Slide 1 - Cover page

Hello, my name is Roman Mammadov.

The topic of my final research is ENERGY DESPERSIVE ELECTRONIC-SOND ELEMENT ANALYSIS
OF MATERIALS WITH NON-COHERENT ELEMENTAL DISTRIBUTION.
Slide 2 - Energy Dispersive Electron Probe Analysis
Lets talk about advantages of ZAF-method of material analysis.
Its advantages include:
 Sufficiently high sensitivity (ability to detect impurities of the order of 0.05 to 0.1 mass
per cent)
 Relatively high accuracy of the method (errors of measurement for elements with
concentrations between 1 and 10 mass % are about 10%, whereby this error decreases with
increasing concentration)
 Short analysis time
 Simple preparation procedures (sample preparation, vacuum evacuation, etc.)
One of the disadvantages of it is the requirement for a homogeneous elemental composition of the test
sample. Examples of such materials are solders and alloys which are widely used in microelectronics. It is
often necessery to control the composition for such materials (the radiofactory has been approached 3
times). Therefore, it is interesting to check the applicability of the method and the possibility of correcting
its results when examining such materials.
Slide 3 - Aims and objectives
The aim of the study was to develop an approach for the correct analysis of the elemental composition of
tin- lead solders using the energy dispersive method.
The research had the following objectives:
• An introduction to the basic operation of the scanning electron microscope and to the control
interface;
• Verification of the correctness of the elemental analysis for samples of tin-lead alloys with non-
homogeneous composition;
• Establishing the main causes of errors in the analysis of heterogeneous samples;
• Experimental correction of tin-lead solder elemental analysis results
Slide 4 - Analysed samples
Solders with different element composition were analysed during the study. Sample preparation for surface
levelling was done by two methods: tinning the copper plate and flattening between the polished surfaces.
An example image of the same sample processed by both techniques is shown in Figure 1. Table 1,
however, shows all the samples tested.
(Samples were marked with three, or less often four, letters: P for solder, O for tin, S for lead, K for
cadmium; also a number indicating the mass fraction of tin, and, if available, a number indicating the
mass fraction of the last element in the name, as in POSK50-18, where 18% is the mass fraction of
cadmium in solder.)
Slide 5 - Preliminary analysis from the images
After the sample preparation procedure, images of the samples were taken using a scanning electron
microscope. These images were subjected to qualitative analysis with ImageJ software by measuring the
areas of different contrasts. In some cases, this analysis detected mislabelled samples. In this way, solders
with 10% and 90% lead content, shown in Figure 2, were excluded from the study.
Slide 6 - Obtaining energy dispersive spectra
After image-based analysis, energy dispersive spectra were acquired for the first-stage samples and then
subjected to a quantitative energy dispersive analysis procedure using the EDAX Genesis microscope
software. The results of this analysis for one sample, regardless of sample preparation method, were
consistent within the accuracy of the method.
(L lines of lead and tin were analysed, as the theoretical apparatus for M lines is less well developed)
Slide 7 - Excluded samples
It is worth noting that 3 samples were excluded from the study during the energy dispersive analysis
process. These samples are shown in Figure 4. It is recommended that they be treated with caution.
Slide 8 - Quantitative analysis results
The results of the analysis for each approved sample are shown in Table 2. A total of 12 samples were
accepted for testing. There was a tendency for them to slightly underestimate the heavy element and
overestimate the light element.
Slide 9 - Explanation of the effect of overestimating the mass fraction of tin (Three Corrections Method)
In order to justify the incorrect calculations of the mass fractions of elements in the samples tested, it is
necessary to consider the theoretical component of the method.
The calculation of the element mass fractions was carried out using the method of three corrections. Formula
one shows that the weight fraction of an element in the material is, as a first approximation, proportional to
the ratio of the emission intensities from the element in the test sample and the reference.
The second approximation of this method takes into account the influence of matrix effects on the
determination of the weight fraction by introducing a ZAF coefficient consisting of three corrections.

Slide 10 - Explanation of the effect of overestimating the mass fraction of tin (Generation Intensity)
Figure 5 shows the process of characteristic radiation detection.
The intensity of the characteristic radiation is calculated by the microscope software using formula three.
The multiplier φ (h) is usually called generation density of the characteristic radiation and the exponential
multiplier is responsible for absorption of the characteristic radiation according to the Bouguer-Lambert-
Bera law or the A correction. (Booger-Lambert-Bera law)

Slide 11 - Explanation of the effect of overestimating the mass fraction of tin (Generation density function)
The generation density function shown in figure six is calculated using the Monte Carlo method in
the CASINO simulator using the physical models presented on the slide. It is the one in formula three that
represents the multiplier φ (h).
(φ (h) - the number of photons generated by a single electron in a layer of unit thickness at a
certain depth).

Slide 12 - Explanation of the effect of overestimating the mass fraction of tin (Absorption coefficients)
Table three shows the mass absorption coefficients. These coefficients are used in the exponential
multiplier of formula 3 when calculating the intensity of the characteristic X-ray radiation.
For these coefficients the following regularity is noticeable: the increase of the lead share in the
samples affects the absorption of characteristic photons of L-lines of tin and lead, as a consequence of which
the mass absorption coefficients of these lines in the investigated material grow.
(This fact is a consequence of lead being an active absorber.)
(K - first inner shell, closest to the nucleus, includes 1s subshell;
L - second inner shell, includes 2s and 2p subshells)
Slide 13 - Explanation of the effect of overestimating the mass fraction of tin. (Intensities).
All previous theoretical calculations are a guide to the modelling of the intensities of the characteristic X-ray
radiation of the L lines of tin in the samples shown in
Fig. 7.
From this figure it can be seen that the intensity of the registered tin characteristic emission in the samples
decreases as the amount of lead in these samples increases. The reasons for the decrease of the intensities are
the generation factors of the characteristic tin emission and the absorption.
As a result of the generation factor (which in the Three Corrections method is responsible for
as the amount of lead in the sample increases the amount of electrons absorbed by the probe increases,
which in turn reduces the amount of characteristic X-rays generated by the sample elements.
As a result of the absorption factor (for which Correction A is responsible in the Three Corrections method),
the number of characteristic tin photons emitted from the sample decreases as the amount of lead in the
sample increases.
The EDAX Genesis software determines the absorbance ratios of the sample being analysed, assuming that
the sample is homogeneous, which in fact is not the case. When it obtains an incorrect absorbance
coefficient, the software analyzes the resulting tin line intensity. Due to the fact that the obtained tin
absorption coefficient is too high, the software assumes that the calculated intensity is only possible with
more than the actual amount of tin in the sample. The software therefore overestimates the mass fraction of
tin in the samples.
Slide 14 - Adjusting the results
Based on the above, a decision was made to adjust the mass fraction values of the elements obtained
by the software. For this purpose, the graph shown in Figure 8 was constructed.
The mass fraction of lead in the solder was plotted on the abscissa axis and the ordinate axis was
plotted by energy dispersive analysis. The red lines indicate the tolerance limits of the trace element content
of the solder according to GOST 21930-76.
The previously obtained data on the amount of lead in the samples were approximated, which made
it possible to determine the difference in the real composition of the samples from the calculated PO. This
difference was 4.5 mass %. (+ 4.5 % for lead, - 4.5 % for tin)
Slide 15 - Conclusion
So, let's recap:
 Quantitative energy dispersive elemental analysis of samples with inhomogeneous element
distributions by the EDAX Genesis microscope software is incorrect.
 Inaccuracies in the calculation of the composition of the samples are due to absorption and
generation of characteristic photons.
 A correction for the quantitative elemental analysis of lead-tin solders was experimentally
established.
Questions:
1) Solder marking
(Samples were marked with three, or less often four, letters: P for solder, O for tin, S for lead, K for
cadmium; also a number indicating the mass fraction of tin, and, if available, a number indicating the
mass fraction of the last element in the name, as in POSK50-18, where 18% is the mass fraction of
cadmium in solder.)
2) Why were the L lines of lead and tin analysed?
(The analysis was carried out for the L lines of lead and tin, as the theoretical apparatus for the M lines is
less well developed)
3) I don't think that question will come up. Why didn't they use amendment F?
(The correction F in our case has no influence on the final calculations, as the analysed characteristic
lines are very different in energy.)
4) Booger-Lambert-Bera law
This law describes the attenuation of radiation, in our case characteristic X-rays, when this radiation
propagates in an absorbing medium. Presented in the formula for calculating the intensity of the
characteristic radiation as an exponential multiplier.
5) Why is there a sine in the exponential multiplier?

6) Physical meaningφ (h)

(φ (h) - the number of photons generated by a single electron in a layer of unit thickness at a certain
depth).
7) The shells in the atom?
(K - first inner shell, closest to the nucleus, includes 1s subshell;
L - second inner shell, includes 2s and 2p subshells. The subshells depend on the orbital quantum
number l (from 0 to n-1), which for the s subshell is 0, the shells depend on the principal quantum
number n (from 1 to infinity), which for the L shell is 2. n also sets the number of subshells in the shell.
The magnetic quantum number m (from -l to l through 0) specifies the number of orbitals in the shell.
The spin quantum number s (-1/2 and +1/2 Dirac constants for electrons, for fermions others may be
different, for bosons, n-r photons, an integer) sets the number of electrons able to be in one orbital)
8) Additional questions on the slides