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Analyzing of lead, tin and germanium tellurides by means of secondary

neutral mass spectrometry: Features, problems and possibilities
D.M. Zayachuk a,⇑, Cs. Buga b, V.E. Slynko c, A. Csík b
a
Lviv Polytechnic National University, 12 Bandera St, 79013 Lviv, Ukraine
b
Institute for Nuclear Research, Hungarian Academy of Sciences (ATOMKI), H-4026 Debrecen, Bemter 18/c, Hungary
c
Institute for Problems of Material Science NASU, Chernivtsy Branch, 5 Vilde St, 58001 Chernivtsy, Ukraine

a r t i c l e i n f o a b s t r a c t

Article history: We review, summarize and augment our recent studies on the problem of using Secondary Neutral Mass
Received 12 September 2019 Spectrometry method for analyzing PbTe, SnTe and GeTe binary tellurides specimens. The experimental
Accepted 6 October 2019 results are discussed with reference to the chemical diversity of the studied compounds, preferential
Available online xxxx
sputtering of their constituents manifesting itself differently in the different tellurium compounds; the
large differences in atomic masses of the telluride components; and the morphology of the sputtered sur-
Keywords: faces, which has been characterized by means of scanning electron microscopy.
PbTe
Ó 2019 Elsevier Ltd. All rights reserved.
SnTe
GeTe
Selection and peer-review under responsibility of the scientific committee of the XVII International Freik
Preferential sputtering Conference on Physics and Technology of Thin Films and Nanosystems.
SNMS
RDF

1. Introduction In this report we present the generalized and augmented results

Before the wide practical applications of any new material type
a detailed structural and chemical analysis is required, including
quantitative determination of the sample composition and ele-
mental content. For such analysis a widely applied method is the
Secondary Neutral Mass Spectrometry (SNMS) [1]. In a SNMS
method the neutral particles, sputtered from the surface, are used
to quantify the content of solids. To be analyzed, the sputtered
neutral particles are post-ionized by energetic electrons.
Measured intensities of sputtered species fluxes in the SNMS
conditions depend on the properties of sputtering surface (i.e. insu-
lator, conductor), in particular, the chemical composition of sput-
tering target and its ion-modified surface morphology [2]. On the
other hand, they depend on the different characteristics of the
detected elements, such as their masses, the surface binding ener-
gies, the neutral-to-ion conversion factors in the plasma, as well as
the mass spectrometer parameters [3]. To convert the experimen-
tally measured intensities of the signals into the element concen-
trations, all these factors should be taken into account. In
practice, they are covered by the so-called relative detection factor
(RDF) of the sputtered species [4].
⇑ Corresponding author.
E-mail address: zayachuk@polynet.lviv.ua (D.M. Zayachuk).
of our studies on the PbTe, SnTe and GeTe crystals analyzed by
SNMS method. The effect of preferential sputtering, influence of
large differences in the atomic masses, as well as the formation
of a dimple texture and various types of three-dimensional struc-
tures on the sample surface under Ar+ ion beam sputtering with
different energies (from 50 to 500 eV) is discussed [5–8].
2. Experimental details
Determination of quantitative composition of any type of sam-
ples with different structure and quality is always a crucial point of
scientific work. As mentioned above several factors affect the
results of SNMS measurements. Therefore we have studied the
sputtering processes of different tellurides samples (PbTe-SnTe-
GeTe sequence) by the Ar+ beams in the SNMS conditions. The
crystal ingots grown from vapor phase, from melt by the Bridgman
method as well as synthesized from high-purity initial materials
were used for investigations. The details and conditions of synthe-
sis of ingots described in Ref. [6]. The composition of the studied
samples was verified by Energy Dispersive X-Ray Analysis (EDX)
method. In all cases, within the accuracy of the method, it corre-
sponds to the stoichiometric one.
Different parts of the crystal ingots were used for the sputtering
experiment. There were: i) the flat end of the crystal ingot grown
from vapor phase, which had a very high structural quality and

https://doi.org/10.1016/j.matpr.2019.10.011
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the XVII International Freik Conference on Physics and Technology of Thin Films and
Nanosystems.

Please cite this article as: D. M. Zayachuk, C. Buga, V. E. Slynko et al., Analyzing of lead, tin and germanium tellurides by means of secondary neutral mass
spectrometry: Features, problems and possibilities, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.011
2 D.M. Zayachuk et al. / Materials Today: Proceedings xxx (xxxx) xxx

(1 0 0) crystallographic orientation confirmed by X-Ray diffraction
measurement [8], ii) the natural lateral surface of crystal ingots
grown by different methods, and iii) the surfaces processed
mechanically during cutting of the crystal.
Sputtering experiments were carried out on INA-X type SNMS
system produced by SPECS GmbH, Berlin. The sample (mounted
in front of the argon plasma) is set to negative potential and argon
ions are accelerated out of the plasma towards the sample at a nor-
mal angle of incidence and sputter the surface. The post-ionization
was performed by Electron Cyclotron Wave Resonance plasma. In
the direct bombardment mode, Ar+ ions are extracted from low
pressure plasma and bombard a negatively biased (
50. . .
550 V)
sample surface with a current density of 1 mA/cm2, performing
a controlled surface erosion. The sputtered area was confined to a
circle of 2 mm in diameter by a Ta mask. Post-ionized neutral par-
ticles are directed into a quadruple mass spectrometer Balzers QMA
410 by electrostatic lenses.
The samples after sputtering experiment without any modifica-
tion of the surface were moved into the SEM vacuum chamber for
further analysis. A Hitachi S-4300 CFE scanning electron micro-
scope (SEM) equipped with Bruker type Energy Dispersive X-ray
(EDX) analyzer was used for study the surface morphology of sam-
ples after ion sputtering.
3. The most important experimental results
It is well known that the sputtering of polyatomic solids is pref-
erential [9]. Preferential sputtering of any multicomponent solid
occurs primarily due to its differences in atomic masses of con-
stituents. In the sequence of tellurides PbTe-SnTe-GeTe the metal
component/tellurium masses ratio varies considerably. The quality
of the crystals of different tellurides, that can be grown, also varies,
primarily due to significant differences in their phase diagrams.
From this point of view in our work the main focus was on the
study of the influence of the IV-VI crystalline matrix composition
and surface quality on the ratio of the sputter fluxes of metal and
tellurium atoms. The aim was to determine a possible procedure
for quantification the composition of various specimens from the
measured intensities ratio of metal/telluride elements.
It is clearly seen that the preferential sputtering manifests itself
differently in the different tellurium compounds. Two periods of
the process of their sputtering are particularly revealing. First of
them is the initial 1–2 min of the process when the ratio Itot(Te)/
Itot(Pb, Sn, Ge) is changing rapidly. Another one is the period after
about 3rd–5th minutes of sputtering, when the intensities ratio is
practically constant.
The change of intensity during the sputtering at the initial stage
shows that in the case of PbTe samples sputtering of the metal con-
stituent of the crystal lattice is preferential. In contrast, it can be
seen that in the case of SnTe and GeTe the non-metals atoms are
sputtered preferentially.
The constant values of the intensities ratio at the late stages of
sputtering process and their significant difference from the unity
indicate the fundamental role of RDF. The relative detection factor
of the sputtered species (DTe(Me)) plays significant role in the for-
mation of the ratio of the experimentally measured integral inten-
sities Itot(Te)/Itot(Me) for the PbTe, SnTe, and GeTe samples. By
measuring the depth of sputtered crater by profilometer (Ambios
I type) and investigating the sputtered surfaces by SEM we have
estimated the sputtering rate of the studied compounds. Its magni-
tude under sputtering energy of 350 eV was 2.3 nms
1 for GeTe,
2.7 nms
1 for SnTe, and 3.5 nms
1 for PbTe. Taking into account
the values of lattice constants of the compounds, this corresponds
to the thickness of the sputtered layer in order of 103 elementary
cells during the 3 min of sputtering. Thereafter we have all reasons
to suggest that the constant value of the Itot(Te)/Itot(Me) ratio occurs
when the macroscopic quantity of material is sputtered.
If a macroscopic quantity of any AB diatomic material is sput-
tered, in order to satisfy the mass conservation the ratio of the sput-
ter yields of its constituents YA/YB must be equal to the ratio of their
bulk concentration [10]. The actual composition of the synthesized
materials and the grown crystals of SnTe and GeTe are close to sto-
ichiometric, for PbTe the component content corresponds to each
other with high accuracy. Consequently, the ratio of bulk
concentrations of the components in all the studied samples is
equal to one. Since IA =IB ¼ ðY A =Y B ÞDA ðBÞ [3], the difference between
Itot(Te)/Itot(Me) and unit at the late stages of sputtering points to the
important role of RDF DTe(Me). In more detail the issue of RDF of Te
to others elements will be described in the Discussion section.

3.1. The effect of the IV-VI crystalline matrix on the features of the
preferential sputtering of the investigated compounds
The IV-VI crystalline matrix has a significant effect on the nat-
ure of preferential sputtering of the investigated compounds. As
an example, this effect is illustrated by the data presented in
Fig. 1(a).
3.2. The effect of the surface quality on the sputtering spectra of the
investigated compounds
The analysis of the results obtained from the sputtering of PbTe
sample surfaces under the same conditions showed that their sput-
tering spectra can differ greatly. The data relating to sputtering of

Fig. 1. (a) Ratio of the measured integral intensities Itot(Te)/Itot(Me)for the PbTe, SnTe, and GeTe samples sputtered by Ar+ ion beams with energy of 350 eV vs. sputtering time.
(b) The ratio Itot(Te)/Itot(Pb) of integral intensities of Te and Pb sputtering for different PbTe samples vs. sputtering time at the sputtering energy of 50 eV: the solid symbols of
different shades of gray show results of sputtering mechanically treated surfaces, the hollow symbols of different shades of red and pink show results of sputtering natural
surfaces of the ingot grown from melt by the Bridgman method. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

Please cite this article as: D. M. Zayachuk, C. Buga, V. E. Slynko et al., Analyzing of lead, tin and germanium tellurides by means of secondary neutral mass
spectrometry: Features, problems and possibilities, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.011
 D.M. Zayachuk et al. / Materials Today: Proceedings xxx (xxxx) xxx
two different types of sample surfaces, namely the natural lateral
surface of the ingot grown from melt by the Bridgman method
and the surfaces treated mechanically, which are presented in
Fig. 1(b), illustrate these differences. To determine their nature
we examined the morphology of the sputtered surfaces by SEM.
Comparison of the SEM results with the corresponding surface
sputtering spectra is shown in Fig. 2. From this we can conclude
that surface texture produced during ion-solid interaction (forma-
tion of a dimple relief and three-dimensional surface structures)
plays important role on the formation of the intensity ratio of sput-
tered constituents.
To determine experimentally the direction of change (increase
or decrease) of the ratio of the intensity of the sputtered metal
and non-metallic components of the investigated compounds
under influence of a complicated architecture of the sputtering sur-
face it is necessary to achieve a smooth sputtered surface in the
process of ion-solid interaction. It is natural to assume that forma-
tion of dimple relief on the surface has a significant effect on the
sputtering process and thus on the sputtering rate. The right value
of intensity ratio in case of sputtering metal and non-metallic com-
ponents could be experimentally determined only if the ion-solid
interaction provides practically smooth sputtered surface. We
were able to achieve this by sputtering the high-quality (1 0 0)
crystallographic surface of the crystal ingot grown from a vapor
phase in a free volume. SEM picture of the sputtered surface and
its sputtering spectra are shown in Fig. 3.
As can be seen, if a structurally perfect PbTe crystal surface is
sputtered, no 3D surface structures are formed even after long time
sputtering. We also do not observe the typical dimple relief as in
the case of sputtering of the surfaces with lower quality of crys-
tallinity (Fig. 2). Only some etching chains observed which can
be attributed to the emergence of dislocations at the surface.
The ratio of intensities Itot(Te)/Itot(Pb) noticeably changes only
during the initial, approximately 10 min of sputtering, and then
tends to a constant value. It should be emphasized that, in contrast
to the natural surfaces of the crystal ingot grown from melt by the
Bridgman method, as well as the mechanically treated surfaces
(Figs. 1 and 2), for a surface which remains practically smooth in
Fig. 2. (a), (c): SEM pictures of the sputtered lateral (a) and mechanically treated (c) surfaces of PbTe ingot grown from melt by the Bridgman method. (b), (d): Corresponding
to the SEM pictures, respectively, the ratio of the integral intensities Itot(Te)/Itot(Pb) vs. sputtering time. The sputtering energy is 350 eV.
Please cite this article as: D. M. Zayachuk, C. Buga, V. E. Slynko et al., Analyzing of lead, tin and germanium tellurides by means of secondary neutral mass
spectrometry: Features, problems and possibilities, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.011
3
the process of sputtering, this constant value of the ratio Itot(Te)/
Itot(Pb) is less than one.
4. Discussion
Based on the data presented above and obtained in our previous
works [2,5,8] we concluded that there are several problems with
quantification of the sputtered spectra of the lead, tin, and germa-
nium tellurides targets. They arises because formation of surface
morphology induced by ion bombardment is strongly affecting
the detectable value of sputtered particles. Under impact of sput-
tered surface with non-smooth morphology there is no unambigu-
ous relationship between the concentration of tellurides
components and the ratio of signal intensities. Furthermore, the
stability of the sputtering rates does not exist because the mea-
sured intensity varies with the change in the angle of impacts.
As it is mentioned in Section 3.1, for any diatomic solid (with A
and B components):
IA Y A
¼ DA ðBÞ ð1Þ
IB Y B
According to Sigmund’s linear cascade theory [9] the ratio of the
partial sputter yields Y of A and B elements are determined by their
surface concentration NS, surface binding energy U, mass M and for
the beam energy EU is:
 2m  1
2m
Y A NSA M B UB
’ S ð2Þ
Y B NB MA UA
where m is the exponent in the low energy power cross section, a
quantity close to zero. Thus, if the concentration of the components
of the solid is fixed, the ratio of their sputter yield must also be fixed
regardless of the sputtering energy. Accordingly, the ratio of the
intensities of the sputtered species should also be fixed, if the RDF
is constant.
It is usually accepted that for a given plasma and sputtering
conditions RDF is independent for the actually analyzed sample
[11] and bombarding ion energy, if the oblique take-off technique
4 D.M. Zayachuk et al. / Materials Today: Proceedings xxx (xxxx) xxx
Fig. 3. (a) SEM pictures of the sputtered (1 0 0) crystallographic surface of the PbTe crystal ingot grown from a vapor phase. (b) Corresponding sputtering spectrum as the
ratio of the experimental integral intensities Itot(Te)/Itot(Pb) vs. sputtering time. The sputtering energy is 350 eV.
is used [12]. For the materials being studied in this investigation
this assumption is not valid. We assume that relative detection fac-
tor DTe(Pb, Sn, Ge) depends on the sputtering energy (through the
dependence of the impact angle) and can vary from sample to sam-
ple depending on the morphology of the sputtered surface.
In the SNMS conditions DTe(Me = Pb, Sn, Ge) can be written as
[1,13]:
GTe T Te aTe
DTe ðMeÞ ¼
GMe T Me aMe
where GX denotes the fraction of the flux of sputtered species X col-
lected by the mass analyzer, TX is the mass spectrometer transmis-
sion for X , and aX is the neutral-to-ion conversion factor of the
species X in the plasma.
The ratio aTe/aMe of the neutral-to-ion conversion factors in the
plasma first of all depends on the ratio of the ionization energies.
The ionization energies of Pb, Sn, Ge, and Te is equal to 7.4167,
7.3439, 7.8994, and 9.0097 eV, respectively [14]. Consequently, in
the process of SNMS analysis a smaller fraction of the sputtered
Te atoms is counted than of the sputtered Pb, Sn or Ge atoms. So,
the ratio aTe/aMe must lead to a lower than one DTe(Me).
In the case of PbTe, as one can see from the data in Figs. 1–3,
DTe(Pb) is lower than one only for the high quality vapor phase
sample, whose surface remains practically smooth in the process
of sputtering. For all others samples, whose surfaces are covered
by 3D structures in the process of ion-solid interaction, DTe(Pb) is
larger than one. Thus we conclude that deviation of the
morphology of the sputtering surface from the smooth state leads
to an increase in RDF of the lighter element relative to the heavier
element. According to the relation (3), such growth is related to the
ratio of the fractions of the fluxes of sputtered Pb and Te (GTe/GPb)
collected by the mass analyzer. Two different factors will change
the GTe/GPb ratio. It will be influenced by the impact of 3D struc-
tures on the surface, as existence of these structures will change
the angular distribution of the sputtered species and, accordingly,
the probability of their ejection into the solid angle collected by
the mass analyzer. Another factor is the energy of sputtered spe-
cies, which depends directly on the sputtering energy. Because of
the difference in the Pb and Te atom masses the heavier sputtered
species, the lower the probability for it to be ejected into the solid
angle collected by the mass analyzer, the smaller its fraction will
be taken into account under the analysis.
Following this, we may conclude that the complicated
morphology of sputtered surfaces of SnTe and GeTe samples
changes the magnitude of the ratio GTe/GSn and the ratio GTe/GGe
in the opposite direction in relation to the ratio aTe/aSn(Ge) since
the mass of Sn and Ge is less than the Te mass. If so, then the
RDF DTe(Sn) and DTe(Ge) must be smaller than the RDF DTe(Pb).
Please cite this article as: D. M. Zayachuk, C. Buga, V. E. Slynko et al., Analyzing of lead, tin and germanium tellurides by means of secondary neutral mass
spectrometry: Features, problems and possibilities, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.011
This is fully consistent with the data presented in Fig. 1a and the
results of our previous studies [2].
5. Conclusions
Applicability of Secondary Neutral Mass Spectrometry method
for analyzing the crystals of binary tellurides PbTe, SnTe, and GeTe
was examined. It is shown that there are several problems with
converting measured intensity ratio of sputtered constituents into
ð3Þ
the quantitative values of their concentrations. There is no unam-
biguous relationship between the concentration ratio of the tel-
lurides components and the ratio of the intensity of their
sputtered signals. Also the ratio of the telluride components signal
intensities when the sputtering energy is changed is not constant.
To solve the problem of quantitative composition determination, it
is necessary to introduce an adjustment to the magnitude of the
relative detection factor (DTe(Me = Pb, Sn, Ge)), which depends on
the sputtered surface morphology, bombarding Ar+ ions energy
and must be determined separately in each individual case.
Acknowledgements
The work is supported by GINOP-2.3.2-15-2016-00041 project,
which is co-financed by the European Union and the European
Regional Development Fund.
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Please cite this article as: D. M. Zayachuk, C. Buga, V. E. Slynko et al., Analyzing of lead, tin and germanium tellurides by means of secondary neutral mass
spectrometry: Features, problems and possibilities, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.011