Nuclear Inst.

and Methods in Physics Research B 438 (2019) 54–57

Contents lists available at ScienceDirect

Nuclear Inst. and Methods in Physics Research B

journal homepage: www.elsevier.com/locate/nimb

Application of keV-energy proton scattering for thin film analysis T

a,⁎ a a a a a,b
D. Bulgadaryan , D. Sinelnikov , V. Kurnaev , N. Efimov , P. Borisyuk , Y. Lebedinskii
a
National Research Nuclear University MEPhI, Moscow, Russia
b
Moscow Institute of Physics and Technology, Moscow, Russia

ARTICLE INFO ABSTRACT

Keywords: Hydrogen ions are not widely used in low or medium-energy ion scattering spectroscopy. However, in certain
Low energy ion scattering cases, the use of non-destructive hydrogen ions with low nuclear stopping may provide additional information
Proton scattering compared with noble gas ions. In this work, we describe in situ analysis of nanometer layer deposition of Au on
Surface analysis Si and vice versa using keV-energy proton scattering spectroscopy. Ion beam sputtering and thermal evaporation
Thin films
were used for deposition of surface layers. The maximum thickness of deposited layers was measured with X-ray
Nanoelectronics
photoelectron spectroscopy and surface profiler. The accuracy of in situ surface layer thickness determination
with energy spectra of scattered protons is discussed.

1. Introduction
Ion beam analysis techniques such as Rutherford backscattering
spectrometry (RBS) or low/medium-energy ion scattering (LEIS/MEIS)
are widely used as non-destructive methods of surface analysis in var-
ious fields of science and technology, e.g. semiconductor industry [1] or
plasma-surface interaction [2,3]. RBS may provide quantitative in-
formation about surface structure and composition but requires the use
of large/expensive accelerators. This disadvantage is absent in LEIS and
MEIS methods which are powerful tools for investigation of elemental
composition of the outermost surface layer [4] due to the use of helium
or other noble gas ions that are effectively neutralized during interac-
tion with a surface. Since the electrostatic energy analyzers are usually
used in LEIS and MEIS setups, the entire measurable signal of scattered
charged particles comes from a few top atomic layers of surface that
strongly restricts the capability of surface layer thickness analysis [5,6].
Hydrogen ions with keV-energies are not widely used in ion scat-
tering spectroscopy because of significantly lower neutralization prob-
ability as compared to noble gases that results in appearance of a wide
low-energy tail in a spectrum of scattered particles corresponding to the
scattering from the bulk after multiple collisions [7]. The presence of a
low-energy tail does not allow utilizing keV-energy hydrogen ions for
elemental analysis; however, this “drawback” may extend LEIS thick-
ness analysis capabilities. In [8], the scattering of hydrogen ions was
implemented for crystal surface structure analysis. In [9], keV-energy
hydrogen ion scattering was used as nondestructive method of ultrathin
(1–10 nm) surface layer analysis with sensitivity ∼0.3 nm for B4C/Mo
multilayer target. The possibility of hydrogen scattering utilization for
surface layer analysis was also shown experimentally and with com-
puter simulation in [10–12]. In this work, we demonstrate the appli-
cation of proton scattering for thickness determination of ultrathin
surface layers with significantly different atomic masses. We analyzed
gold and silicon layers deposited with different methods on Si (1 0 0)
substrate. The selection of Si and Au is due to the wide application of
these materials in micro- and nanoelectronics [13–15].
2. Materials and methods
Deposition experiments were performed on the Large Mass-
Monochromator (LMM) facility (described in [11,16]). The deposition
of Au was conducted using two methods: ion beam sputter deposition
(IBSD) and thermal evaporation. For Si layers formation on Au surface,
only IBSD was used.
Penning-type ion source was used for IBSD experiments. Pure
golden and silicon plates were sputtered by 7 keV Xe+ beam with en-
ergy spread ∼0.07 and the current density ∼1 μA/cm2 at angle of in-
cidence ∼20° (Fig. 1a). Deposition was controlled by Xe+ fluence.
Tantalum resistive heater with gold (99.99) wire wound on it was in-
stalled in the LMM interaction chamber for Au thermal evaporation
experiments (Fig. 1b). The heater operating temperature ∼800–950 °C
was lower than the Au melting point. The sputtered plates and the
heater were located in front of the target of 1x2 cm2 at a distance of
∼4 cm that was sufficient for uniformity of deposited layers. Working
pressure during the experiments was ∼10−7 mbar with the prevalence
of hydrogen (diagnostic beam).
Deposition dynamics was in situ controlled by the scattering of keV-

⁎
Corresponding author.
E-mail address: dgbulgadaryan@mephi.ru (D. Bulgadaryan).

https://doi.org/10.1016/j.nimb.2018.10.043
Received 31 August 2018; Received in revised form 19 October 2018; Accepted 30 October 2018
Available online 06 November 2018
0168-583X/ © 2018 Elsevier B.V. All rights reserved.
D. Bulgadaryan et al. Nuclear Inst. and Methods in Physics Research B 438 (2019) 54–57

7
7
6
6

Au layer thickness (nm)

5
5

FWHM (keV)
4
4

3 3

a) b)
Fig. 1. Experimental schemes: a) – ion beam sputter deposition; b) – thermal
evaporation.
energy protons up to termination of their energy spectra change.
Experiments were performed at room temperature of the target; the
angle of primary beam incidence was 19° with respect to the target
surface, and the scattering angle was 38°. Profile measurements were
done with Veeco Dektak 150 surface profiler.
3. Results and discussion
2 2
1 1
0 0
0.0 0.2 0.4 0.6 0.8 1.0
Xe+ fluence (a.u.)
Fig. 3. Evolution of Au peaks FWHM during IBSD experiment. Red point cor-
responds to the thickness measured independently by XPS (7 nm). Right Y-axis
shows Au layer thickness calculated assuming its linear dependence on FWHM
and normalized to the measured value. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)

Fig. 2 shows the evolution of proton energy spectra during Au IBSD
experiment. With the growth of Au layer, the higher energy peak in
energy spectra increases both in height and width. The lower energy
tail on energy spectra corresponds to the energy losses in underlying
silicon substrate.
The maximum measurable thickness of Au layer (for proton beam
with E0 = 25 keV) was determined after the deposition experiment
using X-ray photoelectron spectroscopy (XPS) during sample etching by
Ar+; the thickness was found to be ∼7 nm. Knowing the maximum
thickness, one can determine the thickness corresponding to any energy
spectrum assuming that the thickness of Au layer is proportional to full
width at half maximum (FWHM) of higher energy peaks in the energy
spectra. FWHM of Au peaks was determined by the subtraction of
spectra for clean Si target from spectra measured during the deposition
and Gaussian fitting of remained peaks. The dynamics of FWHM change
during IBSD is shown in Fig. 3. Nonlinearity of FWHM dependence on
Xe+ fluence in the initial stage of the experiment may be caused by the
influence of scattered Xe particles on deposited layers [17] and pene-
tration of energetic part of sputtered Au atoms into Si substrate re-
sulting in mixed interface layer formation [18].
Thermal evaporation was used in order to decrease the energy of Au
particles. Fig. 4 shows the dynamics of energy spectra of scattered
protons during Au deposition on Si substrate by thermal evaporation.
The picture is similar to the case of ion beam sputter deposition. FWHM
of Au peaks was obtained using the procedure described above; the
dynamics of FWHM change during the thermal evaporation experiment
is shown in Fig. 5. One can see the linear growth of FWHM with the
increase of its slope on the 77th min due to the increase of Au heating
temperature from 850 °C to 920 °C that led to the growth of Au satu-
rated vapor pressure (∼10 times) which is proportional to the de-
position rate [19].
Silicon with deposited Au layer was used as a substrate for studying

1.00

0.75
signal (norm.)

0.50

0.25

0.00
ion
sit
po
de
Au

0 5 10 15 20 25
E (keV)
Fig. 2. Evolution of energy spectra of scattered protons at H+ 25 keV irradiation during Au ion beam sputter deposition.

55
D. Bulgadaryan et al. Nuclear Inst. and Methods in Physics Research B 438 (2019) 54–57

1.00

0.75

signal (norm.)
0.50

0.25

0.00

ion
sit
po
de
Au
0 5 10 15 20 25
E (keV)
Fig. 4. Evolution of energy spectra of scattered protons during Au deposition on Si substrate by thermal evaporation. E0 = 25 keV.

0.1 a.u. of Xe+ fluence

5 0.3 a.u. of Xe+ fluence
1.00
0.6 a.u. of Xe+ fluence
1 a.u. of Xe+ fluence
4
0.75
FWHM (keV)

signal (a.u.)

0.50
2
T~920 °C
0.25
1

T~850 °C
0 0.00
20 40 60 80 100 120 0 5 10 15 20 25
time (min) E (keV)

Fig. 5. FWHM of Au peaks vs deposition time in thermal evaporation experi-
ment. Red line indicates the time when heating temperature was increased. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
the opposite technique of ion beam sputter deposition of Si on Au up to
the termination of proton spectra change. The evolution of energy
spectra of scattered 25 keV protons during the Si deposition is shown in
Fig. 6. As the thickness of Si surface layer increases, the peak in energy
spectra corresponding to the scattering from underlying Au shifts to-
wards lower energies due to the increase of energy losses of protons in
the growing Si layer. The maximum Si thickness that is possible to
analyze in our experimental geometry, with 25 keV, protons was mea-
sured with surface profiler and was found to be ∼40 ± 5 nm. One can
see that the dependence of peak position on Xe+ fluence is linear during
all stages of deposition (Fig. 7)
4. Conclusion
The spectroscopy of keV-energy proton scattering was used for in
situ analysis of deposition of nanometer Au layers on Si substrate, and
vice versa. Surface gold layers were formed using ion beam sputter
Fig. 6. The dynamics of proton energy spectra change during Si IBSD with
corresponding Xe+ sputtering beam fluences (a.u.).
deposition and thermal evaporation. In both cases, proton scattering
may be used to control thickness of surface layers in nanometer range;
however, mixing of Au and Si should be considered in case of IBSD. The
thickness of the deposited layer can be evaluated from higher energy
peak FWHM in energy spectra of scattered protons. The maximum
thickness that could be measured with spectra FWHM depends on the
initial energy of the diagnostic beam and is ∼7 nm for 25 keV protons
at scattering angle 380. Thickness determination error is ≤0.5 nm for
energy analyzer with 0.01 resolution. The results are qualitatively
comparable with computer simulation.
In the case of IBSD of Si on Au surface, surface profiler was used to
determine the maximum thickness that could be analyzed. For 25 keV
protons at the scattering angle 38° it is equal to ∼40 nm. The thickness
corresponding to an arbitrary energy spectrum of scattered protons, in
this case, can be determined using linear dependence of peak position
on layer thickness with 0.35 keV/nm coefficient with error depending
on energy analyzer resolution. The maximum analyzable thickness of
both Au and Si can be enhanced with an increase in the primary proton
beam energy.

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