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DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

What is Surface Analysis?

Surface analysis involves probing a sample with various chemical or


physical probes and detecting the various characteristic emitted species to
yield information about a surface.

Typical probes include:


• Photon
• Electron
• Ion beams.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

Surface Sensitivity

Many analytical techniques used in materials characterization are “bulk”


techniques in the sense that they give a composite measurement of the
atoms in a sample.

In contrast, a surface sensitive technique preferentially provides more


sensitivity to atoms near the surface than in the bulk away from the
surface i.e. the majority of the signal originates from the surface region.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

Surface Analysis Team Capabilities

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

X-Ray Photoelectron Spectroscopy (XPS)


or
Photoemission Spectroscopy
or
Electron Spectroscopy for Chemical Analysis
(ESCA)

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS features:

Qualitative and Quantitative Information: Photoelectrons occur at


binding energies characteristic of elements present and at intensities
proportional to their concentrations;

Chemical State Analysis – BE sensitive to valence states and molecular


environments;

Surface Sensitive – Information depth < 100Å;

Angle Resolved XPS – Grazing take-off angles enhances fraction of


signal from surface confined species;

Depth Profiling/Imaging – Analyzer “scans” to produce images.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS ANALYSIS CAPABILITIES

• Elements detected from Li to U.


• None destructive (some damage to x-ray beam sensitive materials)
• Quantitative.
• Chemical state analysis
• Surface sensitivity from 5 to 75 angstroms.
• Conducting and insulating materials.
• Detection limits that range from 0.01 to 0.5 atom percent.
• Spatial resolution for surface mapping from >10 mm
• Depth profiling capabilities.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

BASIC PRINCIPLES

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS EMISSION PROCESS

An incoming photon causes the ejection of the photoelectron

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

BASIC PRINCIPLES
The working principle of XPS involves radiating the sample with monochromatic
X-ray radiation of known frequency (n) and hence of known photon energy (hn).

With the bombardment by the incident photons of high energy, electrons from the
inner core of the atoms in the sample are ejected out. Once the electrons are
released, some of them travel towards. Electrons which hold enough energy at this
point may abandon the solid material for the surrounding vacuum. Once in the
vacuum, they are collected and measured for their kinetic energy Ek.

The binding energy of the electron Eb which they had before leaving the atom can
then be calculated by means of the following equation:

Eb = (hn) − Ek − w

where w is the so-called work function of the spectrometer, a factor that corrects for
the electrostatic environment in which the electron is formed and measured.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

BASIC PRINCIPLES
The relationship governing the
interaction of a photon with a core
level is:

KE = hn – BE – eF
or
BE = hn – KE – eF

KE = kinetic energy of ejected photoelectron


hn = characteristic energy of X-ray photon
BE = binding energy of the atomic orbital from which the electron originates.
eF = spectrometer work function

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS Instrumentation Diagram of a X photoelectrons


spectrometry system:

(1) X-rays tube;


(2) Sample;
(3) Electronic focusing system;
(4) Spectrometer;
(5) Electrons detector (channeltron);
(6) Data acquisition.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

SURFACE SENSITIVITY

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

BASIC ANALYSIS

Identification of the elements in the sample can be made directly from the
kinetic energies of these ejected photoelectrons.
The binding energy is characteristic of the elemental atom and orbital from
which the electron was emitted. Therefore, it functions as an identification
card for determination of atoms involved.
Each binding energy matches a specific atom type, for example 284.6 eV for
carbon (C) and 532.5 eV for oxygen (O)..

The relative concentrations of elements can be determined from the


photoelectron intensities.
The area under a particular peak is proportional to the number of atoms
being present in the investigated element.By calculating the respective
contribution of each area, chemical composition of the sample can thus be
determined.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

ANALYSIS OBJECTIVE

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS QUANTIFICATION

Quantitative data can be obtained from peak heights or peak areas, and
identification of chemical states often can be made from exact
measurements of peak positions and separations, as well as from certain
spectral features.

The following building blocks are used to provide accurate quantification:


- A standardized set of sensitivity factors.
- The transmission function of the spectrometer.
- Corrections for geometric asymmetry related to the angle between the
X-ray source and the analyzer input lens.

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

An XPS spectrum thus consists of a plot of the number of emitted electrons, or


the power of the electron beam, as a function of the binding energy.

Wide
scan

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS high resolution scan of the Ag 3d region Ag based catalyst on g-Al2O3

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS of Poly(ethylene terephthalate), PET

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS high energy resolution spectra of solar cell before & after KCN
treatment

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS high energy resolution spectra oxidized and reduced CeO2

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

XPS spectra of Ti2p peaks for Ti and TiO2

Ti metal peak (454 eV)

TiO2 (110) with some reduced states

TiO2 peak (459 eV)

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id


DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA

PEAK DECONVOLUTION

High resolution scan of C peak

~284.80 eV : adventitious carbon contamination from the atmosphere


~285 eV: C−C and C−H bonds of the organic matrix.
~286.36 288.96 eV C−O and C=O bonds of the organic matrix, respectively

MMS 8110803- KARAKTERISASI MATERIAL + LAB ahyuwono@metal.ui.ac.id

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