Hole induced local moments in ZnO doped with N

M. Shaughnessy,1, 2 C.Y. Fong,1 and L.H. Yang2

1
Department of Physics, University of California, Davis, CA 95616-8677
2
CMMD, Lawrence Livermore National Laboratory, Livermore, CA 94551
(Dated: February 16, 2011)
We study magnetic properties of the oxygen, O, substituting nitrogen, N, dopant in ZnO. The N
impurity creates a fully spin-polarized hole state with a magnetic moment of 1µB .By comparing local
spin and charge densities, we first investigate how the isolated N-hole alters the spin distribution in
the nearby bonding p states of the semiconductor matrix. The relation between the magnetic state
and the local relaxation around the N impurity is elaborated. To understand the coupling between
the N impurities we compare the N dopant environment in ZnO with the better understood N-doped
MgO. Finally two atom impurity complexes are studied to understand spin-polarized hole couplings.
Key Words: Dilute magnetic semiconductors, magnetic moment, transition metal oxides, sp-
ferromagnetism, d0 ferromagnetism

PACS numbers:

I. INTRODUCTION
Dilute magnetic semiconductors (DMS) are of great
interest to the growing field of spintronics for use in
potential devices in which the electron spin as well as
charge is the operational paradigm. Advantages such
as non-volatility, lower power consumption, and qualita-
tively new functionalities, including quantum computing,
make spintronic technologies appealing. Device materi-
als are the key components because the new functionality
may often be achieved from new properties of the materi-
als themselves. Some of the present-day semiconductors
in which magnetism has been induced by doping are Si,
GaAs, GaN, ZnO and MgO [1–6]. See also [7] and ref-
erences therein. Other materials such as the Heusler al-
loys and transition metal oxides have been considered in
the context of spintronic applications. Modifying mag-
netic properties of present-day, technologically mature
semiconductor materials may expedite the realization of
spintronic devices. In this context, an appealing material
is ZnO.
ZnO is a wide bandgap (3.3 eV at room temperature)
semiconductor used in a variety of applications, including
photoelectronics [8]. It has the wurtzite structure, with
two atoms per unit cell. Inducing magnetic properties in
ZnO would allow it be used in modern applications that
require magnetic, optical and electrical control, such as
polarized light emitting diodes.
Most DMSs are created by doping transition metal
atoms (TMA) into the semiconductor matrix. The re-
sulting p-d hybridization induces a sometimes long-range
spin polarization in the materials. The local moments on
the TM elements are coupled by the free carriers. There
has been extensive theoretical and experimental work on
doping TM elements into semiconductors, but there is
still controversy about the experimental saturation mag-
netization and Curie temperatures [9, 10]. TMA doping
in ZnO has been studied experimentally [11] and theo-
retically [12]. Doping with the proper TMA can yield
ferromagnetic behavior in which the cation sites are cou-
pled by free carriers. A second, less explored, path to
achieve magnetism in semicondcutors is through sp im-
purity doping [13–16] in which sp-defects or the valence
bands become spin-polarized. Because the Stoner cri-
terion for ferromagnetism indicates that the density of
states at the Fermi level must be large, this second path
without the d-electrons from a TM defect is less obvious
because the density of states coming from the s- and p-
states is relatively small. Nonetheless in some systems
this sp-ferromagnetic or so-called d0 mechanism occurs
and is of interest both because it opens up an alternate
way to achieving room temperature ferromagnetism in
present day semiconductor materials but also because it
may help understand magnetic interactions occuring in
the more common d -electron doped semiconductor sys-
tems.
Experiments have aimed at, and succeeded in, produc-
ing p-type ZnO by doping with N [17, 18] and there is
some evidence that ferromagnetism may also occur [19],
particularly in thin films[20, 21]. In C doped ZnO there
is ample theoretical and experimental evidence that O-
substituting C produces above room temperature ferro-
magnetism [22–24]. Theoretical work on N doping in
MgO [25, 26], in CaO[13] and In2 O3 [27] indicate that d0
ferromagnetism may arise in these systems. Droghetti et
al [28] include self-interaction corrections and show the
appearance of Jahn-Teller distortions near the N dopants.
They argue that the resulting spin density will lead to a
lower exchange coupling between dopants. Experiments
on pure ZnO nanowires [29] and theory [30] suggest that
O vacancies may also play a role in ferromagnetism in
ZnO. Ferromagnetism has been studied in N doped ZnO
in [31], where co-doping with Li is also considered, and
in [32], which includes the study of two-dopant super-
cell models. There has been little consideration of the
structural relaxation around the N defect in ZnO and

the residual forces on the atoms in other works [31, 32]
are rather large, 0.01 - 0.02 eV/Å. While the gross mag-
netic properties may not be changed it is important to
know how the structural relaxation alters the details of
the magnetic states, especially given the small observed
energies and magnetic moments. In this paper we use
first principles density functional theory (DFT) to an-
alyze the electronic and magnetic structure of N-doped
ZnO paying special attention to the role of the crystal
structure and structural relaxation in determining the
character of the induced spin polarization.
We use a supercell approach within DFT to study sin-
gle and multiple atom defects of N in ZnO. In section II
we give a brief description of the method used. In sec-
tion III we investigate A.) the spatial character of the
induced spin polarization around the N defect, B.) the
role of the local structural relaxation is studied, and C.)
multi-atom defects in a supercell, which allow us to esti-
mate the short range exchange coupling, are considered
Finally, in D.) we compare the magnetic and electronic
structure of N doping in ZnO to N doping in MgO and
discuss the role played by the differing crystal structure
of these two oxide semiconductors. A summary is present
in section IV.
II. METHOD
We used the VASP code [33] to determine the basic
structural and magnetic properties of the alloys using
projector augmented wave (PAW) psuedopotentials with
the normal electronic configurations. We use supercells
with between 16 and 216 atoms for ZnO and between 16
and 512 atoms for MgO. To begin, the atomic positions
are held fixed at the ideal crystal positions, which are de-
termined for pure ZnO or MgO, and the N atom substi-
tutes one O. The six Zn atoms closest to the N are called
nearest neighbor (nn) Zn and the six closest O atoms are
called first shell O. Because of the doping, the forces act-
ing on the atoms may initially be large and so in our cal-
culations structural relaxation requires all forces on the
atoms are less than 0.006 eV/Å. A planewave basis with
650 eV cutoff energy and a (10,10,10) Monkhorst-Pack k-
point mesh [34] was used for the 16-atom case. As the cell
size increased, we reduced the mesh points according to
the inverse square ratio of the lattice constant of the large
cell to the one of the 16-atom case. The generalized gra-
dient approximation (GGA) of Perdew 91[35] was used to
treat the exchange-correlation of the electrons. We note
that other authors [28] have used hybrid functionals in-
cluding some fraction of exact exchange in order to more
realistically model the d0 ferromagnetism. In the section
concerning the Jahn-Teller distortion we briefly discuss
our results using a hybrid functional (PBE0) for exchange
and correlation, which includes a self-interaction correc-
tion, in 16 atom supercell models of the single N defect in
2
ZnO and MgO. The fraction of exact exchange included
is 0.25, to agree with conventional practice.
III. RESULTS
A. Spin polarized hole density
The isolated N atom takes the place of one O atom,
causing a localized deficit of charge that integrates to ex-
actly one less electron in the entire supercell, per N. The
formation energy of the N defect is -8.253 eV, computed
using a chemical potential for ZnN in the wurtzite struc-
ture with the same lattice constant as the ZnO. In the
128-atom supercell:
63 1
Ef = EZnO + EZnN − EZnO:N (1)
64 64
We also note that the moment per N atom is exactly
1 µB for all supercell sizes we study unless specifically
noted. In order to be confident that the supercell we
use is large enough, we have computed some properties
of supercells up to 216 or 512-atoms for ZnO and MgO.
The 128-atom cell is the smallest supercell large enough
to treat the single N defect as roughly isolated, based
on the magnetic properties and structural relaxation. It
corresponds to a concentration of about 1 at%. We use
this cell size in all further calculations, except during the
investigation of the Jahn Teller distortion, in which the
computational workload imposed by the PBE0 functional
necessitates a 16-atom cell.
We examine the shape of the hole defect by plotting
isocontours of either charge or spin density in a plane
that contains the nn Zn, the N defect and the nearby
O atoms. We calculate the difference densities from the
electronic densities of the models with and without the N
defect. We forbid the local atomic relaxations and hold
the atoms in the N defect model fixed in the positions
specified by the defect-free crystal in order to make the
subtraction as simple as possible. As we will see below
the relaxations are small so they may be safely neglected
in this section, to focus on the qualitative nature of the
local hole due to doping. The shape and size of this hole is
illustrated in the plots of total charge density, ρ = ρ↑ +ρ↓ .
The isocontours of the pure ZnO charge density, ρpure
are shown in Fig.1. Fig. 2 shows the isocontours of the
charge density, ρdoped , in the same cell with the N dopant.
Fig. 3 shows the local density of states on three atoms
in the supercell: the N dopant, a first shell O and a nn
Zn. In accord with the charge and spin density plots, the
majority of the spin polarization is occurring on the N
atom, due to the exchange splitting of the N p-states.
We define a hole density, ρhole , by subtracting the
doped density from the pure ZnO density:
ρhole = ρpure − ρdoped (2)
 3

25
100

20 N Spin−up

Local Density of States (states/eV)

90
15
80
10

70 5

60 0

−5
50

−10
40 Spin−down
−15
30
−20
−15 −10 −5 Ef 5 10
20 Energy Relative to Ef (eV)

10
150

120
10 20 30 40 50 60 70 80 90 100 Zn

Local Density of States (states/eV)

Spin−up
0.5 1 1.5 2 2.5
90
4
x 10
60

30

FIG. 1: The pure ZnO charge density in the vertical plane. −30
The Zn atoms are the brighter upper row −60

−90 Spin−down

−120

−150
100 −15 −10 −5 Ef 5 10
Energy Relative to Ef (eV)

90

25
80
20 O
Spin−up
Local Density of States (states/eV)

70 15

10
60

5
50
0
40 −5

30
−10

−15 Spin−down
20
−20
10
−25
−15 −10 −5 Ef 5 10
Energy Relative to Ef (eV)
10 20 30 40 50 60 70 80 90 100

0.5 1 1.5 2 2.5

4
x 10
FIG. 2: The charge density in the same plane with a N defect.
The resolution is greater to focus on the area near the N atom.
The N atom is slightly dimmer, indicating less charge
FIG. 3: The atom projected local density of states (LDOS)
on the N defect, a nn Zn and a neighboring coplanar O atom.
Densities are defined by integrating in a sphere of radius 0.741
Å, 1.270 Å, and 0.820 Åfor the N, Zn, and O atoms, respec-
tively.

spin polarization, we define a spin density

Fig. 5 shows the isocontours of ρhole around the N impu- s = ρ↑ − ρ↓ . (3)

rity and its neighbors. As might be expected, the hole is
largely concentrated around the N impurity with smaller Because the pure ZnO is not spin-polarized, spure = 0
differences induced in the nearby interstitial regions, on and so shole = sdef ect . Note also that
the nn Zn’s, and on the nearest in-plane (first shell) O
atoms. As shown by Fig 5. the induced hole-densities 1
ρ↑ = (ρ + s) (4)
on the nearby Zn and O atoms show two distinct char- 2
acteristics, namely the induced density on the O atoms
is dipolar but the induced densities on the nn Zn atoms 1
is monopolar. ρ↓ = (ρ − s) (5)
2
In order to investigate the spatial distribution of the
 4

128 Atom Supercell Charge Density Along a Line

9.07 100

90

80

70

60
Charge Density (e’s/Angstrom3)

6.05
50

40

30

20

3.02
10

10 20 30 40 50 60 70 80 90 100

0 50 100 150 200 250 300 350 400 450 500

0
0 3.25 6.5 9.75 13
Distance (Angstrom)
FIG. 6: The spin density of the hole, equal to the defect
spin density. There is a large moment concentrated on the
FIG. 4: Charge density along a line containing the N defect
N atom as well as induced smaller moments on the nearby O
and several co-planar O atoms. The line spans the supercell.
atoms and in the interstitial space between the N its nearest
The N defect is located at about 9 Å and clearly shows a hole
neighbor Zn atoms
character.

100

90 100

80 90

70 80

60 70

60
50

50
40

40
30
30
20
20
10
10
10 20 30 40 50 60 70 80 90 100
10 20 30 40 50 60 70 80 90 100
−60 −40 −20 0 20 40 60 80 100 120 140

−20 0 20 40 60 80 100 120 140 160 180 200

FIG. 5: The hole density ρhole shows the charge difference

between the pure and the defect models. The dominant effect FIG. 7: The majority up spin density for the defect. Note the
is a net surplus of positive charge, integrating to 1 e over the lopsided dumbell shaped induced moments on the O and also
entire supercell. However, there is halo of induced negative the induced moments near the Zn atoms.
charge around the N defect, as well as small dipoles induced
on the nearby O atoms. The positions of the atoms are the
same as in Fig. 2; the neighboring oxygens are located at the
centers of the left- and rightmost positive lobes.
instead a rounder distribution. On the other hand, the
induced up spin density is qualitatively different (Fig. 8);
Comparing the contours of the down spin density of the on the first shell O atoms there is a large negative spin up
hole to the contours for the up spin density of the hole, density and there is little if any induced spin-polarization
we see that the down spin density is increased on both in the vicinity of the nn Zn. Remembering that the spin
the first shell O atoms and on the nearest neighbor Zn densities of the hole are defined by the subtractions in
atoms (Fig. 6). The induced down spin polarization on Eqs. 4 and 5 and glancing at Fig. 7 shows the negative
the first shell O atoms (directly to the left and right of the spin up density is also a spin down density. In summary,
central N in Fig. 7) shows a dumdbell, p-like character, the states on the co-planar O atoms and those on the nn
while the down spin polarization on the Zn atom (above Zn are both spin polarized parallel to the polarization of
right and above left of the central N in Fig 7.) shows the hole state on the N atom.

100
90
80
70
60
50
40
30
20
10
10 20 30 40 50 60 70 80
−100 −50 0 50 100
FIG. 8: The minority down spin density for the defect. For
this spin, the lopsided dumbell shaped contours are present
on the O atoms, but the induced spin toward the Zn atom is
conspicuously absent.
B. Relaxation and Spin-Polarization
In addition to the induced spin-polarization the O-
substituting N defect also induces a structural relaxation
of atomic positions. The two effects are interdepen-
dent because the relaxation changes the available volume
around the N, allowing for more or less spin-alignment
of the electrons governed by the Pauli exclusion princi-
ple. The unrelaxed nearest-neighbor distance in the ZnO
crystal is 2.18 Å. The relaxation draws the neighboring
Zn atoms closer to 2.15 Å toward the N. The coplanar
O atoms are pushed away from the N; the separation is
increased from 2.97 Å to 3.01 Å. The ionic bonds in ZnO
are formed between Zn-O pairs. When the N is present
the nn Zn atoms give three rather than the usual two
electrons to the N to fill its shell. This means these nn
Zn atoms are more strongly drawn toward the N and
away from their O neighbors, because the O neighbors
are less strongly bound to the nn Zn atoms than they
are to the Zn atoms that are not bonding with the N.
So the O atoms will indirectly move away from the N
by moving away from the nn Zn atoms. The energy as-
sociated with this structural relaxation is 234 meV for
the 128-atom cell. The energy scale for the atomic re-
laxation is much larger than for the magnetic relaxation.
Fig. 9 shows the spin polarized energy as a function
of the magnetic moment in the 128-atom ZnO supercell
with relaxed atomic positions. We define ∆EM = E0µB -
E1µB where ExµB is the total energy of a single N defect
supercell with magnetic moment x. The electronic relax-
ation is constrained such that the magnetic moment is x
in order to arrive at these energies. With relaxed atomic
positions ∆EM = 8 meV, while the energy lowers by 234
meV as the atoms relax with the moment fixed at 1.0
5
90 100
150 200
FIG. 9: The magnetization energy as a function of total su-
percell magnetic moment. Structural relaxation is allowed
while the magnetic moment is fixed for each data point.
µB . Because of the large disparity in the energy scales
for the two relaxations and the effect of the atomic re-
laxations on the magnetic energy splittings, we compute
the spin polarization energies using both fixed and re-
laxed atomic positions. The atomic relaxation definitely
alters the magnetic relaxation, too. With fixed atomic
positions, ∆EM = 57 meV. In general the atomic relax-
ations decrease ∆EM significantly.
A second measure of the magnetization energy is the
spin polarization energy, which is the difference in total
energies between a spin polarized and the same non-spin
polarized DFT calculation. The spin polarization energy
difference is only 1.8 meV when the atomic positions are
allowed to relax in both models, while it is 80.3 meV
when all atom positions are fixed. In [36] it is suggested
that the relaxation and associated decreased bond length
between the dopant and the nn Zn leads to increased d-p
hybridization and greater delocalization of the p-states
for C doped ZnO. This increased delocalization reduces
the magnetic moment because the holes are transfered to
the neighboring sites, which are less strongly spin polar-
ized. This weaker polarization on the neighboring sites
is clear in our results particularly the spin distributions
in Figs. 6 and 7. In [36] they claim the holes bound
to the O’s are not spin-polarized, but we see a greater
spin-polarization on the nn O than on the nn Zn (see the
first section of Table 1), In our case the structural relax-
ation does not bring the O atoms closer to the N and
the spin polarization on the O atoms remains the same
before and after relaxation. Although we see a greater
polarization on the O atoms than [36], a similar explana-
tion can account for our result showing a much lower but
still positive ∆EM with structural relaxation; in our case
the squeezing of the N by the nearby atoms makes it en-
ergetically easier, but still unfavorable, for the electrons
to assume the non spin polarized state. The difference is
that in the present study the moment is largely localized
 6

on the N atom, whereas in [36] the moment is spread onto

the neighboring O atoms. In both cases the relaxation
makes the spin-polarization less favorable but through
different mechanisms.
The Jahn-Teller effect refers to a symmetry breaking
atomic relaxation that lifts a degeneracy of electronic
states near the Fermi energy to lower the total energy.
In [28] a self interaction correction (SIC) is included in
the exchange correlation functional because the magneti-
zation comes from a hole whose properties may be espe-
cially sensitive to such corrections. In N-doped MgO, an
FCC crystal, there is a triplet of degenerate states near
Ef . Our calculations using the PBE0 functional show
that in MgO this degeneracy is lifted by a Jahn-Teller
distortion, leading to a spin density localized along one
of three possible mutually orthogonal Mg-N bond axes. FIG. 10: The 128-atom ZnO supercell showing the positions
The distortion is an elongation along one axis of the Mg- for the five N-N separations. The large white atom is the
N bonds and small contractions along the other two di- reference N atom, the same for all five models, and the other
rections. Essentially the Jahn Teller distortion is allowed colored atoms are the second N impurities. Separation A
around the N impurity because the cubic symmetry gives corresponds to the red atom, B to the blue atom, C to the
orange atom, D to the light green atom, and E to the blue
rise to the triply degenerate states near Ef . In ZnO the
green atom.
lower symmetry wurtzite structure yields a splitting of
the p-states near Ef , two of which are doubly denegerate
and one with a higher energy. Neither the structural
relaxation nor the use of the PBE0 functional lifts the
degeneracy of the two states, although Ef shifts position
relative to these states. This result is not surprising when
atoms. This result makes sense in conjuction with the
we remember that the wurtzite structure has the hexag-
observation that the spin densities on the O atoms have
onal symmetry in the x-y plane. The bond lengths in
a more dipolar character and that the structural relax-
the z-direction are already, however, greater than those
ation tends to decrease the magnetic energy splitting as
in the x-y direction and so no additional elongation will
measured by either the spin-polarization energy or ∆EM .
lower the total energy. We conclude that the use of a self
The reason is that when the structural relaxation spreads
interaction correction in the exchange correlation poten-
more of the spin polarized hole density to the O atoms
tial through the hybrid PBE0 functional does not qualita-
the amount of spin density in the dipolar states increases,
tively change the character of the structural relaxation or
as does the spatial extension of the spin-polarization in
the associated spin-polarized hole state on the substitu-
the supercell. The more dipolar, dispersed density is eas-
tional N impurity. In particular no Jahn Teller distortion
ier to polarize, due to smaller effect of the Pauli exclusion
occurs, unlike in MgO, because of the lower symmetry of
because the electronic density is less concentrated and so
the wurtzite ZnO structure.
there is more room for the parallel spin electrons to co-
In addition to a large spin-polarization energy a suffi-
exist. In contrast, when the density is concentrated more
cient extension of the hole impurity state is required for
strongly on the N atom before the structural relaxation it
a high Curie temperature because some overlap is needed
becomes more energetically costly to alter the magnetic
to mediate the exchange. The plots (Figs. 1-7) of charge
moment because the Pauli exclusion is more relevant in
and spin density above give a qualitative sense of the ex-
regions of high density. In summary, the structural re-
tension of the impurity state. To further investigate the
laxation spreads the spin-polarization away from the N,
extent of spin polarization around the single N-defect,
lowering the magnetic energy splitting, ∆EM .
we compute the integrated magnetic moments within a
Wigner-Seitz sphere (Rws = 0.741Å, 1.270 Å, and 0.820
Å for N, Zn, and O respectively) centered on each atom. These results lend credence to the idea that substi-
This information is shown in Table 1. tutional N defects in ZnO produce local moments and
Given that the N has multiple O and Zn neighbors, may contribute to a ferromagnetic state, especially with
a significant fraction of the spin resides away from the relaxation, which tends to spread the spin polarization.
N defect. The structural relaxation alters the distribu- However other types of defects, such as O vacancies or N
tion of the spin density: the spin, especially coming from interstitials may also be relevant for observed magnetic
the p-states, becomes less localized on the N and more properties. These other defects are beyond the scope of
localized on the nearby (both first and second shell) O the present work.
 7

Orbital decomposed and total magnetic moments (µB )

Isolated N (fixed atomic positions)
Atom S P D Total
N 0.09 0.305 0 0.314
nn Zn -0.002 0.001 0.014 0.012
1st shell O 0 0.026 0 0.026
2nd shell O 0.001 0.094 0 0.095
total -0.027 0.748 0.116 0.837
Isolated N (relaxed atomic positions)
Atom S P D Total
N 0.007 0.229 0 0.235
nn Zn -0.002 0 0.013 0.010
1st shell O 0.001 0.030 0 0.030
2nd shell O 0.001 0.102 0 0.104
total -0.020 0.751 0.125 0.856
Two-N complexes
Separation A
N 0.016 0.449 0 0.465
nn Zn -0.00 -0.002 0.037 0.026
sn O 0.004 0.098 0 0.102
total -0.014 1.462 0.232 1.680
Separation B
N 0.011 0.307 0 0.317
total -0.016 0.972 0.162 1.119
Separation C
N 0.010 0.332 0 0.342
total -0.034 1.506 0.247 1.719
Separation D
N 0.011 0.338 0 0.349
total -0.023 1.453 0.230 1.659
Separation E
N 0.009 0.318 0 0.327
total -0.039 1.517 0.246 1.724

TABLE I: The magnetic moments associated with each atom in various models. Both orbital projected (columns 2,3 and 4)
and total (column 5) moments are shown. The moments are got by integrating sdef ect in a atom centered sphere of radius
Rws . For the isolated N defect the nn Zn is the atom closest to the N defect. The 1st shell O is any one of the six coplanar
neighboring oxygens surrounding the N defect. The 2nd shell O is one of the two O atoms in the layers directly above or below
the N defect. For the two-N defect complexes in each case both N’s have the same moments. For separation A the nn Zn is
nearest neighbor to both N atoms, while the sn O is one of the oxygens directly above or below either N. The total row for
each model is the sum of the moments of all atoms in the supercell, excluding only the interstitial regions not covered by any
sphere.

C. Multiple N Atoms separations, should not necessarily be interpreted as rep-

In this section we study different configurations of two
substitutional N dopants to understand the magnetic
coupling between nearby N impurities in ZnO. Fig. 10
shows the relative positions of the two N atoms in the
128-atom supercells for the five different N-N separations
we studied. In all cases each N atom substitutes on O
atom. Because of the size of the supercell only the N-N
complexes with the two defects relatively near to each
other were studied. In fact, for the largest separation
the distance between the two N defects in the supercell
is approximately equal to the distance between N atoms
in neighboring supercells. Because of this problem our
results from these two-atom models, especially for larger
resentative of isolated N-N defect pairs, but rather as
giving an overall estimate of the magnetization energy
for alloys at concentrations greater than a few percent.
Our calculations are strictly applicable to ordered struc-
tures, but such a method has been used in, for example,
[37] and the details of the underlying special quasirandom
structures (SQS) approach can be found in [38, 39].
We define Erel = EtotA - Etoti where Etoti is the total
energy for the two-N defect model having one N at site A
and the other at site i with total magnetic moment 2µB .
Erel gives a measure of the energetic differences between
the various substitutional N atom separations. Similarly,
∆EM = EF M - EAF M , where EF M and EAF M are the to-
tal energies of the models with magnetic moment exactly

Multiple N dopant data (ZnO, fixed atomic positions)
Separation N-N distance (Å)
A 2.708
B 2.969
C 4.019
D 5.417
E 6.178
TABLE II: The unrelaxed two-atom ZnO models. The magnetic moment given is the lowest energy. The Erel and ∆EM are in
eV.
Multiple N dopant data (MgO Unrelaxed atomic positions)
Separation N-N distance (Å) Magnetic Moment (µB )
A 3.013
B 5.181
C 5.991
D 7.337
TABLE III: The unrelaxed two-atom MgO models. The N-N distance and moments are for the the magnetic configuration
with the lower energy. The Erel and ∆EM are in eV.
2.0 µB and 0.0 µB , respectively. This quantity gives a
measure of the energy differences between the ferromag-
netic and antiferromagnetic alignments of the moments
on the N atoms.
Separations A,B and C may be considered as models
of isolated two-atom defect complexes. The trend shows
that the N defects are attracted to each other; the Erel
column is positive for all separations, indicating that sep-
aration A is the lowest energy configuration among the
substitutional defects we study. There is some evidence
that interstitial positions for the N atoms may be most
favorable [40] and that these tend to decrease the ferro-
magnetism. The ∆EM for the three smallest separations
show that the ferromagnetic configuration is slightly fa-
vored, by about 80-90 meV. Recall that for the single N
defect the 1.0 µB state is energetically favored over the
0µB state by 57meV. For this single N case then ∆EM
can be regarded as the energy gained by aligning the
spins of the two halves of the hole on the N site. Then
∆EM for the multiple-atom models is the energy gained
by aligning the spins of two holes on nearby N defects.
For the larger two separations the trend is less clear.
In this case it is more beneficial to remember that the N
defects in the neighboring supercell are relatively nearby.
It is not clear why the anitferromagnetic configuration is
favored, however. In our previous work on TM dopants
in Si [7] we found that the magnetic moments are smaller
(more antiferromagnetic) for smaller supercells, perhaps
due to the k-point modulation of the wavefunctions in
neighboring cells leading to altered overlap integrals.
8
Magnetic Moment (µB ) Erel ∆EM
2.074 0 -0.097
1.407 0.206 -0.079
2.074 0.451 -0.082
1.509 0.193 0.017
1.407 0.360 0.0426
Erel ∆EM
2.0 0 -0.042
2.0 0.339 -0.152
2.0 0.267 -0.152
2.0 0.351 0.2437
D. Comparison with N doped MgO
Table III summarizes the results of two-N defects in
128 atom MgO supercells. Four N-N configurations are
studied. The values of ∆EM and Erel are computed in
the same way as for the ZnO. For all four separations
the lowest energy magnetic state is one with both N mo-
ments aligned, giving exactly 2.0 µB . As in ZnO, the
lowest energy separation is one with the N atoms clos-
est together. The values of ∆EM are roughly twice as
large as those in ZnO, indicating that the ferromagnetic
state in N-doped MgO may be more stable than in ZnO.
We attribute this to the greater symmetry of the fcc MgO
structure which more efficiently exchange couples the mo-
ments on nearby N atoms. We should remember that the
work of Droghetti et al [28] indicates that LDA or GGA
exchange correlation functionals without a SIC qualita-
tively mischaracterize the spin polarized density in this
system. In particular the shape of the spin-polarized hole
state on the N defect is in fact less symmetrical with
the SIC and so the exchange coupling and the associated
Curie temperature is probably overestimated in calcula-
tions without as SIC. However, our results suggest that
the SIC is not as important for the N-doped ZnO and so
the MgO (without a SIC) can be used to compare and
see the effect of the crystal symmetry. One final piece of
data, shown in Table IV, indicates how the spin-polarized
density spreads under the influence of the structural re-
laxation in N-doped MgO. This data should be compared
with the first two parts of Table I. As in the ZnO, the ma-
jority of the spin polarized density is localized on the N.
Because the Mg does not have any d-shell electrons, the
Mg atoms have a much lower spin polarization than the
analogous Zn atoms; the Mg p-states are the only ones

Multiple N dopant data (MgO, relaxed atomic positions)
Separation N-N distance (Å) Magnetic Moment (µB )
A 2.546
B 5182
C 5.991
D 7.337
TABLE IV: The relaxed two-atom models. The magnetic moment given is the lowest energy. The Erel and ∆EM are in eV.
available to yield a net moment, which is very small. The
moment on the surrounding O atoms is also smaller and
some O’s have zero spin polarization. This effect may be
an artifact of the supercell approach to modeling the iso-
lated defect produced by the periodic lattice of N impu-
rities in neighboring supercells. In fact a random alloy of
N-doped MgO at concentrations of ∼ 1% percent would
have few O atoms out of the line-of-sight of all nearby N
dopants, especially given the structural relaxations.
IV. CONCLUSION
We present density functional theory calculations of
the electronic and magnetic structure of single and mul-
tiple O-subsituting N defects in ZnO. There is evidence
for the formation of magnetic moments on the N atoms,
induced spin polarization in the neighborhood of the N
atom and ferromagnetic coupling between nearby N de-
fects. After structural relaxation the magnetic behav-
ior is suppressed due to the greater d-p hybridization
and delocalization of the holes from the N. Estimating
the Curie temperature within mean field theory and the
Heisenberg model, ie. kB TC = 2∆EM /3[41, 42] gives
230 K (using ∆EM / = 0.03 eV). Because the structural
relaxation for the single atom defect and the multiple
atom defects tends to have different consequences on the
magnetic exchange splittings, lowering them for the sin-
gle atom but leaving them more or less unaltered for the
N complexes, we believe the structural relaxation would
not significantly change this estimate, which is based on
the two-atom results. Expectations of ferromagnetism in
ZnO due to O-substituting N defects should be tempered
because of the role of structural relaxations in the single
atom properties. As pointed out in [26] the Curie tem-
perature in N-doped MgO is overestimated within the
Heisenberg model. Other sources of d0 magnetism might
be considered, for example cation vacancies stabilized by
N or Li [43] or contamination with C defects[44].
This work is supported in part by the NSF Grant
No. ECCS-0725902 and work at Lawrence Livermore Na-
tional Laboratory is under Contract No. W-7405-Eng-48.
We acknowledge helpful discussions with Phil Sterne and
Stuart Parkin.
9
Erel ∆EM
0.0 0 0.016
2.0 0.325 -0.268
2.0 0.275 -0.022
2.0 0.453 -0.210
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