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Electronic Structure and Magnetic Properties of Doped GaAs (Zinc Blende)

with Double Impurities and Defects

Article in Journal of Superconductivity and Novel Magnetism · September 2013

DOI: 10.1007/s10948-013-2119-2

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J Supercond Nov Magn
DOI 10.1007/s10948-013-2119-2

O R I G I N A L PA P E R

Electronic Structure and Magnetic Properties of Doped GaAs

(Zinc Blende) with Double Impurities and Defects
H. Zaari · M. Boujnah · H. Labrim · B. Khalil ·
A. Benyoussef · A. El Kenz

Received: 13 December 2012 / Accepted: 5 February 2013

© Springer Science+Business Media New York 2013

Abstract Using ab-initio calculations based on Korringa– The Curie temperature is estimated from the total energy
Kohn–Rostoker coherent potential approximation (KKR- difference between the Disorder Local Moment (DLM) and
CPA) method in connection with the local density approx- the (FM) state by using a mapping on the Heisenberg model
imation (LDA), we study theoretically the electronic and in mean field approximation.
magnetic properties of a system based on GaAs material.
Keywords Ab-initio · Acceptor · Donor · Doped ·
These properties have been studied, with different point de-
Codoped · Point defect · Ferromagnetic · Spin-glass · Curie
fects in GaAs, which are Gallium interstitials (Gai ), Gal-
temperature
lium antisites (GaAs ), Gallium vacancies (VGa ), Arsenic in-
terstitials (Asi ) and Arsenic antisites (AsGa ), Arsenic vacan-
cies (VAs ), and in-doped or codoped system Ga1−x Cox As 1 Introduction
and Ga1−y−z Coy Fez As, respectively. This work presents de-
tailed information about total and local density of states The electronic and magnetic properties of III–V semicon-
at different concentrations of these defects and doped ele- ductor compounds have been extensively studied by various
ments; the stability of the ferromagnetic state compared with techniques over the last few decades [1].
the spin-glass state has been discussed. The result of elec- Recently, the III–V semiconductor compounds have be-
tronic properties shows that codoped GaAs material with Fe come the subject of extensive investigations because of the
and Co become ferromagnetic, also doped GaAs with Co or progress in developing IR lasers, photodiodes, solar cells,
Fe with a defect (hole in Ga) is stable in the ferromagnetic and thermo photovoltaic converters. The GaSb, GaP, and
GaAs-based optoelectronic devices for the 2–4 µm spec-
state.
tral range are of great interest for a wide range of appli-
cations, such as high resolution laser diode spectroscopy
of gases and molecules, and optical fiber communication.
H. Zaari · M. Boujnah · B. Khalil · A. Benyoussef · As is known, the performance of optoelectronic devices is
A. El Kenz ()
LMPHE (URAC 12), Faculté des Sciences, Université strongly influenced by the electronic and chemical proper-
Mohammed V-Agdal, Rabat, Morocco ties of heterostructure surfaces and interfaces. The inherent
e-mail: [email protected] problem of the GaSb-related technology is high chemical
activity of the material, which causes the quick growth of
H. Labrim
surface oxides [2]. But, due to its high mobility, GaAs is
Centre National de l’Energie, des sciences et des Techniques
Nucléaires (CNESTEN), Rabat, Morocco considered among most materials to replace silicon in future
electron devices.
A. Benyoussef Research on gallium arsenide is moving toward multi-
Institute of Nanomaterials and Nanotechnology, MAScIR, Rabat, axis. The most important are: the study of defects and view
Morocco
their effects and their contribution on the stability of the sys-
A. Benyoussef tem, the second is the doping with the transition element and
Hassan II Academy of Science and Technology, Rabat, Morocco seek magnetic contribution and ferromagnetic stability.
 J Supercond Nov Magn

Defects play a key role on the properties of the semi- fects of substitution 3d transition-metal elements, for Ga site
conductors, and are often invoked to explain several effects, in GaAs, on their electronic and magnetic properties in order
such as pinning of the Fermi level, variation in the surface to seek new possible ferromagnetic phase in the III–V based
chemical reactivity, and in the diffusion at surfaces and in- DMSs. For these purposes, we perform ab initio electronic-
terfaces [3]. Among the native defects, the main theoretical structure calculations, and we use the method based on the
interest has been oriented toward monovacancies, anti-sites, Korringa–Kohn–Rostoker coherent potential approximation
and interstitials, but also vacancy complexes such as diva- (KKR-CPA) method in connection with the local density ap-
cancies have been studied [4]. proximation (LDA) [10].
Many studies have been done to control the behavior of
defects in semiconductors, for example, the charge state of
the isolated or clustered defects, influence on the defect- 2 Calculations Details
mediated diffusion, both in the bulk and on the surface. The
diffusion process depends upon the temperature, position of Our present calculations are based on the density functional
the Fermi level, chemical potential, or ambient oxygen pres- theory using the MACHIKANEYAMA 2009 package pro-
sure of the system. Despite this progress, much remains un- posed by Akai [11]. This approach is relying on compu-
known about point defect structure and ionization behavior. tations performed by KKR-CPA method. In our numeri-
The charge state of many bulk and surface defects are de- cal simulations, we explore LDA which is based on the
pendent on structural forms. Charged defects on surfaces parameterization given by Moruzzi, Janak, and Williams
may induce energetically favorable surface reconstructions (MJW) [12]. The relativistic effect has been considered
or lower the energy of the cleaved plane [5]. Many defects using the scalar relativistic approximation. Moreover, the
introduce strain into the crystal lattice. The symmetry of a potential form is approximately given by the muffin tin
point defect after relaxation, as well as the magnitude and model. The corresponding wave functions in the muffin-
tin spheres have been expanded with the real harmon-
direction of the relaxation, typically depends upon charge
ics up to l = 2, where l is the angular momentum de-
state. Local symmetry is often breaking in the presence of
fined at different sites. In what follows, we use higher K-
both neutral and ionized defects, responsible of the Jahn–
points up to 456 in the irreducible part of the first Brillouin
Teller distortions, which produce structural relaxation. The
zone.
distortions occur when a degenerate set of orbitals is occu-
Stability of magnetism in these last native point defects
pied unevenly with electrons, leading to unevenly balanced
in GaAs is discussed; the ferromagnetic state and the disor-
forces [6].
dered local moment (DLM) state are considered. The Curie
On the other hand, Ga and As monovacancies present in
temperature is estimated from the total energy difference
the crystal can form bound pairs with the binding energy of
between the (DLM) and the (FM) state by using a map-
1.44 eV [4].
ping on the Heisenberg model in mean field approxima-
Regarding the doping of GaAs with the element of tran- tion.
sition, it is especially doping with Mn, which is the most
studied. The big attention has been focused on this impor- GaAs Compound Bulk GaAs is routinely grown by Liq-
tant class of material. It has opened up the possibility of uid Encapsulated Czochralski (LEC) or Vertical Gradient
adding magnetism to this material system [7]. The introduc- Freeze (VGF) methods. Such bulk material is thus grown
tion of Mn in GaAs produces an acceptor; the induced hole at temperatures close to the melting point of GaAs, and con-
is believed to interact with the localized orbital of the TM sequently is characterized by rather high concentration of
impurity and mediated ferromagnetism. The exact nature deep traps related to native defects [13].
of the hole-TM interaction is still under debate [8]. How- Like all III–V compound semiconductor, GaAs crystal-
ever, the GaMnAs is the most intensively studied dilute mag- lizes in a zinc-blende structure (see Fig. 1), with lattice con-
netic semiconductor system. The Curie temperature (TC ) of stant a = 5.65 Å [14]. In the space group F-43m, Interna-
GaMnAs was limited to 110 K due to segregation of the sec- tional Tables No. 216 of X-ray Crystallography, we place
ond phase MnAs, when the Mn incorporation exceeded the the Gallium site in the positions (0, 0, 0) and Arsenic site is
solid solubility limit in GaAs [9]. placed in the positions (1/4, 1/4, 1/4).
Our aim in this paper is to study the behavior of different GaAs at ambient pressure crystallizes in the zinc blende
point defects in GaAs, which are Gallium interstitials (Gai ), structure and undergoes a transition to the rock salt structure
Gallium antisites (GaAs ), Arsenic interstitials (Asi ), and Ar- upon compression. It also transforms to CsCl structure at
senic antisites (AsGa ), on the electrical and magnetic prop- very high pressures [15]. Here, we consider the most stable
erties of GaAs. Especially, we want to confirm the results of structure which is zinc blende, it has a direct band gap with
doping of GaAs with impurities in Ga site and study the ef- a value of 1.519 eV (Fig. 2) [16].
J Supercond Nov Magn

Fig. 1 Unit cube of GaAs crystal lattice

Fig. 3 Variation of total energy as function of GaAs type of defect

3 Results and Discussion

3.1 Magnetic Properties and Electronic Structure of Native

Point Defects in GaAs

Point defects are localized defects of atomic dimensions;

they occur in an otherwise perfect crystal lattice. These point
defects can include vacancies, interstitials, intrinsic defects
present in the material also play an important role in the
electronic behavior of GaAs.
In this section, the electronic and magnetic structure of
Gallium interstitials (Gai ), Gallium antisites (GaAs ), Arsenic
interstitials (Asi ), and Arsenic antisites (AsGa ) defects in
GaAs, with zinc blende symmetry, are studied, using the
Fig. 2 Density of states of GaAs KKR-CPA method. Before beginning this type of study, we
have made preliminary magnetic calculations in different
types of point defects mentioned above, in order to identify
the defects having a magnetic behavior in GaAs. The results
The electronic structure of the III–V based DMSs has of this calculation are schematized in Fig. 3.
been studied theoretically from first principles in order Total energy is one of the most important quantities in a
to clarify the nature of the magnetic interaction between solid state system, as it determines the stable configuration
M-spins as well as between M-carrier-spins in GaMAs [18]. So, it can be concluded after the calculations that with
(M = Ti, V, Cr, Mn, Fe, Co, and Ni), it has been confirmed the exception of the VAs defect, which is the n-type, all the
that the ferromagnetic state is half metallic for GaMnAs; other defects are the p-type. It is shown in Fig. 4 that the Asi
i.e., the majority (minority) spin state is metallic (semi- is the type of defect that brings more stabilization in terms
conducting), and is stable compared with other magnetic of energy in GaAs.
states. Furthermore, it has been proposed by Akai based
3.2 Doping GaAs with Transition Metal
on the Korringa–Kohn–Rostker coherent—potential approx-
imation (KKR-CPA) calculations that the double-exchange The ferromagnetic state of a TM-doped GaAs compound
mechanism stabilizes the ferromagnetic state in the III–V is described as (Ga1−x TMx )As and the disordered magnetic
based DMSs. However, the microscopic origin of the ferro- configuration is described as a random alloy (Ga1−x TMX/2up
magnetism in the III–V based DMSs has not yet been fully TMX/2down ) As with zero net magnetization [21].
understood from both experimental and theoretical points of Doping GaAs with Mn, Cr, and V has the effect of in-
view [17]. troducing holes into the semiconductor. Spin-up 3d holes
 J Supercond Nov Magn

Fig. 6 Partial density of states for different concentration of cobalt

Fig. 4 Calculated total energy between the spin glass states and the showing that the exchange mechanism is the superexchange in
ferromagnetic state DMS in GaAs Positive value means that ferromag- Ga1−x Cox As for x = 0.05, 0.1, and 0.150 (Color figure online)
netic state is more stable than the spin-glass state; this consistent with
the results of reference [24]
(DLM). It was found that the most important differences be-
tween the spin up and spin down is the position of 3d bands
derived from the Co atoms. The DLM becomes stable due to
the anti-ferromagnetic superexchanges interaction (Fig. 6).
Doping GaAs with Co causes the states close to the Fermi
level to have opposite spins, weakening the p–d hybridiza-
tion and causing localized e states and t2g states to appear
in the band gap (see Fig. 5). This weakens the migration
properties and allows the anti-ferromagnetic superexchange
interaction to predominate over the ferromagnetic double
exchange interaction, resulting in an antiferromagnetic spin
glass state [20]. There are two possibilities to transform the
DLM state into the ferromagnetic one: by a boost of tran-
sition element and create holes, or by codoping with two
elements of transition.

3.3 Doping GaAs with Impurity and Defects

Fig. 5 Total density of state (red line) and partial density (black line)
3d state for Ga1−x Cox As (x = 0.05) (Color figure online) Ga1−x Cox As have the calculated the total magnetic moment
0.16μB , which is strongly localized on Co sites. The TM
+ + − −
(Co) impurity has 3d 7 (d 7 = e2g t2g e2g t2g ) electron configu-
that are close to the Fermi level mainly enter a t2 state with
strong p–d hybridizations, which allows them to migrate ration due to the substitution of Ga2+ by TM2+ ions, which
through the crystal, resulting in a ferromagnetic half-metal get a high magnetic moment of TM.
states due to the so-called double-exchange interaction aris- It is clear that the charge density came to the Fermi level
ing from the reduction of band energy. In particular, the most by increasing the concentration of defect on GaAs doped
stable ferromagnetic states are achieved with V, Mn, and Cr, with cobalt, which shows the nature of exchange in this case.
and Tc is 983 K for Cr, and 110 K for Ga1−x Mnx As for This is called the superexchange mechanism (Fig. 7) and
0.01 < x < 0.15 [19] (Fig. 4). Tc is calculated, within mean it is one of the important ferromagnetic mechanisms. This
field approximation, from the relation. hybridization between the Co-3d, and As-2p states and the
CPA − E CPA
host valence bands produces effective magnetic field to align
2 EDLM Co magnetic moments and stabilize the ferromagnetic state.
KB TCMFA = FM
3 c As in Table 1 and Fig. 8, we can see that the increase of
From the dos plot reported in Fig. 5, for 5 % of Co, it is concentration of the defect (VGa ) in GaAs doped with the
inferred that this compound is in the disorder local moment Co increases the value of Tc to 318 K. But when the holes
J Supercond Nov Magn

Table 1 Doping GaAs with

cobalt and defect in Ga site Dopant Concentration E (Ryd) Total moment (µb) Tc (K)
(VGa )
Co 10–1 % 9.3910−5 −0.1792 89.99
10–2 % 0.0003384 −0.14796 265.32
10–3 % 0.0004427 −0.1611 317.93
10–5 % 0.0004536 −0.12798 318.80
10–7 % −0.0000065 −0.10136 DLM

Table 2 Codoping GaAs with

Fe and Co Dopant Concentration E (Ryd) Moment (µb) Tc (K) Partial moment (µb)

Fe–Co 7–18 0.001068 0.07417 450.38 For Fe: −3.0237

7–10 0.0005719 0.05494 354.66 For Co: −1.74499
10–5 % 0.0003717 0.25691 261.24

Fig. 7 3d states of codoped in GaAs with a different concentration of Fig. 9 Total density of state (red line) and partial density (black line)
defect (VGa ) in Ga1−x−y Cox VGay As for x = 0.1, y = 0.02, 0.03; 0.05 3d state for Co in Ga1−x−y Cox VGay As for x = 0.10 and y = 0.02
(Color figure online) (Color figure online)

concentration exceeds 5 %, the frustration may appear in the

system and the state is no longer ferromagnetic.
In this study, only the defect of VGa gives a ferromag-
netic state with cobalt, but other types of defects show no
ferromagnetic state.

3.4 Codoping with Transition Metal

It should be noted that the iron-doped GaAs is stable in the

DLM state and is the same for the cobalt. Codoping GaAs
with two elements (iron–cobalt) stabilize a ferromagnetic
state with the increase of Tc by increasing the concentration
of cobalt relative to iron (Table 2).
The band gap of GaAs decreases by doping this com-
pound with TM and it disappears (Figs. 9 and 10) for a con-
centration value greater than 5 %. We note that the choice of
Fig. 8 Variation of curie temperature as function of concentration of defects or impurities concentration is limited by the solubil-
defect VGa in codoped GaAs ity of the system and the frustration.
 J Supercond Nov Magn

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