Photoelectron Spectroscopy (PES)

Photoelectron spectroscopy is based on the photoelectric effect, a physical phenomenon first

characterized by Albert Einstein in 1905. It is primarily used to investigate the chemical composition of
surfaces.

The sample is exposed to monochromatic UV or X-ray electromagnetic radiation that has sufficient
energy (E=h) to ionize the sample. The absorbed energy leads to ejection of electrons. The kinetic
energies (EK) of the released electrons are measured.

The binding energy of each ejected electron (EB) can be calculated using the following equation:
EB= hEK
The frequency of the incoming electromagnetic radiation () and the Planck constant (h=
6.6261034 J s) is known; the kinetic energy of the ejected electron (EK) is determined.

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A photoelectron spectrum is a graph of the number of photoelectrons vs. binding energy.
A typical photoelectron spectrum features peaks at different binding energies. Because electrons in a
particular subshell of an atom have the same binding energy, each of these peaks corresponds to electrons
in a different subshell. The binding energy of a peak tells us how much energy is required to remove an
electron from the subshell, and the intensity of the peak tells us the relative number of electrons in the
subshell.

In the photoelectron spectrum of Al, the peak at the highest energy corresponds to the electron removal
from the 1s subshell. These electrons have the highest binding energy because they are closest to the
nucleus and less shielded by other electrons. The third peak is three times more intense than the first (1s2)
and second (2s2) peaks because the 2p subshell contains three times more (6) electrons. The lowest-
energy peak has the intensity half of the first, second and forth peaks because 3p subshell is populated by
one electron. The energy difference between subshells is smaller than the energy difference between
shells.

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Two types of photoelectron spectroscopy

Depending on the source of ionization energy, PES can be divided accordingly into X-ray Photoelectron
Spectroscopy (XPS) and Ultraviolet Photoelectron Spectroscopy (UPS).

HOMO, LUMO
Energy resolution ~1eV Much higher energy resolution (a few meV)
Higher surface sensitivity than XPS
Interpretation of the spectrum is more difficult

Ultrahigh vacuum environment (pressure < 108 Torr) is used in both methods.

 to eliminate the adsorption of contaminants on the sample

 to avoid electron collision with gas molecules which modifies the kinetic energy of electron

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Ultraviolet photoelectron spectroscopy (UPS): produces a spectrum where the individual peaks are
attributed to molecular orbitals. It uses photons in the ultraviolet spectral range of 10-50 eV (this
corresponds to wavelengths from 124 to 25 nm). This technique is applied to study the valence and
conduction bands.

This technique involves a UV lamp for the radiation source. Ionised helium emits light in the vacuum
ultraviolet range. Depending on the gas density in the ionisation chamber, two different emissions can be
obtained. These emissions are classified according to their energy:
 He I (21.2 eV ≈ 58.5 nm wavelength, light emitted from neutral atoms)
 He II (40.8 eV ≈ 30.4 nm wavelength, light emitted by singly ionized atoms)

Tunable-wavelength very intense light source can be synchrotron radiation.

Scheme of an UPS instrument:

The excitation light penetrates the sample at an average depth of 2.5 nm. Because of the low penetration
depth, UPS can only ionize thin surface layers. The UV light can eject electrons from the outermost
electronic levels – i.e., the valence electrons. The sensitivity of UPS is also a beneficial factor, as it allows
for the resolution (0.01 eV) of components that cannot be probed using XPS. The sensitivity is attributed
to the radiation possessing a very narrow line width, and there is a high flux of photons available from the
radiation source.

UPS can be used for the study of chemisorption on catalysts based on a comparison between the gas
phase spectra and the spectra of the chemisorbed species. The positions of UPS peaks can identify
orbitals participating in gas substrate bonding. Information can be obtained on the orientation of the
chemisorbed species and on reaction products.

UPS spectra for CO gas and chemisorbed CO

the 5σ orbital take part in the bonding to the surface

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X-ray photoelectron spectroscopy (XPS) also called Electron Spectroscopy for Chemical Analysis
(ESCA) or photoelectron spectroscopy for inner shells (PESIS):
Irradiation of the sample with X-rays and measuring the kinetic energy of the photoelectrons emitted from
the surface. X-rays with photon energies between 100 eV-10 keV are used (these values correspond to
wavelengths from 12.4 to 0.124 nm). This technique is applied to probe the deep core electron levels. The
core electrons have binding energies most characteristic of the particular element. It can detect all
elements except H and He. It is not as sensitive as UPS and only has a resolution of 0.3 eV to 0.7 eV.

This technique is useful to analyse

 the quantity and types of elements constituting the sample surface within a few nanometers depth
 oxidation state of element
 chemical formula of the compound
 identification of functional groups
 thickness of the surface layer

Auger Electron Spectroscopy (AES): allows determining the chemical composition of a surface. This
characterisation can be achieved up to 1 nm depth. The smallest surface that can be characterised is a few
nm wide for the best instruments. An electron gun is used as an excitation source.

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The intensity of the peaks after background correction is related to the concentration of the element
within the sampled region. Relative Sensitivity Factors (RSF) for various elements are available in the
literature.

Normally, the sample is radiated with photons of a single energy (K transition of magnesium or
aluminium; the transition from 2p to 1s electron level is called Kα).

X-rays hit all sample area simultaneously permitting data acquisition that will give an idea of the average
composition of the whole surface.

The X-rays penetrate the sample to a depth on the order of a micrometer but the electrons produced by
photoelectric effect from the deeper layers collide with other electrons and lose kinetic energy. Therefore,
they contribute only to the noise signal of the spectrum. Electrons can be released from the upper 2-10 nm
surface layer without the loss of their kinetic energy. Consequently, XPS is sensitive only to the 2-10 nm
layer depth.

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 If an electron is pulled away from the nucleus, the attraction between the electron and the nucleus
decreases and the binding energy of this electron decreases.

Atoms of a higher positive oxidation state exhibit a higher binding energy due to the extra Coulombic
interaction between the electron which will be emitted and the ion core.

Addition of valence electron decreases the binding energy

For example, the binding energy of the 2p electron in Fe2O3 is larger than in metallic iron.

If the atom has positive charge, it is more difficult to remove its core electron than in the case of the same
uncharged atom.

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Different XPS energies are observed for the same element depending on its chemical environment.

High-resolution spectrum of an oxidized silicon wafer in the energy range of the Si 2p signal. The raw
data spectrum (red) is fitted with five components or chemical states, (A, B) metallic Si, (C) very small
amount of Si2O, (D) Si2O3 and (E) SiO2. The oxidized forms of Si (SiOx, x = 1-2) appear at higher
binding energies as broad bands. The so-called metallic form of silicon, which resides below an upper
layer of oxidized silicon, exhibits a set of doublet peaks at (B) 100.30 eV (Si 2p1/2) and (A) 99.69 eV (Si
2p3/2). The fact that the metallic silicon signal can be seen "through" the overlayer of oxidized Si
indicates that the silicon oxide layer is relatively thin (2-3 nm). Attenuation of XPS signals from deeper
layers by overlayers is often used in XPS to estimate layer thicknesses and depths.

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XPS spectra of polyethylene terephthalate (PET)

J. Vac. Sci. Technol. A 38, 063204 (2020);

In a XPS graph it is possible to see Auger electron peaks (upper figure). The Auger peaks are usually
wider than the XPS peaks and their position changes with the alteration of the wavelength of the X-ray
irradiation. The position of the XPS peaks does not move upon the alteration of the wavelength of the X-
ray irradiation. Therefore, Auger peaks can be separated from XPS peaks.

Survey spectra are typically used to obtain basic elemental information and to look for the presence of
unexpected elements in the sample. Figure 4(a) shows that the PET sample contains only carbon and
oxygen as expected.

In the case of C 1s, the binding energy is highly dependent on the electronegativity of the nearest
neighbour elements (Figure 4b). As the neighbouring atom becomes more electronegative, the binding
energy for the C 1s electron increases. XPS can easily distinguish between CC, CO, C=O and CF2
based on this simple electronegativity trend. Therefore, peak assignments for the three C 1s peaks can be
made as shown in Figure 4b. The relative area under each peak is representative of the number of carbon
atoms present in each environment.

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This table demonstrates that the binding energy of the core electrons increases when the electronegativity
of the neighbouring atom grows.

Determination of the amount of the OH and OCH3 groups on a surface

All XPS lines except those from the s orbitals occur as doublets due to spin–orbit coupling. Doublets are
commonly notated with the j quantum number as a subscript. For example, the Ti 2p doublet consists of
the Ti 2p1/2 and the Ti 2p3/2 peaks. The intensity ratios of the peaks in a doublet are also defined by these j
quantum numbers. Relative intensities are determined by 2j+1. For the Ti 2p peaks, the ratio of the
heights should be 2:1 for the Ti 2p3/2 and Ti 2p½ peaks, respectively (2*3/2 + 1 = 4 and 2*1/2 + 1 = 2,
therefore, the ratio is 4:2 or 2:1).

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Tilting the sample is an easy way to change the depth of analysis in XPS.

When the sample is untilted (α = 0°), the escape depth (shown by the double pointed arrow in the top
layer of the sample) and the information depth or sampling depth (shown by the 10 nm blue portion of the
sample) are the same. When the sample is tilted (α = 70°), the escape depth does not change since this is a
physical parameter defined by the electron energies and the material they are traveling through. However,
the path they must take to reach the detector does change, and as a result, the sampling depth is reduced.
In this way, a larger angle of emission enhances the signal from the surface. Analysis at several angles
can provide a non-destructive “depth profile” of the top ∼10 nm.

The Si 2p data from a silicon wafer with a native oxide show elemental Si lines at ∼99 eV and Si(IV)
lines from SiO2 at ∼103 eV. The original data, taken at 0°, do not indicate if this is a layered sample or if
Si and SiO2 are a homogeneous mixture. Comparison of the data at 0° with that at 70° shows a difference
in the relative intensity of these two components. When a thinner layer of the surface is probed during the
experiment at 70°, the SiO2 component is higher in intensity relative to the Si component, indicating that
SiO2 is indeed a surface layer on top of Si. If it were a homogeneous mixture, the relative ratio of the two
components should not change upon tilting the sample.

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