X-ray Photoelectron

Spectroscopy (XPS)
 Submitted by:
Azka Hanan
(bschm-f21-011)
Submitted to:
Dr. Quratulain Amjad
BS Biochemistry 8th
Nanobiotechnology

Table of Content

Content Page#
Background........................................................................................
Introduction......................................................................................
Principle...........................................................................................
Procedure..........................................................................................
Applications......................................................................................
Conclusion........................................................................................
References.........................................................................................
Background of XPS:

X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for Chemical
Analysis (ESCA), was developed in the early 1960s by Kai Siegbahn and his team at Uppsala
University. The technique builds on the photoelectric effect, first explained by Albert Einstein in
1905, where X-rays eject electrons from a material's surface. Siegbahn's groundbreaking work in
developing a spectrometer capable of precisely measuring the kinetic energy of these ejected
electrons led to the birth of XPS. In 1981, he was awarded the Nobel Prize in Physics for his
contributions to the field. This technique revolutionized surface analysis, providing detailed
information about the chemical state, elemental composition, and bonding environment of
materials.

Since its inception, XPS has become an essential tool in materials science, chemistry, and
surface science. It has undergone significant advancements in instrumentation and data analysis,
expanding its applications to fields such as nanotechnology, catalysis, and semiconductor
research. The ability to analyze surfaces with high sensitivity and precision, and to provide both
qualitative and quantitative data, has made XPS an invaluable technique in both academic
research and industrial applications (Andrade, 1985).

Introduction to XPS:
X-ray Photoelectron Spectroscopy (XPS) is a groundbreaking technique that has revolutionized
the way we analyze materials. By using high-energy X-rays to eject electrons from the surface of
a sample, XPS allows scientists to probe the atomic and chemical structure of materials with
unmatched precision. This extraordinary ability to unveil the elemental composition, chemical
state, and electronic properties of a material’s surface has made XPS an indispensable tool in
research and industry. From semiconductors to catalysts, it provides detailed insights that are
critical to advancing technology in fields like nanotechnology, materials science, and surface
chemistry. What sets XPS apart is its incredible sensitivity and depth of analysis. It doesn’t just
tell you what elements are present on a material’s surface; it reveals the exact chemical
environment those elements are in, offering a level of detail that is simply impossible to achieve
with other techniques. Whether it's mapping the distribution of elements across a surface,
identifying oxidation states, or understanding how atoms are bonded together, XPS delivers
answers that can unlock new innovations. In the world of materials analysis, XPS is nothing
short of a game-changer, allowing us to peer into the very building blocks of matter and
transform how we approach scientific challenges (Stevie & Donley, 2020).

Principle of XPS

The principle of X-ray Photoelectron Spectroscopy (XPS) is based on the photoelectric effect,
where a material is irradiated with X-rays, causing the ejection of electrons from the surface of
the sample. Here’s how it works in detail:

1. X-ray Irradiation: When the sample is exposed to X-rays, the energy from the X-rays is
transferred to the core electrons of atoms on the material’s surface. The energy of the X-
rays is sufficient to overcome the binding energy that holds these electrons within their
atomic orbitals. As a result, the core electrons are ejected from the material’s surface.
2. Photoelectron Emission: The energy of the ejected electrons is dependent on two
factors: the energy of the incoming X-ray and the binding energy of the electron within
the atom. The kinetic energy of the emitted electron can be measured directly by the XPS
instrument.
3. Energy Analysis: The measured kinetic energy of the photoelectron is used to calculate
the binding energy of the electron in the atom. The binding energy is the amount of
energy required to remove the electron from the atom and is characteristic of both the
element and the specific chemical state of the element in the material. The relationship is
described by the equation

Eb =hν−Ek −ϕ (explained in Figure 1)

4. Spectral Data: A spectrum is produced by measuring the number of electrons as a

function of their binding energy. This spectrum reveals distinct peaks corresponding to
different elements and their specific oxidation states. Each element’s core electrons have
unique binding energies, and shifts in these binding energies can be used to identify
changes in the chemical environment or oxidation states of the element.
 Figure 1: Principle of XPS

5. Surface Sensitivity: XPS is highly surface-sensitive, typically probing the top 1–10
nanometers of a material. The electrons that are ejected from the surface experience
energy losses due to scattering or inelastic interactions, which is why only those emitted
with sufficient energy to escape the surface layer can be detected.

In summary, XPS provides a detailed chemical analysis by measuring the energies of

photoelectrons ejected from the sample after X-ray irradiation. This allows scientists to
determine the elemental composition, oxidation states, and chemical bonding of the surface
atoms, making XPS an invaluable tool for surface characterization and material analysis (Gurker,
Ebel, & Ebel, 1983).

Working of XPS:

X-ray Photoelectron Spectroscopy (XPS) works by using X-rays to "knock" electrons out of the
surface of a material as shown in figure 2. X-ray Photoelectron Spectroscopy (XPS) works by
irradiating a material with X-rays, causing electrons to be ejected from the surface. By measuring
the energy of these ejected electrons, XPS reveals detailed information about the material's
elemental composition and chemical state.

1. X-ray Exposure: The material is exposed to X-rays, which carry energy. When the X-
rays hit the surface of the material, they give energy to the electrons that are tightly
bound in the atoms' inner shells (core electrons).
2. Electron Ejection: If the X-ray energy is high enough, it knocks some of these electrons
out of the atom. The knocked-out electrons are called photoelectrons.
3. Measuring Energy: The XPS instrument measures how much energy these
photoelectrons have when they leave the surface. This energy tells us two things: how
strongly the electron was bound to the atom and which element it came from.
4. Determining Binding Energy: By knowing the energy of the X-rays and the energy of
the emitted electrons, we can calculate the binding energy of the electrons in the atom.
Different elements and different chemical states have unique binding energies, so this
helps us figure out exactly what elements are present and how they are chemically
bonded.

Figure 2: Working of XPS

5. Creating a Spectrum: The instrument creates a spectrum (a graph) showing peaks at

different binding energies. Each peak represents a different element or chemical state on
the material’s surface.
In essence, XPS works by bombarding the material with X-rays, measuring the energy of the
ejected electrons, and using that data to figure out the material's elemental composition and the
chemical state of the elements on its surface. (Aziz & Ismail, 2017).

Applications of XPS:

X-ray Photoelectron Spectroscopy (XPS) has a wide range of applications across various fields
due to its ability to provide detailed information about a material’s surface composition and
chemical states as shown in Figure 3. Some of the key applications include:

1. Surface Chemistry and Material Characterization: XPS is widely used to study the
surface chemistry of materials. It provides information on the elemental composition of
the surface, the oxidation states of elements, and the chemical bonding environment. This
is crucial for understanding material behavior, surface reactivity, and the properties of
thin films, coatings, and nanoparticles.
2. Semiconductor Industry: In the semiconductor industry, XPS plays a vital role in
characterizing the surfaces of semiconductor materials and thin films. It is used for
analyzing thin oxide layers, understanding contamination, and ensuring the quality of the
materials used in semiconductor devices. It helps monitor the effects of processes like
oxidation, etching, and deposition in microelectronics manufacturing.
3. Catalysis: XPS is crucial in catalysis research, where it is used to investigate the
chemical states and surface composition of catalysts. By studying how catalysts change
during reactions, XPS helps improve catalyst efficiency, stability, and selectivity. It can
identify the active sites on catalysts and understand the interaction between the catalyst
surface and reactants.
 Figure 3: Applications of XPS

4. Corrosion Studies: XPS is often used to analyze the surfaces of corroded materials. By
studying the chemical state of metal oxides and other corrosion products, researchers can
better understand corrosion mechanisms and develop more effective protective coatings
or treatments for materials exposed to harsh environments.
5. Polymer and Coating Analysis: XPS is used to study the surface properties of polymers
and coatings. It can identify functional groups, additives, and contaminants on the
surface, helping improve the performance of materials used in electronics, adhesives,
paints, and medical devices. It also helps in understanding surface modifications such as
plasma treatment or chemical functionalization.
6. Nanomaterials and Nanotechnology: In nanotechnology, XPS is employed to analyze
the surface properties of nanomaterials, such as nanoparticles, nanowires, and
nanostructured films. The surface properties of these materials often differ significantly
from their bulk properties, and XPS helps researchers understand their behavior, stability,
and potential applications in fields like drug delivery, sensors, and electronics.
7. Environmental Studies: XPS is applied in environmental research to study the surface
composition of pollutants, including heavy metals, toxic compounds, and pollutants in air
or water. It helps in understanding how these substances interact with surfaces, such as
soil, sediments, or environmental materials, providing insights for remediation strategies.
 8. Biomaterials and Medical Devices: XPS is used to investigate the surface properties of
biomaterials, such as those used in implants, prosthetics, and medical devices. It can
provide information about surface contamination, functionalization, and how the material
interacts with biological tissues, which is essential for improving biocompatibility and
performance (Arthur, 2006) (Krishna & Philip, 2022).

Conclusion
In conclusion, the working principle of X-ray Photoelectron Spectroscopy, which involves
measuring the energy of photoelectrons ejected from a material’s surface, provides invaluable
insights into its elemental composition and chemical states. This ability to analyze surfaces with
exceptional detail makes XPS a powerful tool across a wide range of applications, from
semiconductor fabrication and catalysis to environmental studies and biomaterial analysis. By
revealing critical surface information, XPS enables advancements in material design, quality
control, and process optimization. Its versatility and precision continue to make it an essential
technique in both research and industrial settings.
References:

Andrade, J. D. (1985). X-ray photoelectron spectroscopy (XPS). In Surface and interfacial aspects of
biomedical polymers: Volume 1 surface chemistry and physics (pp. 105–195).
Stevie, F. A., & Donley, C. L. (2020). Introduction to X-ray photoelectron spectroscopy. Journal of Vacuum
Science & Technology A, 38(6). https://doi.org/10.1116/6.0000012
Gurker, N., Ebel, M. F., & Ebel, H. (1983). Imaging XPS—A new technique, I—Principles. Surface and
Interface Analysis, 5(1), 13–19. https://doi.org/10.1002/sia.740050104
Aziz, M., & Ismail, A. F. (2017). X-ray photoelectron spectroscopy (XPS). In Membrane characterization (pp.
81–93). Elsevier. https://doi.org/10.1016/B978-0-12-803764-1.00005-6
McArthur, S. L. (2006). Applications of XPS in bioengineering. Surface and Interface Analysis: An
International Journal Devoted to the Development and Application of Techniques for the Analysis of Surfaces,
Interfaces and Thin Films, 38(11), 1380–1385. https://doi.org/10.1002/sia.2430
Krishna, D. N., & Philip, J. (2022). Review on surface-characterization applications of X-ray photoelectron
spectroscopy (XPS): Recent developments and challenges. Applied Surface Science Advances, 12, 100332.
https://doi.org/10.1016/j.apsadv.2022.100332