Tools for Nano Characterization:

X-Ray Spectroscopy
Prepared By: Organized By:
Anila Anwar Dr. Abu Bin Imran
Student No: 1018032716 Associate Professor
Dept. of Chemistry, BUET Dept. of Chemistry BUET
X-Ray Spectroscopy:

X-ray spectroscopy is a technique that detects and

measures photons, or particles of light, that have
wavelengths in the X-ray portion of the
electromagnetic spectrum.
Wavelength range of X-Ray 0.01 to 10 nanometer.
Energy range 100eV to 100keV.
Different types of X-Ray Spectroscopy

1. XRD (X-Ray Diffraction)

2. XPS (X-Ray Photon Spectroscopy)
3. XRF (X-Ray Fluorescence)
 XPS
(X-Ray Photon Spectroscopy)
 XPS is a surface sensitive spectroscopic technique to analyze the
structure of atoms and get information about electronic
structure.
 XPS is also known as ESCA (Electron Spectroscopy for Chemical
Analysis) as in often use to investigate the chemical composition
of various materials.
 It is based on photoelectric effect which was described by
Einstein in 1905.
Basic Principle of XPS

 The Working principles of XPS is ejection of electron from the

surface of sample in UHV condition.
 Elements present in sample can be identified on the basis of
kinetic energies and binding energies of their photo electrons.
 Intensities of photoelectron provide information about
concentration of element in a sample.
 The electrons emitted from atoms near the sample surface (10-
100 Angstroms) can escape the sample surface.
Theoretical Background:
Photoelectric Effect:
 When an X-ray (with energy hν) ejects out an electron (by
energy B.E). The ejected electron is called photoelectron
and this effect is called photoelectric effect.
 The atom will release energy by the emission of an Auger
Electron.
Theoretical Background:

The ejected photoelectron has kinetic energy:

K. E = hv - B.E - Ø

 KE → Kinetic Energy
 hv → Energy of photon emitted by X-rays
 Ø → Spectrometer work function
 BE → Binding Energy
Theoretical Background:
 No emission of photon if hν < Ø
 No emission of photon from
levels with BE + Ø > hν
 Increase in KE of photoelectron
cause decrease in BE.
 Require monochromatic beam.
 Each element has different value
of KE for core level electrons.
X-Ray Photon Spectrometer:
Setup of XP-Spectrometer:
Diagram of the Side View of XPS System
 How Does XPS Technology Work?
 A mono energetic x-ray beam
emits photoelectrons from the
surface of the sample.
 The X-Rays either of two energies: 
Al Kα(1486.6eV)
Mg Kα(1253.6 eV)
 The x-ray photons penetrate about 
a micrometer of the sample.
 The XPS spectrum contains
information only about the top 10 -
100 Ǻ of the sample.
 Ultrahigh vacuum environment to
eliminate excessive surface
contamination.
Cylindrical Mirror Analyzer (CMA)
measures the KE of emitted
electrons.
The spectrum plotted by the
computer from the analyzer signal.
 The binding energies can be
determined from the peak
positions and the elements present
in the sample identified.
Sample Preparation:
 Sample preparation is not require usually. We just mount the
sample and place it for analysis
 Removal of Volatile Material with the help of pumping or by
washing with a solvent like ethanol.
 Removal of Nonvolatile Organic Contaminants by freshly
distilled solvents.
 Surface Etching (surface contaminants can remove by ion
sputtering and other erosion techniques).
Analysis: XPS Peak Elemental Shift
 XPS peak is plotted between No. of electrons (CPS) and B.E.
 Electron-nucleus attraction helps us identify the elements.
 Each element and orbital has different binding energy for each electron
present in it.
 The orbit which are closer to nucleus has high binding energy but low K.E
Analysis: Chemical Shift
 It occur due to electronegativity difference and bonding of atoms.
 Higher positive oxidation state has high BE due to interaction between
emitted electrons and nucleus.
 Differentiate between different oxidation state and chemical environment is
major use of XPS.
Chemical Shift
In the figure Ti 2P
spectrum of a pure metal
titanium is compared
with Titanium di oxide.

A chemical shift of about

5eV between the
oxidation state and pure
metal state is observed.
 Advantages and Limitations
Advantages
 Non-destructive technique.
 Surface Sensitive (10-100 Å).
 Detection unit: ppt and some
conditions ppm.
 Quantitative measurements are
obtained.
 Provides information about
chemical bonding.
 Elemental mapping.
Limitations
 Very expensive technique.
 High vacuum is required.
 Slow processing.
 Large area analysis is
required.
 H and He can not be
identified.
 Data collection is slow 5 to
10 min.
 Uses

XPS is used to measure: Applications in the industry:

 Elemental composition of the  Failure analysis
surface (top 1–12 nm usually).  Polymer surface
 Empirical formula of pure  Corrosion
materials.  Adhesion
 Chemical or electronic state of  Semiconductors
each element in the surface.
 Dielectric materials
 Uniformity of composition  Thin film coatings
across the top surface.
References:

 http://www.casaxps.com/help_manual/XPSInformation/XPSInstr.htm
 http://www.lanl.gov/orgs/nmt/nmtdo/AQarchive/04summer/XPS.html
 https://www.spectroscopynow.com/
 https://en.wikipedia.org/wiki/X-ray_photoelectron_spectroscopy