Oxidation of nickel by low-energy ion

bombardment studied using XPS

Patrick Seleš

University of Rijeka
Department of Physics
Radmile Matejčić 2, 51000 Rijeka
Croatia

June 5, 2017
 Abstract

Metallic Ni and formation of thin oxide film on pure Ni were studied

by XPS. Ni surfaces were cleaned by argon sputtering and then bombarded
with 2 keV O2 + . It is shown that oxidation is efficient in creating thin NiO
film on the Ni surface. In addition the surface morphology of ZnO film
grown by Atomic Layer Deposition (ALD) was investigated by SEM.
Keywords: Ni, ion beam, XPS, SEM

1 Introduction

It is well known that metals in contact with the oxidizing enviroment will
corrode, for instance an inert [1] oxid layer forms on the surface of Ni. Such
metallic oxide films are important because they provide protection between metal
and enviroment. Nickel oxide (NiO) is used in a wided range if applications, from
from electrochromic devices or chemical sensors to antiferromagnetic layers in
spin valve structures, due to its excellent durability and chemical stability. The
initial stages of oide formation are of particular interest in understanding the
oxidation mechanism of Ni.

In this study X-ray photoemission spectroscopy (XPS) tecniqe is em-

ployed in probing the oxidation initiating by O2 + . XPS has the ability to
distignuish atoms of the different oxidation states (by their chemical shifts in
photoemission spectra). In addition, the surface of zinc-oxide (ZnO) was de-
terminated by SEM. ZnO is a wide gap-band semiconductor with a variety of
useful properties like applications in thin film transistors (TFTs) and optoelec-
tronic [3].

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2 Experimental techiques

2.1 X-ray Photoelectron Spectroscopy

For the oxidation studies of Ni a 0,5 nm thick nickel foil (Alfa Aeser,
99,994 wt.% Ni) was used. Before oxidation, the foil was bombarded by 2 keV
Ar+ ions at room temperature within the UHV XPS chamber. This sample is
reffered to as clean sample. Ni surface was then bombarded with 2 keV O2 + ions,
within the current density of around 2 µAcm-2 . X-rays cause the photoemission
of electrons of excitatied atoms from the surface and their signal is meassured by
electronic energy analyzer. Importantly, energy of electron depends of orbital
angular momentum of the electron, which means that contributions of orbit-
splitting [4] can be seen in Ni2p spectra . The XPS analysis was performed using
SPECS spectrometer in ultra high-vacuum (10-7 Pa) at room temperature and
with the monochromatic Al Kα source producing X-rays of energy of 1486,7 eV.
Spectra were analyzed using UNIFIT software. The mixed Gaussian-lorentzian
functions, defined in software, were used for fitting spectras. The meassurement
was performed with the constant energy pass of 10 eV.

2.2 Scanning Electron Microscope

Scanning Electron Microscope was used for studying surface morphol-

ogy of the ZnO film grown by ALD and the mesaurment of the film thickness.
The film thickness was determinated using the upper electron detector at 10 kV
accelerating voltage. In the gentle beam mode at 0,7 kV accelerating voltage
using the upper electron detector the surface image were acquired. ZnO films
were grown by using ALD tecnique. Diethyl zinc (DEZ) and H2 O are precursors
for zinc and an oxidant. ZnO grown at 200◦ C.

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3 Results and discussion

3.1 SEM

SEM micrograph of ZnO thin film are shown in figure 1. Granes in

the ZnO film grown at 200◦ C are small and has a round shape, whereas some
has longish shape like a worm. The worm-like shape of the grains in the ZnO
films may be due to incomplete thermal decomposition of the reactants [2]. The
thickness of ZnO films determinated by SEM measurements was 300 nm.

Figure 1: SEM micrograph of ZnO thin film grown on Al2 O3

3.2 XPS
3.2.1 Metallic Ni

Figure 2 shows Ni 2p3/2 spectrum meassured on Ni foil, cleaned by argon.

Cleaned Ni 2p3/2 spectrum is characterized by three peaks - main assymetric line
and other two are satellite peaks1. Strong spit-orbit coupling in Ni 2p state is
responsible for the splitting of Ni 2p signal into doublet. Because of separation
1Satellite peaks are caused by losing energy in photoemission

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of Ni 2p3/2-1/2 peaks (17 eV) there is no interference between states, hence only
more pronounced 2p3/2 signal was analised.

Figure 2: Fitting of Ni 2p3/2 photoemission peak for clean nickel surface

Deconvulation of experimental curve give metallic Ni 2p3/2 peak at

binding energy (BE) of 853,15 eV, and satellites peak; 1’ at BE of 859,15 eV
and 1” of 856,65 eV as shown in Figure 2 [1].

3.2.2 Ion bombardet Ni

Oxydation of Ni induces several changes in the shape of Ni 2p3/2

photoemission signal. New peaks related to Ni oxide appears in the spectrum.
Therefore, we conclude that after oxidation thin oxide film is formated on the
surface, for strong metallic Ni peak 1 is still present in spectrum as shown in
Figure 3.

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 Figure 3: Ni 2p3/2 photoemission peak, obtained for Ni sur-
face bombarded with 2 keV oxygen ions, and fitted with mixed
gaussian-lorentzian functions

Figure 3. shows Ni 2p3/2 peak aften ion bombardment, fitted with mixed
gaussian-lorentzian function. In Figure 3, peaks related to NiO are colored
blue, and peaks related to metallic Ni are colored red. Bombarded spectrum is
charecterized by three peaks from clean Ni; peak 1, and two satellite 1’ and 1”
(these three peaks have same energy position and FWHM as in Fig. 2) and five
peaks related to NiO. Peak 2 at BE of 854,45 eV, peak 3 at BE of 856,15 eV and
satellite peaks 4,5,6 at BE of 861,35 eV, 864,55 eV and 866,85 eV [1].

The process of Ni oxydation by ion implanation can be explained by the

diffusion of Ni cations and O anions throught the defects in material, enhanced
by bombardment process. [1]

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4 Conclusion

In summary, different grain shape of ZnO film indicates on polycrys-

talline structure. In metallic Ni spectra are shown main assymetric line and two
satellite peaks. Because of formation of NiO layers, in ion bombarded spectra
is annotatied appearance of new lines.

5 Acknowledgements

The author acknowledges the help of Dr Robert Peter for XPS measure-
ments and Dr Ivna Kavre Piltaver for SEM.

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