Oxygen vacancies in ZnO

Anderson Janotti, and Chris G. Van de Walle

Citation: Appl. Phys. Lett. 87, 122102 (2005); doi: 10.1063/1.2053360

View online: https://doi.org/10.1063/1.2053360
View Table of Contents: http://aip.scitation.org/toc/apl/87/12
Published by the American Institute of Physics

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 APPLIED PHYSICS LETTERS 87, 122102 共2005兲

Oxygen vacancies in ZnO

Anderson Janotti and Chris G. Van de Walle
Materials Department, University of California, Santa Barbara, California 93106-5050
共Received 22 March 2005; accepted 28 July 2005; published online 14 September 2005兲
The electronic properties of ZnO have traditionally been explained by invoking intrinsic defects. In
particular, the frequently observed unintentional n-type conductivity has often been attributed to
oxygen vacancies. We report first-principles calculations showing that the oxygen vacancy VO is not
a shallow donor, but has a deep ␧共2 + / 0兲 level at ⬃1.0 eV below the conduction band. The negative-
U behavior that causes the 1 + charge state to be unstable is associated with large local lattice
relaxations. We present a detailed configuration coordinate diagram, which allows us to provide a
detailed interpretation of recently reported ODEPR 共optically detected electron paramagnetic
resonance兲 measurements 关L. S. Vlasenko and G. D. Watkins, Phys. Rev. B 71, 125210 共2005兲兴.
© 2005 American Institute of Physics. 关DOI: 10.1063/1.2053360兴

Zinc oxide is a wide-band-gap semiconductor with nu-
merous applications, for instance in varistors, phosphors, and
sensors. Recent progress in crystal growth has also opened
up prospects for optoelectronic devices. Such applications
are currently hampered, however, by the lack of control over
conductivity. ZnO is typically n-type, and high-resistivity
material has been difficult to obtain; p-type doping has been
reported,1,2 but reliability and reproducibility are serious is-
sues. Understanding the source of unintentional conductivity
is a crucial step towards control of doping. The accepted
wisdom is that the unintentional n-type conductivity is due to
native point defects.3 Oxygen vacancies have been most
widely discussed, but most of the arguments have been based
on circumstantial evidence, in the absence of unambiguous
experimental observations.
Recent computational studies4–7 have cast doubt on the
categorization of the oxygen vacancy 共VO兲 as a shallow do-
nor. However, the reported electronic levels display wide dis-
crepancies. In this Letter we present a comprehensive theo-
retical study which not only provides more reliable
electronic levels for the defect, but also addresses the unusu-
ally large atomic relaxations that occur in its various charge
states. These result in the 1 + charge state being thermody-
namically unstable, i.e., VO behaves as a ”negative-U” cen-
ter. Since the 1 + charge state is paramagnetic 共with VO +
con-
taining an unpaired electron兲 this instability has important
repercussions for observations of VO based on electron para-
magnetic resonance 共EPR兲: no EPR signal should be ob-
served in equilibrium, and an excitation process 共illumina-
tion兲 is necessary to produce the paramagnetic state. Our
calculated formation energies indicate that VO is too high in
energy to play any significant role in as-grown n-type mate-
rial. However, it is expected to act as a compensating center
in p-type ZnO and it can also be formed during irradiation
and ion implantation. Our calculated configuration coordi-
nate diagram allows a consistent interpretation of recent ex-
periments by Vlasenko and Watkins8 which have provided
the most detailed information to date about EPR and optical
transitions associated with VO.
Our investigation is based on state-of-the-art first-
principles calculations using density-functional theory,
pseudopotentials, and plane-wave expansions of wave func-
tions and potentials.9,10 A supercell geometry with 96 atoms
in the cell was employed, and a 2 ⫻ 2 ⫻ 2 mesh of special
k-points for integrations over the Brillouin zone. All of our
calculations are carried out at the theoretical equilibrium lat-
tice constants,11 which is essential in order to avoid spurious
effects when calculating relaxations. We derive the formation
energy E f , which determines the likelihood for a defect to
form during growth. The formation energy of a native defect
D in charge state q is defined as12
E f 共Dq兲 = Etot共Dq兲 − Etot共ZnO兲 + nZn␮Zn + nO␮O + qEF . 共1兲
Etot共Dq兲 is the total energy of the supercell containing the
defect D in the charge state q, and Etot共ZnO兲 is the total
energy of the ZnO perfect crystal in the same supercell. The
Fermi energy EF 共which will be referenced to the top of the
valence band Ev兲 enters because the defect can occur in vari-
ous charge states, and the electrons that are removed from
the defect need to be placed in their reservoir, with energy
EF. ␮Zn and ␮O are the chemical potentials of Zn and O, i.e.,
the energies of the reservoirs with which Zn and O atoms are
exchanged. For displaying our results below, we choose Zn-
rich conditions 共␮Zn = ␮Zn共solid兲兲, the most extreme case for
favoring formation of oxygen vacancies.
From the formation energies E f 共Dq兲 we can calculate
transition levels ␧共q / q⬘兲.12 Since the local density approxi-
mation 共LDA兲 severely underestimates band gaps, a correc-
tion is necessary to compare the calculated ␧共q / q⬘兲 with ex-
periment. We base the correction on calculations performed
using the LDA on the one hand, and the “LDA+ U”
approach13 on the other hand. The idea of the LDA+ U
method is to separate electrons into two subsystems: local-
ized d electrons for which the strong Coulomb repulsion U
should be taken into account via a Hubbard-like term in a
model Hamiltonian, and delocalized electrons which can be
described by an orbital-independent one-electron potential.
The LDA+ U approach lowers the energy of the Zn d states,
thus reducing their repulsion with the O p states at the top of
the valence band, and increasing the band gap.11 The LDA
+ U thus provides a partial but physically important correc-
tion of the band gap, the remaining correction arising from
the intrinsic LDA error 共see Table I兲. However, we can use
the LDA and LDA+ U results to extrapolate to the experi-
mental gap. Indeed, the shift of the transition level is deter-
mined by its relative amount of valence-band versus
conduction-band character, and this information is contained
in the shift of ␧共q / q⬘兲 between LDA and LDA+ U. Table I

0003-6951/2005/87共12兲/122102/3/$22.50 87, 122102-1 © 2005 American Institute of Physics

122102-2 A. Janotti and C. G. Van de Walle Appl. Phys. Lett. 87, 122102 共2005兲

TABLE I. Calculated band gaps and transition levels ␧共q / q⬘兲 for oxygen
vacancies in ZnO 共in eV兲. LDA, LDA+ U, and extrapolated values are
listed.

Eg ␧共2 + / + 兲 ␧共+ / 0兲 ␧共2 + / 0兲

LDA 0.81 1.30 0.16 0.73
LDA+ U 1.50 1.73 0.64 1.18
Ext. 3.43 2.90 1.94 2.42

shows the LDA and LDA+ U results as well as the extrapo-

lated ␧共q / q⬘兲, which is given by
FIG. 2. 共Color online兲 Ball and stick representation of the local atomic
relaxations around the oxygen vacancy in the 0, 1+, and 2 + charge states.
␧共q/q⬘兲LDA+U − ␧共q/q⬘兲LDA The position of the a1 state is also shown for the equilibrium configuration
␧共q/q⬘兲 = 共Eexp LDA+U
g − Eg 兲 of each charge state.
ELDA+U
g − ELDA
g

+ ␧共q/q⬘兲LDA+U , 共2兲 and VO 2+

where ELDA and ELDA+U are the band gaps given by the LDA
g g
and LDA+ U approximations, and Eexp is the experimental
g
gap.14 Table I shows that the transition levels exhibit signifi-
cant upward shifts when the band gap is corrected. This is to
be expected, since the VO defect states are composed of dan-
gling bonds on the neighboring Zn atoms, which exhibit
mainly conduction-band character. The extrapolated values
for the transition levels are also very close to results obtained
using self-interaction-corrected pseudopotentials,15 enhanc-
ing confidence in the approach.
Figure 1共a兲 shows the formation energy of the oxygen
vacancy VO as a function of Fermi level EF for the three
possible charge states VO 0
, VO+
, and VO2+
, corrected according
to the procedure described above. Under p-type conditions,
where EF is near the top of the valence band, the oxygen
vacancy is stable in the VO 2+
charge state and therefore acts as
a compensating center with low formation energy. Under
n-type conditions, however, where EF is near the bottom of
the conduction band, the oxygen vacancy is in the neutral
charge state. The calculated 共2 + / 0兲 transition level is located
deep in the band gap, at ⬃1.0 eV below the bottom of the
conduction band, indicating that VO will not provide elec-
trons to the conduction band at room temperature. In addi-
tion, the formation energy of VO under n-type conditions is
very high 共⬃3.5 eV兲, indicating that it is unlikely to form
even at high temperatures during growth. We conclude that
oxygen vacancies are not the source of unintentional n-type
conductivity.
Figure 1共a兲 also shows that the 1+ charge state is not
+ 0
stable: the formation energy of VO is higher than that of VO
FIG. 1. 共a兲 Formation energies vs Fermi level for oxygen vacancies in ZnO
in the 0, 1+, and 2 + charge states, under Zn-rich conditions, calculated using
the procedure described in the text. 共b兲 Position of ␧共2 + / 0兲 with respect to
the top of the valence band Ev in ZnO compared to that in ZnSe, taking into
account the natural valence-band offset.
for all values of EF. This is related to the fact that the
␧共2 + / + 兲 transition level is located higher in the gap than the
␧共+ / 0兲 level, an unusual ordering based on the expected
Coulomb repulsion that occurs when electrons are added to a
defect. Since the 1 + charge state is not stable in equilibrium,
any EPR measurements claiming to identify VO without pro-
viding any excitation should be treated with suspicion. In
fact, those papers systematically claim to identify VO based
on a line with g ⬇ 1.96. In reality, VO corresponds to a line
with g ⬇ 1.99, and the reports16,17 that correctly make this
identification have in common that 共1兲 electron irradition
was used to produce the defect 共since, in agreement with our
calculations, the starting n-type material contains only a neg-
ligible concentration of VO兲 and 共2兲 optical excitation was
found to be necessary to observe the EPR signal, in agree-
+
ment with the calculated metastability of VO .
The effective correlation energy U 共no relation to
the parameter in the LDA+ U approach above兲 is defined
as the difference between the relevant transition levels, i.e.,
U = ␧共+ / 0兲 − ␧共2 + / + 兲 = E f 共VO2+兲 + E f 共VO0兲 − 2E f 共VO+兲. Our
calculations yield ␧共+ / 0兲 = 1.9 eV and ␧共2 + / + 兲 = 2.9 eV,
and, hence, U = −1.0 eV. The negative value reflects the fact
that atomic relaxations play a major role in stabilizing par-
ticular charge states. Our calculations indeed show that the
lattice relaxations around VO are large and very different in
0
different charge states. For VO , the four Zn nearest neighbors
are displaced inward by 12% of the equilibrium Zn–O bond
+ 2+
length, whereas for VO and VO the displacements are out-
ward by +2% and +23%, as shown in Fig. 2. Note that the
symmetry of the wurtzite structure does not impose that the
relaxations of all four Zn atoms are identical; however, we
find that to a good approximation the Zn atom along the c
axis relaxes by the same amount as the other three Zn neigh-
bors 共to within 0.01Å兲, and the magnitude of this breathing
relaxation is very similar to that obtained from calculations
for the zinc-blende structure.
The origin of these large lattice relaxations lies in the
electronic structure of VO. The removal of an oxygen atom
from a perfect ZnO crystal leaves four Zn dangling bonds,
each contributing 1 / 2 electron to a neutral vacancy. The in-
teraction of these dangling bonds results in a completely
symmetric a1 state 共which lies in the band gap兲 and three
almost degenerate higher energy states 共resonant in the con-
0
duction band兲. For VO , the a1 state is occupied by two elec-
trons, and its energy is lowered when the four Zn atoms
approach each other, with the gain in electronic energy ex-
ceeding the cost to stretch the Zn–O bonds surrounding the
vacancy. The resulting a1 state 共identified by the Kohn–Sham
122102-3 A. Janotti and C. G. Van de Walle
FIG. 3. Calculated configuration coordinate diagram for VO0, VO+, and VO2+. In
共a兲 the Fermi energy is located at the conduction-band minimum Ec and in
共b兲, at the valence-band maximum Ev. The arrows indicate light absorption
Ea and light emission Ee.
level in our calculated band structures兲 lies near the top of
the valence band 共see Fig. 2兲. In the VO +
configuration, the a1
state is occupied by one electron, and the electronic energy
gain is too small to overcome the strain energy; the four Zn
atoms are displaced slightly outward, moving the a1 state
near the middle of the gap. In the VO 2+
configuration, the a1
state is unoccupied and the four Zn atoms strongly relax
outward, assuming almost planar configurations with respect
to their oxygen neighbors. This relaxation strengthens the
Zn–O bonds, and the empty a1 state lies near the bottom of
the conduction band. This large relaxation significantly re-
2+ + act as a compensating center in p-type ZnO. Our calculated
duces the formation energy of VO with respect to VO , mak-
ing the oxygen vacancy a negative-U center.
One may wonder why the transition levels associated
with the anion vacancy in ZnO lie so much higher in the
band gap than the levels associated with, for instance, the
selenium vacancy in ZnSe,18 since in both cases the elec-
tronic states have mainly Zn dangling bond character. In fact,
the positioning of the levels is consistent provided one takes
the alignment of band structures on an absolute energy scale
into account 关see Fig. 1共b兲兴. The large difference in energetic
position of the anion p states that determine the valence-band
maximum 共O 2p versus Se 4p兲 causes a large valence-band
offset between ZnSe and ZnO.19 Given this large discontinu-
ity, it should be no surprise that Zn-related states occur at
very different relative positions in the band gap.
The large difference in the local lattice relaxations of
2+ + 0
VO , VO , and VO leads to large Stokes shifts in the optical
spectra according to the Franck-Condon principle. Figure 3
shows our calculated configuration coordinate 共cc兲 diagram,
obtained by calculating the formation energy in the different
charge states for a series of atomic positions across the range
of relaxations. Figure 3共a兲 shows that the peak in the light
excitation spectrum of VO 0
→ VO+
is predicted to occur at
⬃2.0 eV, in reasonable agreement with the measured value
of 2.3 eV 共530 nm兲.17,20 The calculated emission is predicted
to occur at 0.7 eV, corresponding to a Stokes shift as large as
1.3 eV. Excitation of the center to the +1 charge state may
lead to persistent photoconductivity. The calculated thermal
barrier to escape out of the +1 charge state back to the
ground state is 0.30 eV. Therefore persistent photoconductiv-
ity 共as well as a persistence of the VO +
EPR signal after the
exciting light is turned off兲 is expected to be observed only at
low temperatures.
Finally, we turn to an interpretation of recent experi-
ments by Vlasenko and Watkins using optical detection of
electron paramagnetic resonance 共ODEPR兲 in electron irra-
diated ZnO.8 They observe a spin-dependent process:
Appl. Phys. Lett. 87, 122102 共2005兲
+
EM0 + VO → EM+ + VO
0
, 共3兲
corresponding to signals in a broad photoluminescence 共PL兲
band which is centered at 600 nm 共2.07 eV兲 and has a zero-
phonon line around 500 nm 共2.48 eV兲 . The authors propose
two possible models. In the first, the 共+ / 0兲 transition level is
placed at 0.9 eV above the top of the valence band, and the
luminescence results from the transfer of an electron from an
effective-mass donor 共EM兲 to the vacancy, i.e., the spin-
dependent process is the luminescence process itself. In the
second model, the 共+ / 0兲 transition level is placed at 2.48 eV
above the top of the valence band and the luminescence re-
sults from hole capture by the neutral vacancy.
Our computational results strongly favor the second
model. Indeed, the cc diagram of Fig. 3共b兲 indicates a zero-
phonon line transition from VO 0 +
to VO at ⬃2.0 eV, with an
emission band centered at ⬃1.5 eV. Furthermore, Fig. 3共a兲
shows that the spin-dependent electron-capture process in
Eq. 共3兲 is predicted to produce luminescence at ⬃0.7 eV
and, indeed, the PL spectra in Ref. 8 show a weak broad
band centered around 1500 nm 共0.8 eV兲.
In summary, we have shown that the oxygen vacancy is
a deep donor in ZnO with the 共2 + / 0兲 transition level at
⬃1.0 eV below the bottom of the conduction band. There-
fore, VO is not responsible for the unintentional n-type con-
ductivity often observed in as-grown ZnO, although it may
configuration coordinate diagram provides a consistent inter-
pretation of recent ODEPR measurements.8
The authors would like to express our gratitude to Pro-
fessor G. D. Watkins for making Ref. 8 available to us prior
to publication and for many enlightening discussions. This
work was funded by AFOSR under Grant No. F49620-02-1-
1163 through a subcontract from the Palo Alto Research
Center Incorporated, and made use of MRL Central Facilities
supported by the NSF MRSEC Program under award No.
DMR00-80034, and the CNSI Computing Facility under
NSF grant No. CHE-0321360.
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