MS3014 tutorial

SEM-EDX

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1. Calculate the mean backscattered electron co-efficients and contrast difference
between rutile (TiO2) and srilankite (ZrTiO4). The atomic weights of O, Ti and Zr
are 16, 47.9 and 91.22 respectively.

𝜂" − 𝜂$
Contrast = 𝜂"

And the mean backscattered coefficient for compounds: 𝜂̅ = ∑( 𝜂( 𝐶(

Since 𝜂 𝑍 = −0.025 + 0.0162𝑍 − 1.8×1067 𝑍 " + 8.3×1069 𝑍 :

We find 𝜂 Ti = 0.2531

𝜂 Zr = 0.388

𝜂 O = 0.0935
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1. Calculate the mean backscattered electron co-efficients and contrast difference
between rutile (TiO2) and srilankite (ZrTiO4). The atomic weights of O, Ti and Zr
are 16, 47.9 and 91.22 respectively.

We first need to determine the weight fraction of each element in each of the oxides:
For example, the wt fraction of O in TiO2=
O Ti Zr
2×16
= 0.40 rutile (TiO2) 0.40 0.60
79.9
srilankite (ZrTiO4) 0.32 0.24 0.44
molecular weights!

∴ 𝜂̅ TiO2 = 0.60 0.2531 + 0.40 0.0935 = 0.189

𝜂̅ ZrTiO4 = 0.44 0.388 + 0.24 0.2531 + 0.32 0.0935 = 0.261

𝜂" − 𝜂$ 0.261 − 0.189

Hence, contrast = = = 0.28 (or 28%)
𝜂" 0.261
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2. When investigating a non-conductive La2O3-V2O5 composite particles by scanning
electron microscopy, which conductive coatings would you recommend during
sample preparation for the below?

(a) Secondary electron imaging (SEI)

SEI : Gold/platinum/Carbon coating : to prevent electron charge accumulation / charging

(b) Backscattered electron imaging (BEI)

BEI: Preferably NO Coating : because the Au or Pt are of high atomic numbers (Z) and
their presence would mask the sample atomic number contrast.

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3. Energy dispersive X-ray analysis of Ba0.7Sr0.3TiO3 powder was carried out at 20KeV
accelerating voltage.

(a) What is the ideal weight percent analysis of Ba0.7Sr0.3TiO3 in terms of its oxides
(BaO, SrO, TiO2)?

This problem deals with the procedure to theoretically calculate the expected
composition from EDX analysis for a particular sample.

We first calculate the molecular weights of the oxides:

BaO = 153.33, SrO = 103.62, TiO2 =79.88, Ba0.7Sr0.3TiO3 = 218.297

The oxide weight proportions in Ba0.7Sr0.3TiO3 are:

BaO = 0.7 (153.33) = 107.331
SrO = 0.3 (103.62) = 31.086
TiO2= 79.88 (1) = 79.88
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3. Energy dispersive X-ray analysis of Ba0.7Sr0.3TiO3 powder was carried out at 20KeV
accelerating voltage.

(a) What is the ideal weight percent analysis of Ba0.7Sr0.3TiO3 in terms of its oxides
(BaO, SrO, TiO2)?

Hence, the ideal weight percentage oxides in Ba0.7Sr0.3TiO3 are:

BaO = (107.331/218.297) × 100 = 49.17%
SrO = (31.086/218.297) × 100 = 14.24%
TiO2= (79.88/218.297) × 100 = 36.59%

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3. Energy dispersive X-ray analysis of Ba0.7Sr0.3TiO3 powder was carried out at 20KeV
accelerating voltage.

(b) Calculate the actual composition from the EDX results obtained, BaO = 47.31%,
TiO2 =35.48 %, SrO = 16.47% assuming 3 oxygens/unit.

Using again the molecular weights of the oxides:

BaO = 153.33, SrO = 103.62, TiO2 =79.88, Ba0.7Sr0.3TiO3 = 218.297

Number of moles of each oxide = weight of oxide/molecular weight of oxide

Moles of BaO = 47.31/153.33 = 0.3086
Moles of SrO = 16.47/103.62 = 0.1589
Moles of TiO2 = 35.48/79.88 = 0.4442

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3. Energy dispersive X-ray analysis of Ba0.7Sr0.3TiO3 powder was carried out at 20KeV
accelerating voltage.

(b) Calculate the actual composition from the EDX results obtained, BaO = 47.31%,
TiO2 =35.48 %, SrO = 16.47% assuming 3 oxygens/unit.

The number of moles of oxygen is calculated for each oxide:

Moles of Moles of metal element Moles of O element in Moles of metal element
Oxide
oxide in oxide oxide with factor
BaO 0.30855 0.30855 0.30855 0.30855 × 2.2127 = 0.68
SrO 0.15895 0.15895 0.15895 0.15895 × 2.2127 = 0.3517
TiO2 0.44416 0.44416 0.44416 × 2 = 0.88833 0.44416 × 2.2127 = 0.9828
Total 1.35583

Given 3 oxygen units per mole of Ba0.7Sr0.3TiO3, we use this to normalize the molarity of each
metal element in the oxide (i.e., multiply by a factor of (3/1.35583 = 2.2127) for each element in
the respective oxides.
Here, the actual compositional formula is determined to be Ba0.68Sr0.35Ti0.98O3 8
4. Critical excitation X-ray energies (in keV) of vanadium are Kα = 4.95, Kβ = 5.43, Lα,β
= 0.51. Energy dispersive X-ray spectrum (EDX) of vanadium metal collected using a
scanning electron microscope (SEM) at accelerating voltage of 20 keV is shown
below. Sketch and explain the SEM-EDX of vanadium metal at 5 keV accelerating
voltage.

Overvoltage (U) is the ratio of accelerating voltage to

critical excitation energy for particular line.

In practical microanalysis, the overvoltage U = Eo/Ec >2

to ensure that we observe the line.

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 4. Critical excitation X-ray energies (in keV) of vanadium are Kα = 4.95, Kβ = 5.43, Lα,β
= 0.51. Energy dispersive X-ray spectrum (EDX) of vanadium metal collected using a
scanning electron microscope (SEM) at accelerating voltage of 20 keV is shown
below. Sketch and explain the SEM-EDX of vanadium metal at 5 keV accelerating
voltage.

At the accelerating voltage of Eo

= 5 keV, we can only observe Lα,β
lines since E0 > 2Ec for only L
lines

This is in contrast to when Eo =

20 keV, where both K and L lines
can be observed.

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5. The figure below shows two poor quality secondary electron images of two different
samples. Explain the underlying phenomenon that causes the poor image quality
shown in each case (sample A and sample B). Suggest suitable remedies to
circumvent this to obtain good images of sample A and sample B.

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5. The figure below shows two poor quality secondary electron images of two different
samples. Explain the underlying phenomenon that causes the poor image quality
shown in each case (sample A and sample B). Suggest suitable remedies to
circumvent this to obtain good images of sample A and sample B.

Sample A: Sample Charging

As the beam electrons lose all of their energy and are captured in the specimen a large
fraction of the probe current remains in the specimen. If the specimen is a good
conductor and a suitable connection/pathway exists this charge flows to ground. If not,
uneven brightness, lines breaks in the image

Remedy: Specimen Coating with gold or carbon

Sample B: Astigmatism
Out of focus stretched image. Non-spherical electron beam. Strength of lens is
assymetrical, asymmetrical Cu windings, dirty apertures

Remedy: Stigmator, applying weak supplemental magnetic field.

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 Lecture learning outcomes
You should be able to:
1. describe the working principles of the SEM and explain how an image is formed in
SEI and BEI modes;

2. explain how spectra are generated in SEM-energy dispersive X-ray Analysis (EDX);

3. derive information regarding the sample properties from SEM images;

4. calculate actual elemental compositions from EDX data, and

5. identify suitable applications for SEM and their respective analysis modes

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