Accepted Manuscript

Nickel ion implantation effects on DC magnetron sputtered ZnO film prepared on Si

(100)

Rabia Younas, Naveed Afzal, Mohsin Rafique, M. Imran, Murtaza Saleem, R. Ahmad

PII: S0272-8842(19)31158-7
DOI: https://doi.org/10.1016/j.ceramint.2019.05.060
Reference: CERI 21512

To appear in: Ceramics International

Received Date: 24 January 2019

Revised Date: 11 April 2019
Accepted Date: 6 May 2019

Please cite this article as: R. Younas, N. Afzal, M. Rafique, M. Imran, M. Saleem, R. Ahmad, Nickel ion
implantation effects on DC magnetron sputtered ZnO film prepared on Si (100), Ceramics International
(2019), doi: https://doi.org/10.1016/j.ceramint.2019.05.060.

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 ACCEPTED MANUSCRIPT

Nickel Ion Implantation Effects on DC Magnetron Sputtered ZnO

Film Prepared on Si (100)
Rabia Younas1, Naveed Afzal1*, Mohsin Rafique1, M. Imran2, Murtaza Saleem3, R. Ahmad2
1) Centre for advanced Studies in Physics, GC University, Lahore
2) Department of Physics, GC University, Lahore

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3) Department of Physics, SBASSE, Lahore University of Management Sciences, Pakistan
Tel. No. +92 42 99211589, Fax No. +92 42 99213379
*Email: Naveed.phys@gmail.com

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ABSTRACT

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This paper presents structural, optical and electrical properties of nickel ion (Ni+) implanted ZnO

film at different fluences. The ZnO films were grown on Si (100) using DC magnetron sputtering

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of pure zinc target at room temperature. The Ni+ of energy 300 keV were implanted in the films
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at various fluences of 1.8×1012, 1.8×1013, 5.6×1013 and 1.1×1014 ions/cm2 by Pelletron

Accelrator. The ZnO films were found to be preferably oriented along (002) plane as indicated
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by the x-ray diffraction analysis. The Ni+ implantation in ZnO up to 1.8×1013 ions/cm2 caused a

decrease in the film’s crystallinity, however, the crystallinity of the film was improved with
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further increase in the ion fluence. The surface morphology results revealed beans-shaped
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granular structure of ZnO that became prominent after ion implantation at lower ion fluence. The
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energy dispersive x-ray spectroscopy validated an increase in the nickel contents with increase of

ion fluence. The ultraviolet-visible (UV-vis) reflectance spectroscopy depicted an increase in the
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film’s band gap from 3.37 eV to 3.49 eV after Ni+ implantation up to the fluence of 1.8×1013
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ions/cm2. However, the band gap was decreased with further increase in the fluence. The

electrical resistivity of the film was measured using four probe technique. The resistivity was

decreased from 952 to 68 Ω-cm after Ni+ implantation up to 5.6 ×1013 ions/cm2. However, at

higher fluence (1.1×1014 ions/cm2), the resistivity was significantly increased.

Keywords: Nickel ions, Pelletron Accelerator, ZnO, lattice parameter, resistivity, defects
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INTODUCTION
Zinc oxide (ZnO) is a direct and wide band gap semiconductor (3.37 eV) that exhibits

potential applications in electronic and optoelectronic devices [1]. ZnO has attracted significant

attention from the scientific community due to its remarkable inherent properties such as wide

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band gap, good thermal stability and large exciton binding energy. ZnO has hexagonal wurtzite

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crystal structure and it exhibits n-type conductivity [2-3]. Various synthesis techniques such as

chemical vapor deposition, spray pyrolysis, hydrothermal, sol-gel method, pulsed laser

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deposition, atomic layer deposition, electro-deposition, chemical bath deposition, molecular

beam epitaxy, thermal oxidation/evaporation, DC and RF magnetron sputtering [4-19] were used

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by different researchers to synthesize ZnO thin films/nanostructures. In these methods, the
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magnetron sputtering is thought to be better to fabricate thin films with good uniformity and

repeatability.
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Doping of various elements in ZnO films has been an active research area for the last one
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decade. This technique helps to modify the optical and electrical properties of these films, as the
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untreated ZnO is generally not active to carrier transmission and also not effective for the solar

energy absorption. In this regard, significant effort has been made to study the effects of metallic
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and nonmetallic elements doping in ZnO film prepared using chemical methods [20-25]. In

addition to doping by chemical methods, ion implantation in thin films is equally an important
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technique that is used to incorporate ions into semiconductors to enhance their electrical and
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optical properties. The survey of literature shows that a limited work was carried out to study ion

implantation effects in ZnO film than that of the chemical doping effects [26-31].

The ZnO films prepared using RF magnetron sputtering method were implanted with various

ions such as Ag, Al, Sb and Sn co-doped with TiN using an ion-implantation source. The

experimental results of this study demonstrated an increase in the electrical conductivity of the
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films after the ions implantation [26]. This increase was attributed to enhanced carriers

concentration in the film due to the implanted ions. Kohiki et al. [27] studied Al, Ga and B ion

implantation effects on the electrical properties of ZnO films. The authors found that the increase

in electrical conductivity of ZnO was more prominent in the case of Ga implanted film due to

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smaller electronegativity difference between Ga and Zn as compared to other metals. Similarly,

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Hartmann and co-workers [28] showed that the increase in the electrical conductivity of copper

implanted ZnO film is due to Cu+ oxidation state that occurs due to the film’s annealing. Singh

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et al. [29] reported that the crystallinity of RF sputtered ZnO film improves by implanting 120

keV Ag ions in it. However, the transmittance of the films was considerably decreased at higher

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ion fluence (3×1016 ions/cm2) due to ion induced defects in the ZnO film. Khan et al. [30]
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investigated the effects of 700 keV gold ions (Au+) fluence (ranging from 1×1013 to 5×1014

ions/cm2) on different properties of ZnO film prepared by pulsed laser deposition. The authors
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observed that the crystallinity of the films improve at the higher ion fluence (5×1014 ions/cm2)
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whereas the optical band gap initially decreases after ion implantation up to 2×1014 ions/cm2 and
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then increases by further increasing the ion fluence. The changes in band gap of ZnO were

correlated with the changes in the film’s crystallinity with increase of the ion fluence.
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Nickel (Ni) is a metallic element having atomic number (28) closer to Zn (30) and the ionic

radius of Ni (0.69 Å) and Zn (0.74 Å) are also near to each other. As a result, the Ni ions can be
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efficiently incorporated into the ZnO lattice. However, there are limited studies available on the
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Ni ion implantation in the ZnO film [31]. In this work, we investigate the influence of 300 keV

nickel ion implantation on the structural, optical and electrical properties of ZnO film. The ion

implantation experiment was performed at different ion fluences ranging from 1.8×1012 to
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1.1×1014 ions/cm2 to observe the changes in the crystallinity, electrical resistivity and optical

band gap of the film.

1. Experimental work

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Zinc oxide (ZnO) thin films were deposited on Si (100) substrate by direct current (DC)

magnetron sputtering technique. Samples were cut from as received Si wafers into pieces of 1.5

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x 1.5 cm2. The ZnO sputter deposition on Si (100) was carried out using DaON 1000S

magnetron sputtering system. The samples were fixed on substrate holder that was fixed inside

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the sputtering system. The target material Zn was mounted on the target holder inside vacuum

chamber. The vacuum chamber was evacuated and then filled with high purity Ar and O2 gasses

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at 80:20 ratio. Before entering the gasses, the base pressure was noted to be 2.2 x 10-5 mbar. The
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sputtering of Zn target was conducted at 30 W in Ar:O2 with working pressure of 1.1×10- 3 mbar.
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The time duration for the deposition of ZnO film was one hour. The thickness of the deposited

films was 300 nm. In order to investigate the effect of nickel ions (Ni+) on ZnO thin films, the
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Ni+ of energy 300 keV were implanted in the films by Pelletron Accelerator at different fluences.
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An image of Pelletron Accelerator used in this work is shown in Fig. 1 (a) whereas the schematic

diagram of Ni implantation in ZnO is presented in Fig. 1 (b). The Pelletron Accelerator is an

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electrostatic particle accelerator which is similar to Van de Graff generator. Electric charges

generated are mechanically and these are transported by chain of pallets that is used to build up
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high voltages on the Pelletron terminal. The Ni+ were implanted in ZnO films for 1 min, 10 min,
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30 min and 60 min in different sets of experiments. The Ni+ fluence was calculated using the

beam current and implantation time. The fluence values were noted to be 1.8×1012, 1.8×1013,

5.6×1013 and 1.1×1014 ions/cm2. The detail of implantation parameters are given in Table 1.
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The penetration of Ni+ inside ZnO film was obtained from the Stopping and Range of Ions in

matter (SRIM) software [32]. The depth profile of 300 keV Ni+ inside ZnO is shown in Fig. 1

(c). The ion range was found to be about 181 nm. The crystalline structure of the films was

examined by x-ray diffractometer (XRD) using Cu K-alpha radiations in the 2θ range of 20o-80o.

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Surface features of the untreated and Ni+ implanted films were studied by field emission SEM.

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Energy dispersive x-ray spectroscopy was utilized for the elemental analysis. The optical

properties of ZnO were studied by UV-vis reflectance spectroscopy. Electrical resistivity was

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measured by four probe method to analyze the electrical behavior of the ion-implanted films.

2. Results and Discussion

3.1 Structural Analysis

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The crystal structure and orientation of untreated and nickel ion (Ni+) implanted ZnO
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films were investigated through x-ray diffraction (XRD) technique. Fig. 2 shows the grazing

incident angle XRD patterns of untreated and Ni+ implanted ZnO films. The figure indicates the
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formation of ZnO film along (002) plane in all the cases. A small diffraction peak of ZnO
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corresponding to (103) plane is also seen from the figure, however, the ZnO film exhibits

preferred orientation along (002) plane as shown by the XRD results. This demonstrates that the
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ZnO film formed has hexagonal wurtzite structure. This type of structure is formed due to the

lowest surface energy of the (002) plane in the ZnO lattice as compared to the other planes. The
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(002) orientation of magnetron sputtered ZnO film in our experiment is consistent with the
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previous studies [33-34]. The figure 1 shows that the ZnO (002) peak broadens after the Ni+

implantation at 1.8 ×1012 and 1.8 ×1013 ions/cm2 thus indicating a decrease in the film’s

crystallinity. However, with further increase in the ion fluence, the crystallinity was improved as

noticed from a decrease in the peak broadening.

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In order to estimate the crystallite size ‘D’ of ZnO along (002) plane, the Debye-Scherer

formula = was used [35]; Here is FWHM of the (002) peak, λ is the x-ray

wavelength, k is the constant and θ is the Bragg’s angle. The variation in crystallite size with ion

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fluence is shown Fig. 3 (a). As seen from the figure, the crystallite size reduces after the Ni+

implantation at 1.8 ×1012 and 1.8 ×1013 ions/cm2, whereas when the ion fluence increases to 5.6

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×1013 ions/cm2 and above, the crystallite size starts increasing. The reduction in crystallite size is

due to ion implantation induced lattice defects such as vacancies and interstitials that produce

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lattice disorder [31]. When an energetic ion interacts with a target lattice then it displaces the

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target atoms from their normal lattice sites thus creates vacancies and interstitials. The displaced
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primary knock on atoms (PKAs) further produce atomic displacements and subsequently,

displacement cascades process takes place. In addition to this, the electronic stopping of ions
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inside the material occurs through excitation and ionization. The energy lost during cascade

collisions and in the ionization/excitation process produce intense heat, causing an increase in the
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temperature of the localized region [32, 36]. Due to the thermal spike, the ion induced damage in
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the film is reduced. The remaining defects produce changes in the crystallite size of the material.

In our experiment, the results of crystallite size show that the crystallite size decreases when the
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Ni+ are implanted in ZnO at lower ion fluences (1.8 ×1012 and 1.8 ×1013 ions/cm2), however at
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higher fluences, the crystallite size increases (1.1×1014 ions/cm2). The decrease in the crystallite
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size is attributed to ion implantation created damage inside the ZnO film. At higher fluence, the

number of Ni+ in the film are increased that might produce more atomic collisions/electronic

energy losses, thus heating effects occur within the lattice and consequently the crystallite size

decreases. The dislocation density ‘δ’ (δ = ) and lattice strain ‘ε’ (ε = ) inside untreated

and ion-implanted films along (002) plane were also estimated [37]. The values of dislocation
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density and lattice strain in ZnO film before and after Ni+ implantation as function of ion fluence

are shown in Figs. 3 (b) and 3 (c) respectively. The dislocation density and strain inside the film

increase at lower ion fluences and then decrease at higher fluences.

The XRD results also show ZnO (002) peak shifting at higher angle which becomes

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pronounced with increase of the ion fluence. This suggests a decrease in the atomic spacing ‘d’

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and hence the lattice parameter of ZnO after the ion implantation. The c-axis lattice constant ‘c’

for the hexagonal (002) oriented ZnO film was obtained through the following relation [38];

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= + (1)

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Here, a and c are lattice parameters of ZnO, h k l are atomic planes whereas d is the atomic
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spacing. The variation in lattice parameter ‘c’ with ion fluence is shown in Fig. 3 (d). The lattice

parameter decreases with increase of the ion fluence. This decrease in the lattice parameter is
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attributed to the incorporation of Ni+ on the Zn+ sites in the ZnO lattice. The relatively smaller
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ionic radius of nickel (0.69 Å) as compared to Zn (0.74 Å) causes atomic spacing to decrease

that subsequently increases the lattice parameter [31]. The decrease in lattice parameter of Ni+
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implanted ZnO is more significant at higher dose (1.1×1014 ions/cm2) which is attributed to an
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increase in the number of nickel ions occupying on the substitutional Zn sites in the ZnO lattice.

Furthermore, the localized thermal effects at 1.1×1014 ions/cm2 are increased that might facilitate
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the diffusion of nickel towards the Zn sites. Consequently, the decrease in the lattice parameter
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of the Ni implanted ZnO film at 1.1×1014 ions/cm2 becomes more prominent.

3.2 Surface morphology

The surface morphology of ZnO films was studied using field emission scanning electron

microscope (FESEM). The morphological features of untreated and Ni+ implanted films are

shown in Fig. 4 (a-e). In the case of untreated film, the grains are in different shapes. Some of the
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grains are rounded whereas few others are of bean-shaped. After ion implantation at lower

fluences (1.8×1012 and 1.8×1013 ions/cm2), the beans-shaped granular structure becomes

dominant and the shape of the grains is distorted as compared to the untreated film. This

distorted shape of the grains might be due to the defects created by Ni+ implantation in the film.

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On the other hand, the Ni+ implantation at higher fluences (5.6×1012 and 1.1×1013 ions/cm2)

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recovers the shape of the distorted grains which is almost similar to the grains of the untreated

film. This recovery might be due to localized heating effects that occurred at higher ion fluence.

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The localized heating of the sample releases strain within the grains and thus the distortion in the

shape of grains decreases. A schematic diagram of untreated and Ni+ implanted ZnO is shown in

Fig. 5. This diagram shows

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a variation in the grain shape and size of ZnO film at different ion
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fluences. The FESEM results are in good agreement with the XRD results as discussed above.

2.2 Energy Dispersive X-ray Analysis

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The energy dispersive x-ray spectroscopy (EDS) was used to confirm the presence of Ni+
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inside the ZnO film. The EDS spectra for untreated and ion-implanted ZnO films are shown in
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Fig. 6. The wt % composition of Zn, O, Ni and Si are given in Table 2. From the table, one can

observe that the amount of Ni increases and the amount of Zn decreases with increase of the ion
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fluence. This confirms that Ni+ were implanted on the Zn+ sites in the film. The appearance of Si

is due to the reflection of x-rays from the substrate.

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3.4 UV-Visible Spectroscopy

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UV-visible reflectance spectroscopy results of untreated and Ni+ implanted ZnO films are

shown in Figs. 7 and 8. The Fig. 7 shows the UV-visible reflectance spectra of ZnO before and

after the ion implantation whereas in Fig. 8, the band gap of ZnO film is plotted against the ion

fluence. The UV-visible spectra were obtained through UV-vis spectrometer for the wavelength
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ranging from 200 nm to 800 nm. The Fig. 7 shows that all the spectra exhibit interference fringes

that vanish near to the wavelength that corresponds to the band gap of ZnO film. These

interference fringes occur due to multiple reflections of the light from the film and substrate

interfaces [39]. The cut-off wavelength for each reflectance spectrum was noted and the

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following relation was used to calculate the band gap of ZnO film;

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Eg= (2)

Here, Eg is the band gap energy, h is the Planck’s constant, c is the speed of light and λ is the

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wavelength of the light. The variation in band gap of ZnO film with ion fluence is shown in Fig.

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8. The band gap energy (Eg) for the untreated ZnO film is found to be 3.37 eV. However, after
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the Ni+ implantation up to 1.8 ×1013 ions/cm2, the band gap value increases to 3.49 eV. With

further increase in the ion fluence, the band gap of Ni+ implanted ZnO film decreases. The band
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gap at 5.6 ×1013 and 1.1×1014 ions/cm2 is found to be 3.45 eV and 3.34 eV respectively. The

increase in the band gap of ZnO film after ion implantation at lower fluences is attributed to the
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structural defects created during the ion implantation. These defects might include oxygen
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vacancies and zinc (Zn) interstitials inside the ZnO lattice. It is well known that these defects
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create their energy states near to the conduction band of the ZnO and act as electron donors [40].

Consequently, the Fermi-level is shifted up (referred as Moss-Burstein shift) inside the

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conduction band which results in the widening of the band gap. However, at higher Ni+ fluence
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(5.6 ×1013 and 1.1×1014 ions/cm2), an increased number of Ni+ are incorporated on the Zn+ sites

whereas the ion implantation induced defects in ZnO are reduced due to the localized heating

effects [30]. This thermal recovery reduces the chances of Zn interstitials and oxygen vacancies

in ZnO film, thus lowering the Fermi-level and hence the band gap of the film. The band gap

results of ZnO are well correlated with the XRD results in which at lower fluences, crystallinity
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of the films was deceased whereas at higher fluences the crystallinity was improved due to

localized heating effects.

3.5 Electrical properties

Electrical resistivity (ρ) of ZnO films was measured using four-point probe method by

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#
using the formula ρ= % [41]. Here, I and V are current and voltage respectively, t is the
!" $

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film thickness and !"
is the correction factor. The electrical resistivity of ZnO films was

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measured as a function of ion fluence before and after Ni+ implantation. The resistivity variation

with ion fluence is shown in Fig. 9. The resistivity of the untreated ZnO film is found to be 952

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Ω-cm which reduces to 68 Ω-cm with increasing the ion fluence up to 5.6 ×1013 ions/cm2.
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However, at the highest fluence (1.1 ×1014 ions/cm2), the resistivity is considerably increased

(4.7×103 Ω-cm). The decrease in resistivity of Ni+ implanted ZnO film is probably due to
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oxygen vacancies or Zn interstitials that minimize the ZnO formation and as a result the

electrical conductivity increases and consequently the electrical resistivity decreases. Another
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possible reason for the decrease in the resistivity is that more carriers (electrons) are produced
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due to the donor level defects inside the ZnO film that improves the electrical conductivity of the

film [40, 30]. However, at the fluence of 1.1 ×1014 ions/cm2, the significant increase in the
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resistivity of Ni+ implanted ZnO film is due to less donor defects such as oxygen vacancies and
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Zn interstitials which improves the film’s crystallinity. As a result of reduced donor defects, the
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number of charge carriers for the electrical conduction are decreased and hence the resistivity of

the film increases.

4. Conclusions

The following conclusions can be extracted from the present work;

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ZnO films grown using DC reactive magnetron sputtering exhibits highly c-axis oriented

wurtzite structure. The lattice parameter of Ni+ implanted ZnO thin films decreases with increase

of the ion fluence due to smaller ionic radius of nickel as compared to the zinc. The crystallinity

of ZnO films declines after Ni+ implantation up to 1.8 ×1013 ions/cm2 whereas by further

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increasing the ion fluence, the crystallinity improves. The band gap of ZnO film increases at

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lower fluences up to 1.8 ×1013 ions/cm2 due to Burstein-Moss shift. However, further increase in

the ion fluence decreases the band gap due to localized heating effects. The electrical resistivity

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of ZnO film decreases with Ni+ implantation up to 5.6 ×1013 ions/cm2, however Ni+ implantation

at ion higher fluence increases the resistivity.

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M
D
TE
C EP
AC

Fig. 1 (a) Image of Pelletron Accelerator (b) Schematic diagram of Ni+ layer in ZnO film
(c) Damage Profile of Ni+ implanted in ZnO film
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♦
♦ ZnO (002)
♣ ZnO (103)

PT
♦ ♣ 1.1×1014 ions/cm2

RI
♣ 5.6×1013 ions/cm2
♦
Intensity (a.u)

♣ 1.8×1013 ions/cm2

SC
♦

♣ 1.8×1012 ions/cm2

U
♦
AN
♣ As-depsoited ZnO
M

20 30 40 50 60 70 80
2θ (degree)
D
TE

Fig. 2 X-ray diffraction graphs of untreated and Ni+ implanted ZnO film
C EP
AC
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12
500

Dislocation Density (× 10 cm )
-2
10
400

14
Crystallite Size (nm)

300
8

PT
200
6

RI
100

4
0

SC
0 20 40 60 80 100 120 0 20 40 60 80 100 120
12 2 12 2
Ion fluence (×10 ions/cm ) Ion fluence (×10 ions/cm )

(a) (b)

U
AN
0.008 5.6

)
0.007 Å 5.5
Lattice parameter 'c' (
M

0.006
5.4
strain

0.005
5.3
TE

0.004
5.2

0.003
EP

5.1
0 20 40 60 80 100 120 0 20 40 60 80 100 120
12 2 12 2
Ion fluence (×10 ions/cm ) Ion fluence (×10 ions/cm )
C

(c) (d)
AC

Fig. 3 Variation in structural parameters of ZnO film with ion fluence

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PT
RI
(a) As-depsoited (b) 1.8×1012 ions/cm2

U SC
AN
M

(c) 1.8×1013 ions/cm2 (d) 5.6 ×1013 ions/cm2

D
TE
C EP
AC

(e) 1.1 ×1014 ions/cm2

Fig. 4 (a-e) Surface morphology results of untreated and Ni+ implanted ZnO films
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PT
RI
U SC
AN
Fig. 5 Schematic diagram of surface morphology of ZnO film at different Ni+ fluence
M
D
TE
C EP
AC
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PT
(a) Untreated (b) 1.8×1012 ions/cm2

RI
U SC
AN
(c) 1.8×1013 ions/cm2 (d) 5.6×1013 ions/cm2
M
D
TE
EP

(e) 1.1×1014 ions/cm2

C

Fig. 6 (a-e) EDS results of untreated and Ni+ implanted ZnO films
AC
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12 2
1.2 As-deposited 1.2 1.8×10 ions/cm

1.0 1.0

0.8
Reflectance (%)

0.8

Reflectance (%)
0.6 0.6

0.4 0.4

0.2
0.2

PT
0.0
0.0

-0.2
-0.2

300 400 500 600 700 800

300 400 500 600 700 800

RI
Wavelength (nm)
Wavelenght (nm)

SC
13 2 13 2
1.2 1.8×10 ions/cm 1.2 5.6×10 ions/cm

1.0 1.0

0.8
Reflectance (%)

0.8
Reflectance (%)

U
0.6
0.6

0.4
AN
0.4

0.2
0.2

0.0
0.0
M

-0.2
-0.2
300 400 500 600 700 800
300 400 500 600 700 800
Wavelength (nm)
Wavelenght (nm)
D

14 2
1.2 1.1×10 ions/cm
TE

1.0

0.8
Reflectance (%)

0.6
EP

0.4

0.2

0.0
C

-0.2
AC

300 400 500 600 700 800

Wavelength (nm)

Fig. 7 UV-visible spectra of untreated and Ni+ implanted ZnO films

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3.52

PT
3.48

RI
Band gap (eV)

3.44

SC
3.40

3.36

U
AN
3.32
M

0 20 40 60 80 100 120
12 2
Ion fluence (×10 ions/cm )
D

Fig. 8 Variation in band gap of ZnO film with ion fluence

TE
C EP
AC
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5000

4000

PT
Resistivity (ohm-cm)

3000

RI
2000

SC
1000

U
AN
0 20 40 60 80 100 120
12 2
Ion fluence (×10 ions/cm )
M

Fig. 9 Variation in electrical resistivity of ZnO film with ion fluence

D
TE
C EP
AC
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Table 1 Nickel Ion Implantation Parameters

Ion Fluence Current Time Energy (keV) Ion Range

(ions cm-2) (nA) (min) (nm)

1.8×1012 20 1 300 181

PT
1.8×1013 20 10 300 181

RI
5.6×1013 20 30 300 181

1.1×1014 20 60 300 181

U SC
AN
M
D
TE
C EP
AC
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Table 2 Elemental composition of ZnO film before and after Ni+ implantation

Wt%

Element As-deposited 1.8×1012 1.8×1013 5.6×1013 1.1×1014

(ions cm-2) (ions cm-2) (ions cm-2) (ions cm-2)

PT
O 22.68 22.50 22.42 22.64 22.64

Si 43.65 44.55 46.04 45.98 46.93

RI
Zn 33.67 32.93 31.50 31.32 30.33

SC
Ni -- 0.02 0.04 0.06 0.1

U
AN
M
D
TE
C EP
AC