Microscopic Composition Measurement at Nanoscale

DSSC Seminar

Lin Wang

April, 2005
 Outline

ƒ General Introduction
ƒ Energy Dispersive Spectroscopy (EDS)
ƒ Wavelength Dispersive Spectroscopy (WDS)
ƒ Electron Energy Loss Spectroscopy (EELS)
ƒ Auger Electron Spectroscopy (AES)
ƒ X-Ray Photoelectron Spectroscopy (XPS)
ƒ Summary
 General Introduction

When High Energy Electron Beam Meets Material…

{AEM with EDS}

Take a thin Transmitting

Specimen as an example

(AEM with EELS)

ƒ By Analyzing Emitted X-Ray

Energy Dispersive Spectroscopy (EDS) + SEM/ TEM Analytical
Wavelength Dispersive Spectroscopy (WDS) + SEM Electron
Microscope
ƒ By Analyzing Inelastically Scattered Electrons (AEM)
Electron Energy Loss Spectroscopy (EELS) +TEM
ƒ By Analyzing Emitted Auger Electrons
Auger Electron Spectroscopy (AES)
Surface
When X-Ray Meets Material… Characterization
ƒ By Analyzing Emitted Photoelectrons
X-Ray Photoelectron Spectroscopy (XPS)
 Principles of EDS

Energy Dispersive (X-Ray) Spectroscopy (EDS)

ƒ X-Ray counting is done by measuring the x-ray photon energies with a
Si(Ni)solid state detector

ƒ Different characteristic X-Ray lines of elements represent the types

and relative amounts of elements in the sample
ƒ The number of counts of each peak may be converted to weight
concentration using standard (more accurate) or standardless
calculations
 Principles of EDS (cont.)

With SEM With TEM

ƒ Energy Resolution (Peak Broadening) measured by FWHM (Full Width
at Half Maximum of the peak)

Gaussian Distribution
Y=AAexp{-1/2*[(EA-E)/σ ]2}

FWHM=2.355σ

ƒ Peak overlap
 Capacities of EDS

Usage
Add analytical capability on element concentration of SEM or TEM

Sample Requirements
ƒ Solids(polished), powders (compacted) or composites;
ƒ sample size: in SEM only limited by the stage size
ƒ in TEM 3mm diameter thin foil
ƒ Not destructive to sample

Limitation
ƒ Lateral resolution: typically about 0.5μm
as small as 1nm for thin samples in STEM
Sampling depth: 1μm, can achieve 0.02μm depending on Z and
electron beam energy
ƒ Detection limits: 100-200ppm for isolated peaks in elements with Z≥ 10
1-2%wt. for Z<10 or overlapped peaks
ƒ Accuracy: with standards ±4-5% deviation for concentrations >5%
 Application Examples of EDS
1-D Profiling
EDS Line Profile Software automation
allows simplified composition profiling at
nanometer resolution using EDS.
Sample: Si80Ge20 islands grown on Si at
800ºC followed by Si capping.
2-D Mapping Point
Analysis
EDS Mapping - EDS Mapping allows
visualization of the phase separation
process, which can be coupled with point-
by-point quantitative analysis.
Sample: Cu50Ag50 ball milled at 230 º C
 Principles of WDS

Wavelength Dispersive (X-Ray) Spectroscopy (WDS)

X-Ray counting is done by using a Bragg
reflector to wavelength-filter the x-rays on their
way to the detector

Bragg’s Law
Nλ=2dsinθ

With SEM
 Capacities of WDS

Advantages
ƒ Superior spectral resolution (X10 times better than EDS)
ƒ Can detect light element Z ≥ 4
ƒ Can detects 0.1%-several ppm
ƒ More accurate

Disadvantages
ƒ The equipment is more expensive
ƒ More Time consuming
ƒ More difficult to use

Usage
• Identification of spectrally overlapped elements such as W or Ta in Si,
or N in Ti
• Detect of low concentration species (down to 100 or even 10ppm)
such as P or S in metals
• Analysis of Low atomic number elements such as oxidation in metals
 Comparison between EDS&WDS

EDS: WDS:
ƒ Normally detects Z≥ 10(below ƒ Detects Z≥ 4
Na) thus typically can’t be
detected O, N, C. Sometimes if
using windowless or thin
window it can detect Z≥ 4

ƒ Parallel technique ƒ Serial technique

Can quickly scan for a wide slow but can provide excellent
rang of possible elements resolution

ƒ Good for use both with SEM or ƒ Requires very high x-ray
TEM specimen generation rates thus TEM
samples can’t provide high
count (x-ray generation) rate

ƒ Time of a typical run take a few ƒ Time of a typical run take hours
minutes
 Principles of EELS

Electron Energy Loss Spectroscopy (EELS)

With TEM
 Principles of EELS (continued)

Electron Energy Loss Spectroscopy (EELS)

 Capacities of EELS

Usage
Light element spectroscopy for concentration, electronic and chemical
structure analysis at ultrahigh lateral resolution

Sample Requirements
ƒ Solids and specimens must be transparent to electrons with about 10-
200nm thickness;
ƒ sample size: 3mm diameter thin foil
ƒ Not destructive to sample

Limitation
ƒ Range of elements: Z=3-92
ƒ Lateral resolution: 1nm-10μm, depending on the diameter of the incident
electron probe size and the thickness of the specimen
Sampling depth: with thickness of specimen 10-200nm
ƒ Detection limits: 10-21g
ƒ Accuracy: with standards ±1-2 at.%, without standards ±10-20 at.%
 Application Examples of EELS

EELS Mapping - The breakdown of the Li/Ni ordering at the surface

can be seen as changes in the EELS fine structure and Ni-to-O ratio.

Sample: LiNi0.80Co0.20O2 from Li-Ion battery after aging

 Principles of AES

Auger Electron Spectroscopy (AES)

 Capacities of AES

Sample Requirements
ƒ vacuum compatible materials
ƒ no destruction except to electron beam sensitive materials and during
depth profiling

Vacuum Requirements: 10-10 torr

Limitation
ƒ Range of elements: All except H and He
ƒ Lateral resolution: 10-30nm for Auger analysis and even less for imaging
Sampling depth: 0.5-10nm
ƒ Detection limits: 0.1-1at.%
ƒ Accuracy: ± 30% if using published elemental sensitivity
±10% if using standards that closely resemble the sample
 Applications of AES

• Composition analysis of the 0-3nm region near the surface for all
elements except H and He
• Scanning Auger Microscopy

• Depth-composition profiling and thin film analysis

• High lateral resolution surface chemical analysis and
inhomogeneity studies to determine compositional variations
• Surface diffusion and segregation
 Principles of XPS

X-Ray Photoelectron Spectroscopy (XPS)

 Capacities of XPS

Sample Requirements
ƒ vacuum compatible materials, flat samples preferred
ƒ no destruction except to X-ray sensitive materials and during
depth profiling

Limitation
ƒ Range of elements: All except H and He
ƒ Lateral resolution: 5mm-75μm
Sampling depth: 0.5-5nm
ƒ Detection limits: 0.01-0.3at.%
 Applications of XPS

‰ Routinely used in industry and research whenever elemental or

chemical state analysis is needed at surfaces and interfaces as well as
spatial resolution requirements are not demanding (typically greater
than 150μm).

‰ Eg.’s:
ƒ examination for and identification of surface contaminations
ƒ Evaluation of materials processing steps (cleaning, plasma etching, thermal
oxidation, silicide thin-film formation etc.)
ƒ Evaluation of thin-film coating or lubricants
ƒ Failure analysis for adhesion between components(air oxidation , corrosion
etc.)
ƒ Tribological (or wear) activity
ƒ Effectiveness of surface treatment of polymers or plastics
ƒ Surface composition differences for alloys
 Summary

ƒ All of the five methods can give both microscopic imaging function
and qualitative plus quantitative composition analysis function
ƒ Quantitative composition measurement will be more accurate with
standards esp. standards in similar composition range
ƒ For EDS, the major limitation is the peak broadening and light element
incapability
ƒ For WDS, comparing with EDS, it has high spectral resolution but it
takes longer for each run
ƒ EELS can detect light element and has a high lateral resolution
ƒ AES and XPS are surface composition detection techniques but AES
has a nm-scale lateral resolution which is much better than XPS
 Reference
ƒ J. Goldstein, D. Newbury, D. Joy, C. Lyman, P. Echlin, E. Lifshin, L,
Sawyer, J. Michael, Scanning Electron Microscopy and X-Ray
Microanalysis, Kluwer Academic / Plenum Publishers (2003)
ƒ C. Brundle, C. Evans, S. Wilson, L. Fitzpatrick, Encyclopedia of
Materials Characterization, Butterworth-Heinemann (1992)
ƒ D. Williams, C. Carter, Transmission Electron Microscopy, Pledum
(1996)
ƒ D. J. O’Connor, B. A. Sexton, R.St. C. Smart, Surface Analysis Methods
in Materials Science, Springer (2003)
ƒ http://cmm.mrl.uiuc.edu/Gallery/STEM/STEMGallery.htm