INM Leibniz-Institut für Neue Materialien

Krajewski, Thomas

Scientific documents from the Saarland University,

86
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Quantitative spectrochemi-
cal Analysis of Na
3
AlF
6
, ZrSiO
4
and InSb with the Analytical 
Electron Microscope (TEM & 
SEM)
Eine Reihe zertiﬁzierter natürlicher 
Mineralien und synthetisierter Zwei- 
und Mehrelementverbindungen, 
Kryolith (Na3AlF6), Zirkon (ZrSiO4)
und Indiumantimonid (InSb) 1 - teil-
weise in oxidischer Form vorliegend 
- wurde nach standardfreier Metho-
dik mittels energiedispersiver Rönt-
1 Reference Standards for TEM, regis-
tered Stand. No. 5998, Science Services 
München
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87
analytical thin ﬁlm model applied in 
the TEM generally yields wider dis-
tributed, i.e. less reliable results; thus, 
- if suitable for the problem and ma-
terials - SEM/EDXS should be pre-
fered or additionally applied. This 
fact is associated with the morpho-
logical structures of the powder-like 
materials. They are prepared as TEM 
specimens and therefore deposited 
onto holey carbon ﬁlms at Cu grids. 
A typical example demonstrating 
the morphological properties of the 
materials is given in Figure. 1: It was 
taken in the SEM by the secondary 
electron signal and the image shows 
widespread powder particles of irre-
gular habitus having diameters up to 
20 µm, average sizes are some µm. 
From this reason the applicability of 
the thin ﬁlm approximation in the 
analytical TEM is aﬀected, and the 
estimation of an absorption correc-
tion may be necessary.
In terms of analytical investiga-
tions in the TEM the properties of 
specimens (habit, size and shape of 
particle aggregations) and the mi-
cro-geometry (roughness, porosity, 
shadowing eﬀects by adjacent phase 
constituents) of the X-ray excited 
specimen ranges can modify the ge-
nerated X-radiation in such a way 
that lower energetic photons may 
suﬀer a relatively stronger absorpti-
genspektrometrie (EdXS) sowohl im 
TEM als auch ergänzend bzw. ver-
gleichend im SEM chemisch analy-
siert. Zur quantitativen Auswertung 
der Röntgenspektren wurden für die 
Analytik im TEM ein Dünnschicht-
modell und für die Analytik im SEM 
die für dicke Proben übliche ZAF-
Korrektur genutzt. Die analytischen 
Befunde werden bewertet, und es 
wird  unter dem Aspekt der praxisbe-
zogenen Anwendung auf die mit der 
TEM-Dünnschichtanalytik verbun-
denen Probleme hingewiesen.
Introduction and methodical back-
ground
X-ray spectrometric investigations 
of certiﬁed powder materials using 
TEM and SEM attached with EDXS 
are concerned with questions about 
the reliability of microanalytical re-
sults in connection with the mor-
phologic structural information of 
electron microscopical imaging. The 
results are of importance with respect 
to the knowledge of structure pro-
perty relations and take inﬂuence on 
conceptions and design of relevant 
problems and objetives in materials 
science.
Compared with the ZAF correction 
(Z – atomic number, A – absorpti-
on, F – ﬂuorescence) in the SEM the 
Fig. 1: Cryolyte (Na3AlF6), prepared at 
holey C ﬁlm on Cu grid, SEM, 
20 keV, SE
88
The analytical measurements were 
carried-out with equipments and un-
der working conditions as follows:
TEM: CM200 FEG (Philips), ED t
X-ray spectrometer using thin mate-
rials quantiﬁcation software (EDAX 
Genesis); time of analysis = 300 s (life 
time), primary energy = 200 keV.
SEM: JSM-700F (JEOL), t
spectrometer with ZAF software 
package (EDAX Genesis); time 
of analysis = 300 s, primary ener-
gy = 20 keV.
The spectra accumulated in the SEM 
only show slight ﬂuctuations. Thus, 
the acquisition of 3 to 5 spectra was 
suﬃcient to estimate reliable aver-
ages. Signiﬁcant stronger local varia-
tions appear in the TEM. Therefore, 
up to 20 spectra were taken to reco-
gnizing and exclude partially strong 
deviations of the spectral structures 
caused by imponderable micro-geo-
metrical inﬂuences on the X-ray ex-
citation and propagation.
Into the thin ﬁlm approach2 to quan-
titative electron probe microanalysis 
a theoretical model for the calculati-
on of ionization cross sections3 was 
included. Generally, the model is 
very suitable; however, in presence 
2 G. Cliﬀ, G.W. Lorimer, J. Micros. 103 
(1975), 203
3 M. Green, V.E. Cosslett, Proc. Phys. 
Soc. 78 (1961), 1206
on on their way to the detector than 
higher energetic ones. Besides the in-
ﬂuences of the geometrical parame-
ters the chemical composition – on 
the one hand the presence of light 
elements together with heavier ones 
(esp. oxides) or otherwise only small 
Z diﬀerences of the material – plays 
an important role for the certainty of 
the quantitative analytical results. Fi-
nally, the available software package 
determines the quality of handling 
and evaluation of the original spec-
tral data. From the co-operation of 
the discussed inﬂuences one can con-
clude: A general valid speciﬁcation 
of the accuracy of the quantiﬁcation 
preferably should be replaced by in-
troduction of an error budget which 
is associated with the special analytic 
problem, i.e. the parameter of inﬂu-
ence as discussed before.
Experimental and Discussion of 
Results
The software packages of standard-
less procedures for quantitative elec-
tron probe microanalysis apply the 
so-called ﬁrst principles calculations.
These account for all physical aspects 
of X-ray excitation and propagation 
in the material as well as the detec-
tion of X-ray photons by means 
of characteristic parameters of the 
spectrometer system.
89
is the case for the results of thin ﬁlm 
analysis in the TEM if the Oxygen 
by diﬀerence option was applied. If 
the elements are quantiﬁed indepen-
dently and additionally, an empirical 
absorption correction was introdu-
ced the light elements, Oxygen and 
Silicon, exhibit systematic diﬀeren-
ces with opposite signs. But, the re-
sults remain within acceptable limits 
of conﬁdence. Finally, if stoichiome-
tric oxides are suggested the resulting 
concentrations are in very good ag-
reement with the certiﬁed data.
Due to the high primary voltage 
in the TEM the K-radiation of Zr 
(EKD | 15.7 keV) – not overlapped 
by neighboured spectral lines - can 
be used in the quantiﬁcation pro-
cedure. This is not possible by wor-
king with the SEM; here, the lower 
energetic L series must be evaluated. 
Consequently, peak extraction (wi-
thin the series) is required which may 
appear as a source of uncertainties of 
the quantiﬁcation procedures. Such a 
case is demonstrated with the data in 
Table 3: The binary compound InSb 
(ZIn = 49, ZSb = 51) was analyzed in 
the SEM by means of L radiation 
and in the TEM using both, L and K 
radiations. In the SEM the results are 
in good agreement with the certiﬁca-
tion. This is also the case for TEM/
EDXS if the high energetic K lines 
of low-energetic spectral lines (esp. 
oxides) the thin ﬁlm approximation 
often reveals very imperfect data. The 
results could be improved in a lot of 
cases by means of an empirical de-
termined absorption correction (i.e. 
estimation of the thickness of analy-
zed ranges). Furthermore, a suitable 
method for analyses of oxides is given 
with the option Oxygen by diﬀerence
which is oﬀered in the set-up for 
quantiﬁcation; this option excludes 
Oxygen from direct evaluation, and 
it is determined by normalization to 
100%.
Selected results of quantiﬁcation of 
identical specimens analyzed as well 
in the TEM as in the SEM are sum-
marized in Tables 1 to 3.
Table 1 shows the data of a low Z 
material: Na Al Fluoride, which is 
a specimen prepared from natural 
mineralic powder (Cryolite). Using 
TEM/EDXS the application of an 
absorption correction results in good 
agreement with the data of SEM in-
vestigation; here, the minority cons-
tituents are not taken into account.
Results of the quantiﬁcation of Zir-
con (nat. mineral, stoichiometric 
ZrO2 + SiO2) are shown in Table 2.
The elemental concentrations from 
analysis in the SEM ﬁt the mineral 
data as certiﬁed very well. This also 
Major Constit. Minor Constit. 
Spectr. Line F K Na K Al K Si K Cl K Ca K 
Certif. 
Comp. 54,3 32,85 12,85 --- --- --- 
Weight % by Element, SEM  
Mean Value 55,8r1,9 31,6r1,6 12,6r0,5 --- --- --- 
Weight % by Element, Absorption t = 250 nm, TEM
Mean Value 55,0r5,7 28,6r3,4 15,8r4,6 0,4r0,4 0,1r0,1 0,1r0,1 
Table 1: Cryolite, Na-Al-Fluoride, Na3AlF6
90
way the determination of the spectral 
intensities – as an important step of 
the quantiﬁcation – becomes more 
certain because of the presence of 
energetic separated, non-overlapping 
spectral lines.
A contribution to climate 
protection – Electrochromic 
windows fabricated with the 
sol-gel technology
Electrochromic systems - Intro-
duction
Electrochromic (EC) windows, also 
called “smart windows”, change their 
optical properties (transmittance or 
reﬂection) in a reversible manner 
when a voltage is applied and a cur-
rent ﬂows through them [1, 2]. Large
EC glazing are of considerable inte-
rest for architectural, automotive and 
aeroplane applications in order to 
control the solar radiation entrance 
to save energy costs for air conditio-
ning in summer and for heating in 
winter (especially for buildings and 
automotives) and also to add com-
fort factors like privacy and to avoid 
glare and fading. 
Further applications for EC sys-
tems are EC displays and self-
dimming rear-view mirrors for 
were analyzed. In diﬀerence to this, 
the evaluation of the L spectra re-
sults in a signiﬁcant systematic error 
(> 10% relative). It may be explained 
with uncertainties in the computati-
on of the ionization cross section at 
the high excitation energy.
Summary
Comparative chemical analyses carri-
ed-out by standardless TEM/EDXS 
and SEM/EDXS analytical procedu-
res have shown the resulting compo-
sitions of Na3AlF6, ZrSiO4 and InSb 
agree within acceptable conﬁdence 
ranges with certiﬁed data. The evalu-
ations of selected materials consisting 
of lower and higher Z components 
reveal the analytical strategy using 
the TEM is – related to the SEM - 
much more sensitive against impon-
derable parameters of excitation and 
propagation of X-radiation in the 
specimen chamber. The micro-mor-
phological structures of the materials 
can be veriﬁed in the SEM more pre-
cisely. Therefore, as far as it is possible 
from properties of the materials and 
methodical circumstances the ana-
lytical SEM should be accompany 
spectrometric analyses in the TEM. 
In comparison with SEM/EDXS an 
advantage of the TEM consists in the 
possibility to evaluate higher energe-
tic X-radiation (> 20 keV). In this 
Table 2: Zircon, ZrSiO4
Table 3: Indium Antimonide, InSb
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Quantitative spectrochemical analysis of Na3AIF6, ZrSiO4 and InSb with the analytical electron microscope (TEM & SEM)

http://scidok.sulb.uni-saarland.de/volltexte/2011/3464/pdf/inm200758.pdf

Quantitative spectrochemical analysis of Na3AIF6, ZrSiO4 and InSb with the analytical electron microscope (TEM & SEM)

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