International Journal of Innovative Technology and Exploring Engineering (IJITEE)

ISSN: 2278-3075, Volume-9 Issue-3S, January 2020

First Principles Research on The Magnetic

Properties of Na and Cl doped ZnO
Mauludi Ariesto Pamungkas, Setiawan Ade Putra, Irwansyah, Heru Harsono

 (room temperature) conditions only when covered with

Abstract: ZnO is considered as a wide bandgap material defective p-type molecules, and vice versa for Co: ZnO films
because it has a 3.4 eV direct bandgap. This wide bandgap N-type defects the conditions supported RT ferromagnetism.
characteristic causes good transparency, high electron mobility This led to numerous studies to identify the magnetic
and luminescence at room temperature.The unique and tuneable
properties of ZnO with various n- and p-type dopants[4].
properties of nanostructured ZnO shows excellent stability in
chemically as well as thermally stable n-type semiconducting N-type doping is relatively well developed by
material with wide applications such as in luminescent material, substitution of Group III (Al, Ga, In) elements, resulting in
supercapacitors, battery and solar cells. To be applied to a n-type ZnO with high conductivity. All previous attempts to
variety of needs, price control bandgap is needed. Likewise, achieve a reliable p-type doping in ZnO, however, remained
control over the magnetic nature. Therefore we need a study largely unsuccessful. Some materials whose valence bands
related to bandgap modification, one of them is by giving
are relatively close to the vacuum level have good p-type
impurity atoms. Atom Na and Cl were chosen as representatives
of donors and acceptors. Atomistic calculations use the conductivity. In contrast, materials having a valence band
Functional Density Theory method which is implemented in relatively far from the energetic position of the vacuum level,
ABINIT software. Relaxation and convergence research results such as ZnO, exhibit good n-type conductivity. In general,
are used to find the most stable energy value of ZnO.. The results elements in group III donate electrons to Zn. While, elements
showed Magnetic Properties in ZnO doping Na obtained such as Li, Na, K, Cu, and Ag recive electron from Zn [5].
magnetization values of 1.4802 𝜇𝐵 greater than pure ZnO that is it was reported that the Na-doped p-type ZnO
0.9394 𝜇𝐵 while ZnO doping Cl obtained magnetization values
experiment was successfully performed by Piao et al [6][7].
of 0.8593 𝜇𝐵 smaller than pure ZnO. In conclusion the ZnO
doping magnetic properties of Na increase magnetization and Cl The results show that the magnetic properties of ZnO
doping also change the magnetic properties by decreasing ZnO increased the saturation magnetic properties by 0.008
magnetization. emu/cc. In DFT (Density Functional Theory), d-type Na
doping with ZnO has not yet occurred. Therefore, this study
Keywords : : First Principle, ZnO, Na, Cl, Magnetic . was conducted to determine the effect of magnetic properties
on the doping of Na-ZnO using DFT. Na was also chosen
I. INTRODUCTION because Sodium is the fourth most abundant element that can
Diluted magnetic semiconductors (semiconductors be found on earth. Sodium is an alkali metal, in group one of
containing small amounts of magnetic impurities) and oxides the periodic table, because it has an electron in its outer shell
are interesting for fundamental science and applications[1]. that is easily donated, creating positively charged atoms in
Doping oxides such as zinc oxide (ZnO) are among the best the form of Na+ cation and is an alkali metal material which
candidates for the DMS industry due to the multifunctional may have ferromagnetic properties due to the holes created.
ZnO in opto-magnetic applications. In particular, ZnO-based Additionally, in the study by Wang et al [7] doping has
DMS with properties such as visual transparency and been carried out on ZnO with nonmagnetic elements such as
piezoelectricity has aroused great interest in science as a Li, Mg, and Al, which make ZnO X (X = Li, Mg and Al).
strong candidate for spin-transistor and spin-polarized These non-magnetic impurities have reduced the energy
light-emitting diode fabrication[2]. formation of ZnO vacancies, which in turn affects the
At room temperature, the ferromagnetism shown in ZnO magnetic properties of ZnO. Therefore it is necessary to try
semiconductors under certain conditions has led to the impurities instead of magnetic impurities other than these
argument that the defect could be the origin of elements. So in this calculation we use the Cl element as a
ferromagnetism [3]. Kittilstved and Gamelin ( reported that non-magnetic impurity. The Cl element is also the second
Mn: ZnO nanoparticles and thin films had ferromagnetic RT most abundant halogen atom on earth and is often used in the
manufacture of advanced technologies such as processors,
semiconductors and electrical components submission to the
Revised Manuscript Received on January 10, 2020.
* Correspondence Author journal, rectification is not possible.
Mauludi Ariesto Pamungkas*, Jurusan Fisika (Physics Department),
Universitas Brawijaya ,Malang, Indonesia. Email: [email protected] II. COMPUTATIONAL METHODS
Setiawan Ade Putra, Jurusan Fisika (Physics Department), Universitas
Brawijaya ,Malang, Indonesia. We performed first
Irwansyah, Jurusan Fisika (Physics Department), Universitas Brawijaya
,Malang, Indonesia. principles
Heru Harsono, Jurusan Fisika (Physics Department), Universitas electronic-structure
Brawijaya ,Malang, Indonesia.

Retrieval Number: C10400193S20/2020©BEIESP Published By:

DOI: 10.35940/ijitee.C1040.0193S20
182 Blue Eyes Intelligence Engineering
& Sciences Publication
 First Principles Research on the Magnetic Properties of Na and Cl doped ZnO

calculations based on the spin polarized density-functional ZnO structure is wurzite consisting of 4 atoms including
theory (DFT) implemented in ABINIT package[8]. An two Zn atoms and two O atoms which are determined using
exchange correlation potential was evaluated via a the wurzite crystal vector (see Figure 1). In cartesian
generalized gradient approximation (GGA). coordinates, the basic atomic vectors are (0,0,0), (0,0, uc), a
described by the Perdew-Burke-Ernzerhof (PBE) (1/2, √ 3 / 6, c / 2a) and a (1/2, √ 3 / 6 , [u + 1/2] c / a).
scheme[9]. Plane-wave cutoff energy is set at 400 eV and the
Doping of atom Na is performed by substituting Zn atoms
Brillouin-zone integration is performed with a k-points
(Figure 2), the size of the Na atom is 1.86 Å which is not
mesh which is generated automatically by the
much different from the Zn atom which is 1.34 Å so that can
Monkhorst-Pack scheme[10].
be replaced by substitution. Figure 2 shows the supercell ZnO
after doping the substitution of Na atoms with Zn atoms in
position (0.66667, 0.33333, 0.69239). While doping of Cl
atom is performed by substitution of oxygen atom as
displayed by Figure 3.

Results and Discussion

Magnetic property is the ability of a material to attract
objects around it. This is caused by the spin and orbital
motion of electrons, giving rise to a current and the current
causes magnetization. In studies of three-dimensional
structures such as ZnO, magnetic properties are analyzed by
calculating polarized density of state (DOS). In the polarized
density of state (DOS) there are density of state of spin ups
and spin downs. If the two density of states are symmetrical,
Fig. 1. Crystal structure of pure ZnO then the material that we study is nonmagmetic, in contrast,
if the DOS of spin-up and spin-down plot shows
asymmetrical results, then the material is ferromagnetic.
It was found that pure ZnO according to the results of this
study has an asymmetrical DOS (Density of State) as seen in
Figure 4 which also has a total magnification value of 0.9394
µB which indicates pure ZnO already has magnetic
properties. Adding Na aton on Pure ZnO to the cell position
(0.66667, 0.33333, 0.69239) produces a magnetic moment of
1.4802 µB and with a plot of density of state shown by Figure
4.b. This magnetic moment has increased up to 1.5756 times
the magnetic moment produced by pure ZnO. When the ZnO
supercell atom is doped with a Na atom, the Na atom will
contribute to the spin-up electron orientation because the
valence electron in Sodium is 1 different from the Zn orbital
Fig. 2. Crystall structure of Na-doped ZnO fully charged at 4s2. The plot results show that spin up and
dpin down are asymmetrical.
The DOS graph of ZnO doped with Cl atoms in the cell
position (0.66667, 0.33333, 0.49035) shows that the spin up
and down are asymmetrical so that ZnO doped with Cl still
has magnetic properties as shown in Figure 4.3c, but has a
magnetic moment of 0.8593 µB. This magnetic moment has
decreased to 0.91473 times of the magnetic moment
produced by pure ZnO. This is similar to what reported by
Wang et al., (2012), that when ZnO doped with nonmagnetic
elements oxygen vacancy will appear which leads to
reducing its formation energy and ZnO system will be stable
again after oxygen atom is substituted with Cl atom to a
certain extent. That is agree well with the energy values
obtained in this calculation, which are listed in Table 1,
formation energy of Cl doped ZnO is lower than that of pure
ZnO .

Fig. 3. Crystall structure of Cl-doped ZnO

Retrieval Number: C10400193S20/2020©BEIESP Published By:

DOI: 10.35940/ijitee.C1040.0193S20
183 Blue Eyes Intelligence Engineering
& Sciences Publication
 International Journal of Innovative Technology and Exploring Engineering (IJITEE)
ISSN: 2278-3075, Volume-9 Issue-3S, January 2020

a)

b)

c)
Figure 4. Polarized Density of States of a. Pure ZnO , b. Na doped ZnO, c. Cl doped ZnO

Retrieval Number: C10400193S20/2020©BEIESP Published By:

DOI: 10.35940/ijitee.C1040.0193S20
184 Blue Eyes Intelligence Engineering
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 First Principles Research on the Magnetic Properties of Na and Cl doped ZnO

Table-I. Formation Energy of the three ZnO systems

No. System Formation Energy (eV)
1 Pure ZnO -3.0897 x 10-4
2 Na doped ZnO -2.9413 x 10-4
3 Cl doped ZnO -3.0868 x 10-4

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Ghosez P, Giantomassi M, Goedecker S, Hamann D R, Hermet P, Jollet
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ZnO, Na doped ZnO, and Cl doped ZnO, it is found that all First-principles approach to material and nanosystem properties Comput.
systems are ferromagnetic due to the asymmetrical spin Phys. Commun. 180 2582–615
9. Perdew J P, Burke K, Ernzerhof M, of Physics D and Quantum Theory
up-down state. The magnetization value of Na doped ZnO Group Tulane University N O L 70118 J 1996 Generalized Gradient
is 1.4802 µB greater than magnetization of pure ZnO, which Approximation Made Simple Phys. Rev. Lett. 77 3865–8
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integrations Phys. Rev. B 13 5188
magnetization value of 0.8593 µB smaller than that of pure
ZnO. AUTHORS PROFILE
Mauludi Ariesto Pamungkas, obtained his doctor’s
ACKNOWLEDGMENT degree from Universtiy of Science and Technology
(Korea) in the field of Nanomaterials Science and
The author thanks to Universitas Brawijaya for its Engineering. His current resaerch focuses on
financial support through professor and doctor research computational material. Now, he is head of simulation and
project scheme. modeling laboratoryat physics department Universitas
Brawijaya. In Indonesia.
uthor-1
Phot o
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DOI: 10.35940/ijitee.C1040.0193S20
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