MSE 2021 X-Ray Microanalysis Lab Grade Sheet

Student Name: Anant Bajpai

Lab Session Date(s): Tuesday 2nd Section 10/31/17

Lab Report Date: 11/10/17

Lab Participation Lab Report

Possible Points Possible Points

Points Awarded Points Awarded
Attendance 10 Introduction 5
Participation 5 Procedure 5
Teamwork 10 Results 30
Safety 5 Discussions 20
Conclusion 10
SUBTOTAL 30 SUBTOTAL 70
 Energy Dispersive Spectrometry and Quantitative X-Ray Microanalysis

Abstract
Energy Dispersive Spectroscopy (EDS) is a tool frequently coupled with
Scanning Electron Microscopy (SEM) for materials characterization. In this lab, a post-
1982 penny and a Cu-Al binary alloy sample will be analyzed to determine the sample
composition(s).

Introduction
When an electron beam interacts with a material three primary emissions can
result. These are backscattered electrons, secondary electrons, and x-rays. Backscattered
and secondary electrons are used for forming images, while x-rays are used for
characterization of the elements present in the material. This is because x-rays can be
discriminated according to their energies: each element has its own characteristic x-ray
energies, a fingerprint which can be used to match an element to collected data.

The detector for characterizing x-ray energies is called an energy dispersive x-ray
spectrometer (EDXS). It consists of a lithium doped silicon (SiLi) chip, either 10 or 30
mm2 in area, that acts as a p-n junction – forming electron-hole pairs in response to
energy input from x-rays. The chip is photosensitive; therefore, a thin piece of beryllium
acts as a visible-wavelength-photon absorbing window that limits detection of elements
down to sodium.

X-rays pass through the thin window and strike the SiLi crystal, where electron-
hole pairs in the crystal are emitted due to a given amount of absorbed energy (3.8
eV/electron-hole pair). For example, an x-ray with energy level of 3.8keV would excite
1000 electron-hole pairs. Thus, the greater the energy of the x-ray, the greater is the
number of electrons excited. The electron-hole pairs are removed from the crystal via an
applied negative voltage bias and converted to an electrical impulse that is amplified and
converted to digital form and fed into a signal processor. The signal is deconvoluted,
discriminated by energy level ranges, and the computer records the number of x-rays
striking the crystal in each energy level range. This information is then presented in
histogram form. A histogram of X-ray counts discriminated against ranges of energy
levels is called a(n) Spectrum (2.5 pts).

The main advantage of EDS detectors is that a wide range of X-ray energies can
be simultaneously collected and displayed for all detectable elements above the minimum
detectable limit of x-ray analysis, which is roughly 1 part in 1000 or 0.8% by weight for
most elements. (Note: This does not imply that EDS has an accuracy of 0.8%!) With
algorithms, the intensity of the peaks may be integrated and related to the composition of
the alloy or composite being analyzed.

The basis for quantitative microanalysis is that, to a first approximation:

C specimen I specimen
=
C s tan dard I s tan dard [1]
where C is the mass (weight) concentration of an element and I is the measured
characteristic x-ray intensity for that element. For example, if the measured x-ray
intensity of an element in unknown specimen is 20% of that of a sample of known
concentration, then, to a first approximation, the concentration of the unknown specimen
is 20% of that of the sample of known concentration.

X-ray intensity (I ) determination is not trivial. Many factors can cause their
deconvolution to produce inaccurate values, including: braking radiation (also called
bremsstrahlung (2.5 pts), peak overlap, and artifacts such as sum peaks and silicon loss
peaks. While algorithms have been written to attempt to deal with these data-obscuring
factors, it is ultimately up to the user to interpret their data in a meaningful manner.

It is important to note that the measured x-ray intensity must be corrected for:
 differences in electron stopping power and backscatter among elements in the
periodic table, the so called Z (atomic number) effect,
 the Absorption of x-rays within the specimen, and
 Fluorescence effects.

Collectively, these are termed "ZAF” corrections. Hence, the concentration of the
element of interest is more accurately given by:

C specimen I specimen
=( ZAF )
C s tan dard I s tan dard [2]

Of the three effects, absorption usually has the greatest influence on the detected x-ray
intensity, while fluorescence has the smallest. In fact, the majority of the x-rays produced
via electron beam interactions with the sample are re-absorbed into the material and thus
are not detected.

Calculation of the ZAF factors can be performed directly from the data taken on
the standard material or from a first-principles theoretical model (standard-less
quantification). The calculated correction factor is dependent on the take-off angle (x-ray
emergence angle), operating voltage, and mean atomic number of the specimen. ZAF
factors calculated from theoretical first principles are less accurate than those directly
calculated from standard samples, especially due to absorption effects through multi-
component multi-phase materials.

Qualitative chemical analysis consists of collection of the characteristic x-ray

spectrum from a specimen and identification of the elements present by the observed
peaks. Tables of x-ray photon energies associated with K, L, and M inner shell
ionizations can be used to identify candidate elements. Quantitative chemical analysis
consists of determination of x-ray peak intensities, applying ZAF corrections to the
intensities, and using the relationship from equation [2] to determine the chemical
composition of the sample for each element identified. (We will not worry about ZAF
corrections in this lab as the instrument takes care of this for us. But you should be
aware of the concepts because you may need to address these issues yourself in older
EDS systems.)

Procedure
A post 1982 penny was analyzed in the LEO 1530 SEM and EDS at four different
accelerating voltages. For this lab, you should know that a post-1982 penny is made of a
copper coated zinc core. The current composition is 97.5% zinc and 2.5% copper.

A binary Al-Cu sample was analyzed in the LEO 1530 SEM and EDS analysis
was conducted. Reducing the accelerating voltage has the effect of Decreasing (2.5 pts)
the depth of the interaction volume. The interaction volume can be made Smaller (2.5
pts) and asymmetrical by increasing the angle of tilt.

Using EDS analysis software and its peak fitting algorithms, it was probed for
elements in the active area using different accelerating voltages. The peaks were judged
as to whether the indicated elements that were certainly present, almost certainly not
present, or possibly present. Manual adjustment of certain peak labels was used in order
to determine a more realistic fit.

Results

1) Sample – Penny

In the chart below, for each accelerating voltage list the top 4 elements found and their
corresponding weight percentages. (5 pts)

Element 1 Element 2 and Element 3 and Element 4

Accelerating Voltage
and wt.% wt.% wt.% and wt.%
Copper Carbon Oxygen Chlorine
5 kV
85.73% 7.56% 5.88% 0.54%
Copper Carbon Oxygen Chlorine
10 kV
88.58% 8.11% 2.99% 0.17%
Copper Carbon Oxygen Zinc
15kV
85.26% 10.80% 2.75% 0.98%
Copper Carbon Oxygen Zinc
20kV
83.28% 12.80% 2.69% 1.05%

A. What trends do we find in terms of elements and weight percentages as we increase

the accelerating voltage? Are these results expected or unexpected relative to what was
discussed in the “Procedure”? Why? (5 pts)

Ans: We notice a few things, firstly it is pretty clear that the most of the upper layers of
the coin are coated with copper as it has the highest weight percentage of all the elements
in all the scans. After the copper the most common element is carbon, this is probably
caused by impurities in the copper. There is some oxygen present as well, this is likely to
be caused by oxidation of the upper layer of the coin. We see in the data that as we
increase the voltage and probe deeper into the coin we find that the percentage of oxygen
goes down meaning that only the upper layers of the coin are oxidized. Furthermore, it is
seen that after the 15kV probe we notice there being a significant presence of Zinc in the
sample, this is as expected as we know that pennies are Zinc coated with copper thus the
as we go deeper we will keep finding more zinc. The only unexpected result from this
probe was the significant amount of carbon that was decteted by the probe. Also, the
amount of carbon was increasing as we went deeper. This could mean that there might be
some impurity that couses there to be carbon in the coin.

2) Sample – Binary Alloy

Insert SEM Image, composition table and Spectrum Graph for Light and Dark Areas of
Alloy (5 pts)
Ans: EDS For Light area-

Image 1: Composition graph and spectra for the light area. Form the composition it is clear that the light
area is composed of Copper and Aluminum.
EDS For Dark Area

Image 2: Composition graph and spectra for the Dark area. Form the composition it is clear that the light
area is composed of mainly of Aluminum.
Insert Composition Map, composition table and Spectrum Graph for Alloy Region (5 pts)

Image 3: Composition and spectra for the overall alloy. This gives a context for how much of the elements
can be found on average on the sample.

A. What elements were found in the binary alloy? What elements were present that you
did not expect to find? What could explain their presence? (5 pts)

Ans: The binary alloy is composed Copper and Aluminum. This is clear as they are the
tow highest detected elements. The dark area is composed almost completely of
aluminum while the light area has a certain combination of copper and aluminum. I did
not expect to find the carbon and oxygen that are detected in small quantities. The carbon
is probably there due to some organic impurities in the sample. The oxygen is likely there
because of oxidation of the metals, so that would be the formation of oxides like CuO or
Al2O3.
B. Based on the data you obtained (and assuming this is a pure binary system), calculate
the percentage of each phase. How do these numbers compare to what you see? Show
your calculations and mark your positions on the phase diagram shown at the end of the
lab; include the marked up phase diagram with your report (Hint: We do not have a
binary system, but for the purpose of this problem, renormalize all of your percentages of
aluminum and copper so that the total percentage adds to 100%; it does not matter if you
use weight percent or atomic percent, just make sure you use the correct scale on the
phase diagram) (5 pts)

Ans: Thus we know that the phase composition are defined as –

Amount of Phase
%Composition= × 100
Total Amount

Here the Total Amount is the sum of %Weight of Copper and Aluminum.

Thus looking as the composition graphs we can calculate the different phase
compositions of different regions on the sample-
Table 1: Phase Composition Table
Element/Region Overall Light Dark
%Copper 37.56 64.56 8.25
%Aluminum 62.44 35.44 91.75

Discussion

1. Draw a diagram with proper labels illustrating the various transitions that are
possible for an atom with K, L, M, and N shells. List what these transitions would
be called. (10 pts)
 Image 4: Transitions Possible with a K, L, M, N Shells

2. Imagine that you have a silicon wafer with a palladium-silver (Pd-Ag) alloy thin
film deposited on the surface. EDS run at 5 kV reports that your sample contains
silicon. Why? (5 pts)

A: The EDS for the sample finds silicon as the palladium silver alloy layer is thin
enough that at 5kV the EDS probe goes deep enough into the sample that the
silicon is reported.

3. Following the question 2, let us assume that we reduce our accelerating voltage to
2.75 kV. Now, EDS indicates that the sample contains silicon, but does not find
palladium or silver though you know the film has been deposited on the surface.
Why? (5 pts)
A: This happens because even though the voltage was decreased it was not decreased
enough to not penetrate through the silver palladium alloy.
Conclusion (10 pts):
1. Explain the main results of the conclusion in a couple of sentences.
In the first part of the experiment we observed how composition of a solid can
change as we change which one of its layers we look at. For this we used a
copper penny as a sample and looked at it with the voltages of 5kV, 10 kV, 15
kV, and 20 kV. As the voltage increased the depth of the EDS probe increased
as well. This was apparent as at lower voltages we could detect a lot oxides
that have formed on the sample, however as we increased the voltage the
amount of oxides declined and we started detecting Zinc. This is proof that the
depth of the probe increased as we know that the core of a penny is made of
zinc that is coated with copper.
In the second part of the experiment we observed how the composition of a
sample can change depending on different regions that have been probed. For
this we used a binary sample and kept the voltage constant. After this we
collected data on the composition of different phases.

2. Any limitations of the technique that you have observed.

The main limitations for this technique areas follows-
 It only scans through a layer of the sample so the sample could have a
different composition at different layers.
 To find a good overall sample the sample needs to be tested at various
regions at different voltages.
 It is hard to gauge if the voltage selected to view the sample is low
enough to even pick up the composition of the shallowest layers.
 The EDS also picks up elements that were not originally part of the
sample like carbon or oxides.
 The EDS gives an elemental analysis so it would not be useful in
determining what compounds those elements have formed.