPS has become one of the most highly used and important
tools for surface analysis. Throughout its history is has been applied
to obtain information about nanostructured materials and such
applications are increasing along with the growth of nanomaterials
research. Nonetheless, several indicators suggest that the need for
characterization of the surfaces of nanoparticles and other nano-
materials has been not fully appreciated.
Because of a common size among some materials’ nanostruc-
tures and different levels of biological systems as well as the
area of nanbiotechnology, there are common analysis needs and
challenges that link characterization of nanostructured materials,
biomaterials, and biological systems. The application of XPS to
microbes and true natural biological systems is much less com-
mon and faces additional complications in comparison to analysis
of nanostructured materials
Because of the long history of application of XPS to nanostruc-
tured materials, a good deal is known about how nanostructure
influences the peak intensities, signal backgrounds, and the bind-
ing energies of photoelectron peaks of nanostructured materials,
and a variety of methods have been developed to use those effects
to learn about the nanostructures being measured. In spite of the
tools and capabilities available to learn more about the nature of
the nanostructure, examination of the literature suggests that many
users analyze most samples with the assumption that they are flat
and that XPS signals come from a flat layer of uniform composition.
A good deal of additional information could be obtained.
As a consequence of their environmental sensitivity, ease
of damage, time-dependent properties, the presence of unusual
phases or properties, as well as the impact of coatings and con-
tamination, analysis of nanoparticles and other nanomaterials is
often more difficult than expected by many researchers. Important
information is frequently not collected or reported. More charac-
terization effort and an increased amount of care in collecting such
data are needed.
Although XPS is an increasingly valuable tool for the character-
ization of nanostructured and biological materials and organisms,
its value often lies in the combination of information from XPS and
a variety of other tools. The multi-method approach provides con-
firming or complementary information need to fully characterize
the materials. Although XPS does not generally have the spatial
resolution to examine individual nanosized objects, its quantita-
tive ability often provides information that provides a foundation
for other sometimes less quantitative data from other techniques.
The knowledge of electron path lengths allows XPS data to
be interpreted to obtain important nanoscale information that is
not easily obtainable by other techniques. However, some of the
impacts of the nanosize on electron transport behavior are not
fully understood and likely limit the quantitative accuracy what
can currently be learned.
The development of physically based models of electron emis-
sion and transport are increasing the ability to extract high-quality
information from XPS data. Careful application of these models
will both provide useful data about nanostructures and provide
the information needed to improve understanding and advance the
methodology.
In some ways the application of XPS to biomaterials is a simple
extension of approaches and methods applied to other materi-
als characterization efforts. However, the application of XPS to
microbes and other true biological systems is much less frequent.
Much of the data currently collected involve quantifying the rela-
tive peak intensities of different functional groups that appear at
the microbe surface. A few studies look for the sorption of trace
elements or the impact of environment on the chemical state of
specific elements.
Some research groups have developed some degree of exper-
tise in specific areas. Although other groups may also have similar
expertise, a few are mentioned as examples. As noted on its web-
site, the Université Catholique de Louvain [126] have an expertise
in using XPS for analysis of microbial cells, and work involving Y.F.
Dufrene and P.G. Rouxhet has been noted in this paper [126]. For
 D.R. Baer, M.H. Engelhard / Journal of Electron Spectroscopy and Related Phenomena 178–179 (2010) 415–432
many years B.D. Ratner and D.G. Castner at University of Washing-
ton have hosted the National ESCA and Surface Analysis Center for
Biomedical Problems (NESAC/BIO) which is funded by the National
Institute for Biomedical Imaging and Bioengineering of the National
Institutes of Health [127]. We also note and D.Q. Yang and E. Sacher
of the Engineering Physics Ecole Polytechnique of Montreal have
many recent publications and a web page discussing XPS analysis
of nanostructured materials [4].
Acknowledgements
This paper has evolved from research programs supported by
the U.S. Department of Energy (DOE) and research conducted as
part of the Environmental Molecular Sciences Laboratory (EMSL)
User Program. It has benefited from interactions with colleagues
from around the world and input from experts associated with ISO
TC 201 Surface Chemical Analysis and ASTM E42 Surface Analysis.
We particularly want to thank Dr. P. Nachimuthu for suggestions on
the manuscript and to Drs. Cedric Powell, M. Seah and L. Kover for
their encouragement. Aspects of the work have been supported by
the DOE Offices of Basic Energy Sciences and Biological and Envi-
ronmental Research. Portions of this work were conduced in the
EMSL, a national scientific user facility sponsored by the US Depart-
ment of Energy’s Office of Biological and Environmental Research
and located at Pacific Northwest National Laboratory.
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