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Relevance of non-equilibrium defect generation

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DOI: 10.1063/1.4932225

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 Relevance of non-equilibrium defect generation processes to resistive switching in
TiO2
Samir Abdelouahed and Keith P. McKenna

Citation: Journal of Applied Physics 118, 134103 (2015); doi: 10.1063/1.4932225

View online: http://dx.doi.org/10.1063/1.4932225
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 JOURNAL OF APPLIED PHYSICS 118, 134103 (2015)

Relevance of non-equilibrium defect generation processes to resistive

switching in TiO2
Samir Abdelouahed and Keith P. McKennaa)
Department of Physics, University of York, Heslington, York YO10 5DD, United Kingdom
(Received 24 July 2015; accepted 21 September 2015; published online 6 October 2015)
First principles calculations are employed to identify atomistic pathways for the generation of
vacancy-interstitial pair defects in TiO2. We find that the formation of both oxygen and titanium
defects induces a net dipole moment indicating that their formation can be assisted by an electric
field. We also show that the activation barrier to formation of an oxygen vacancy defect can be
reduced by trapping of holes which may be injected by the electrode. The calculated activation
energies suggest that generation of titanium defects is more favorable than generation oxygen
defects although activation energies in both cases are relatively high (>3.3 eV). These results pro-
vide much needed insight into an issue that has been widely debated but for which little definitive
experimental information is available. V C 2015 Author(s). All article content, except where

otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
[http://dx.doi.org/10.1063/1.4932225]

I. INTRODUCTION In this article, we provide insight into this fundamental

The resistive switching effect in metal oxide films is
currently the focus of intense research owing to its potential
as a low-power, high-speed, high-endurance, and non-
volatile memory technology (ReRAM).15 First documented
in the 1960s,69 the effect involves reversible switching
between high and low resistance states by application of
voltage pulses and has been observed in many oxide materi-
als, including TiO2, HfO2, SrTiO3, and Ta2O5.1015 Recent
years have seen significant progress in understanding resis-
tive switching; however, uncertainty still remains over the
microscopic mechanisms responsible for the effect. There is
a consensus that for many oxide materials the low resistance
state involves an oxygen deficient conductive filament that
bridges the electrodes.4,1618 In most cases, as grown devices
are subjected to a forming step (in which a voltage stress is
applied) to establish this filament.11 Switching to the high re-
sistance state then involves partial reoxidation of the fila-
ment.4,19 One key issue often debated is whether defect
generation under electrical bias, i.e., the rupturing of bonds
leading to the creation of vacancy defects in the lattice, is
important (particularly for forming). The generation of such
defects, assisted by a non-equilibrium electric field and
charge injection, is often discussed in the literature and
included explicitly in some device simulations.11,2026
However, resistive switching models are also developed con-
sidering field driven diffusion of pre-existing defects only,
without defect generation.2729 Experimentally, definitive
evidence for one view over the other has proven extremely
challenging to obtain, and the uncertainty that remains
presents an obstacle to addressing pressing technological
issues, such as controlling cycle-to-cycle and device-to-de-
vice variability, increasing endurance, and improving
reliability.
a)
Electronic mail: keith.mckenna@york.ac.uk
issue by investigating defect generation processes using first
principles theoretical approaches. In particular, we consider
TiO2, which is a useful model system as it is both a candidate
material for ReRAM and finds many other applications
where non-equilibrium defect generation under electrical
bias may be relevant (e.g., electrodes in rechargeable bat-
teries, gas sensors, photocatalysts, and solar-cells3032). The
equilibrium properties of a wide range of defects in TiO2
have been addressed theoretically using both semi-empirical
and density functional theory based approaches.14,3350 Here,
we determine the lowest energy pathway to creation of a va-
cancy defect on both oxygen and titanium lattice sites, with
the displaced ion occupying a neighboring interstitial site.
The predicted activation barriers associated with generation
of the initial vacancy-interstitial defect pair are 7.3 eV (oxy-
gen) and 3.3 eV (titanium). Furthermore, we show that the
activation barrier to formation of an oxygen vacancy defect
can be reduced to 4.9 eV by trapping of holes which may be
injected by the electrode. These relatively high activation
energies suggest that diffusion of pre-existing oxygen vacan-
cies (characterized by an activation energy of about 2.6 eV
(Refs. 5154)) is much more likely than defect generation in
TiO2. However, both oxygen and titanium defect creation
processes are associated with generation of a net dipole
moment which may serve to reduce the activation barrier
under very high local electric fields (for example, as may be
present during the set operation). These results provide much
needed atomistic models of defect generation processes in a
metal oxide material and provide key parameters needed to
assess the role they play in resistive switching.
The rest of this article in organized in the following way.
In Sec. II, we detail the first principles methods; we employ to
predict the properties of defects in TiO2. In Sec. III, we pres-
ent our results, including the structure and formation energies
of intrinsic defects in TiO2, the structure and activation ener-
gies associated with formation of vacancy-interstitial defect

0021-8979/2015/118(13)/134103/7 118, 134103-1 C Author(s) 2015

V

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 134103-2 S. Abdelouahed and K. P. McKenna
pairs, and the effect of charge trapping on defect formation.
Finally, in Sec. IV, we discuss the results and implications in
detail before presenting our conclusions.
II. METHODS
The properties of defects in TiO2 are described using
density functional theory (DFT) and the projector augmented
wave method as implemented in the VASP code.55,56 The
Perdew, Burke, and Ernzerhof (PBE) approximation is
employed for exchange and correlation,57 and electronic
states are expanded in a plane wave basis with an energy cut-
off of 500 eV. To correct the self-interaction error associated
with localized electrons and holes, DFT U corrections
implemented within the Dudarev scheme are applied on both
O 2p and Ti 3d states.58 We employ values of U that have
been shown to reproduce spectroscopic properties of TiO2
defects and also ensure good linearity of the total energy
with electron occupation as required by a self-interaction
free functional (UTi 4.20 eV and UO 5.25 eV).59 Using
this approach, the optimized lattice parameters of rutile TiO2
(space group P42/mnm) are obtained as a b 4.670 A and
c 3.034 A and the single electron band gap is 2.4 eV. These
predicted lattice constants are within 2.5% of experiment
while the band gap is underestimated by about 0.6 eV.60,61
All defect calculations are performed using a 3  3  4
supercell containing 72 Ti atoms and 144 O atoms, and a
2  2  2 Monkhorst-Pack grid is used for k-point sampling.
The stability of intrinsic defects are characterized by calcula-
tion of the formation energy
X that since the DFT U approach is parameterized, to
Ef fli g; EF Eqdef  Eideal Dni li qEF : (1)
i
In this equation, Eqdef is the total energy of the supercell con-
taining a defect in relative charge state q and Eideal is the
total energy of the ideal bulk supercell. Dni is the difference
between the number of atoms of species i in the defective
and ideal supercells, li is the chemical potential of species i,
and EF is the electron Fermi energy. Total energies are cor-
rected for potential alignment and image charge interactions
as described in Ref. 62.
In order to estimate activation energies for defect forma-
tion, we first perform a linear interpolation of atom coordi-
nates between the ideal bulk supercell (rideal ) and the
i
def
defective supercell (ri ),
ri t trdef ideal
i 1  tri ; (2)
where t is a parameter ranging from 0 (ideal crystal) to 1 (de-
fective). We then perform a constrained minimization where
the diffusing ion forming the vacancy is held fixed but all
ions within a spherical shell of radius 6 A are fully opti-
mized. The minimized total energy of a set of configurations
spanning range t 0  1 represents an upper bound to the
minimum potential energy surface for defect formation. This
approach was adopted as attempts to employ the nudged
elastic band method, which in general is a more rigorous
approach,63 met issues with convergence.
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J. Appl. Phys. 118, 134103 (2015)
Some of the defects discussed in this article induce a net
dipole moment relative to the bulk crystal. We estimate this
dipole moment using the optimized coordinates from the
constrained minimization described above ropt i t and the
ionic charges obtained by Bader analysis of the correspond-
ing charge density64 Qi(t). The induced dipole moment is
calculated as
X opt
pt ri tQi t  ropt
i 0Qi 0; (3)
i
where the sum is restricted over ions within a spherical
centered on the defect.
region of radius 6 A
III. RESULTS
A. Intrinsic defects
Before presenting results on defect formation, we sum-
marize the calculated structure and formation energies of the
intrinsic vacancies and interstitial defects in TiO2, which can
be considered as the building blocks of the vacancy-
interstitial pair defects discussed in Sec. III B. We consider
both Ti and O vacancies and intersitials representing the four
key intrinsic defects in the TiO2 crystal. We perform a series
of structural optimizations starting from different initial geo-
metries and spin densities in order to determine the most sta-
ble structure for each defect type and charge state. Defect
formation energies are calculated using lO E(O2)/2 (i.e.,
half the energy of an oxygen molecule) corresponding to ox-
ygen rich conditions. Once lO is fixed, the chemical poten-
tial of Ti is also defined since lTiO2 lTi 2lO . We note
describe defects in TiO2 rather than the oxygen molecule for-
mation energies defined in this way may suffer from a sys-
tematic error. In principle, this could be corrected for by
comparison to experiment; however, we do not attempt such
a correction here since the main focus of this study is on
defects which maintain the stoichiometry of TiO2 and so
their stability does not depend on the choice of the reference
chemical potential.
The most stable structure of each defect is shown in Fig.
1 with corresponding defect formation energies summarized
in Table I. The dependence of the formation energy on the
electron Fermi energy for all intrinsic defect types is shown
in Fig. 2. In the following, we discuss the properties of each
of the defects in detail with comparison to previous results
wherever available.
The neutral oxygen vacancy (VO in Kroger-Vink nota-
tion) is predicted to have a formation energy of 4.0 eV with a
triplet ground state (S 1) involving two electrons localized
on neighboring Ti ions consistent with recent results
obtained by electron paramagnetic resonance65 (Fig. 1(a)).
This result is also in agreement with numerous previous
studies using a range of methods such as GGA U, HSE,
and sX (with formation energies ranging from
4.45.7 eV).4143,45,46 Also consistent with previous studies,
we find that only the q 0 and q 2 charge states are sta-
ble across the entire range of Fermi energies, characteristic
of a negative-U defect (Fig. 2). The charge transition level
 134103-3 S. Abdelouahed and K. P. McKenna J. Appl. Phys. 118, 134103 (2015)

FIG. 1. The predicted structure of intrinsic defects in rutile TiO2 (red and green spheres represent oxygen and titanium ions respectively). (a) Oxygen vacancy
(q 0). (b) Oxygen interstitial (q 0). (c) Titanium vacancy (q 0). (d) Titanium interstitial (q 4). For defects with unpaired electrons, spin density isosur-
faces are shown in blue.

(i.e., the Fermi energy for which the q 0 and q 2 have
equal formation energy) is located 0.65 eV below the con-
duction band minimum. This is consistent with recent results
obtained using the non-local screened exchange functional.45
The neutral oxygen interstitial (Oi) defect is predicted to
adopt a dimer configuration by displacing one of the lattice
oxygen ions. The defect can be considered as an O2 2 species
formed through the bonding of the neutral oxygen interstitial
with a lattice oxygen ion which has a formal charge of 2
(i.e., O0 O2 ! O2 2 ). This species which is not stable in
the gas phase is stabilized in the TiO2 lattice by the electro-
static environment and is characterized by an O-O bond
length of 1.49 A . This prediction is in good agreement with
previous studies;45 however, our exhaustive search for the
most stable defect configuration has revealed two possible
neutral oxygen interstitial dimer configurations. One in
which the axis of the O-O bond is aligned with respect to the
local crystal symmetry (which we refer to as planar) and one
in which the dimer axis of the O-O bond is slightly rotated
(which we refer to as tilted). We find that these two configu-
rations have similar formation energies (within 70 meV) but
with the tilted dimer being the ground state with a formation
energy of 2.4 eV (Fig. 1(b)). We estimate that the barrier to
rotate the dimer between the planar to the tilted orientation is
around 100 meV, suggesting both configurations may be
readily accessible under typical conditions. The oxygen in-
terstitial is able to trap an additional one or two electrons
(leading to a corresponding increase in O-O bond length to
1.90 and 2.15 A ), consistent with previous studies.46,66 For
the negatively charged oxygen interstitial defects, only the
planar dimer structure is found to be stable. Similar to the
case for the oxygen vacancy, only the q 0 and q 2
charge states are thermodynamically favored over the full
range of electron Fermi energies (Fig. 2). Again, the agree-
ment between these predictions and non-local screened
exchange functional results is extremely good.45
The neutral titanium vacancy (VTi) is predicted to have
a formation energy of 5.0 eV and adopts a S 2 spin configu-
ration with four holes localized on neighboring O ions (Fig.
1(c)). We are not aware of any previous studies of the Ti va-
cancy in rutile TiO2, but the predictions are qualitatively
similar to results obtained for the same defect in anatase
TiO2.67 As the charge of the defect is decreased from q 0
to q 4, each of the holes surrounding the Ti vacancy is
removed one by one reducing the net spin from S 2 to
S 0. These charge transitions involve the sequential filling
of hole states predominantly localized on a single oxygen
ion providing a good indication that the self-interaction error
in these calculations is small. The charge transition levels
are clustered around 0.5 eV above the valance band maxi-
mum (Fig. 2).
The titanium interstitial defect (Tii) is predicted to
occupy an octahedral position (Fig. 1(d)) and can exist in ei-
ther a 3 or 4 charge state consistent with previous stud-
ies.45 Further electrons added to the defect localize on

TABLE I. The formation energies of intrinsic defects in rutile TiO2 calcu-

lated using Eq. (1). Values are given in eV for oxygen rich conditions
(lO E(O2)/2) and EF EVBM (where EVBM is the energy of the valence
band maximum in bulk TiO2).

Defect q Ef(E(O2)/2, EVBM)

VO 0/1/2 4.02/2.47/0.52
Oi (tilted) 0 2.36
FIG. 2. The calculated formation energy of intrinsic defects in rutile TiO2
Oi (planar) 0/1/2 2.43/4.26/5.55 under oxygen rich conditions (lO E(O2)/2). For each type of defect, only
VTi 0/1/2/3/4 5.03/5.57/5.83/6.37/6.92 the most stable charge state at any given electron Fermi energy is shown
Tii 0/1/2/3/4 6.83/4.76/2.99/1.26/0.18 (the charge is also indicated on the figure). The filled circles indicate the
charge transition levels.

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 134103-4 S. Abdelouahed and K. P. McKenna
nearby Ti lattice sites and so are better described as weakly
bound electron polarons rather than true defect charge states.
The formation energies and charge transition levels predicted
are again in good agreement with previous calculations45
(Fig. 2).
The results presented in this section demonstrate that the
DFT U method we employ is able to describe the proper-
ties of all four types of intrinsic defect in rutile TiO2 in very
reasonable agreement with previous calculations employing
higher level methods such as non-local hybrid functionals.
Importantly, the DFT U method is much less computation-
ally expensive than hybrid functional approaches, allowing
us to perform calculations on relatively large supercells,
which is important for modeling the defect formation proc-
esses discussed in Sec. III B.
B. Frenkel defect formation
With the structure of intrinsic defects in rutile TiO2
determined, we now turn to address the possibility of defect
formation in the perfect lattice. In particular, we consider
processes where an atom is displaced from its lattice site into
a neighboring interstitial site (i.e., the creation of a Frenkel
defect). Since vacancy and interstitial defects are stable in a
number of charge states in rutile TiO2, there are different
possibilities for the Frenkel defect formation which can con-
veniently be expressed in Kroger-Vink notation as follows:
OXO ! VO  O00i 6:1 eV;
OXO ! VO  O0i 6:7 eV;
OXO ! VXO  OXi 6:4 eV;
0000
TiXTi ! V
Ti  Tii 6:7 eV;
000
TiXTi ! V
Ti  Tii 7:6 eV:
We note that since formation of a Frenkel defect involves no
net change in the number of ions or electrons in the system,
the corresponding formation energy does not depend on the
electron or oxygen chemical potential. The numbers given in
the square brackets above are the Frenkel defect formation
energies for the reactions calculated by summing the forma-
tion energies of the individual intrinsic defects (Table I).
Calculated in this way, these formation energies correspond
to the formation of vacancy and interstitial pairs that are suf-
ficiently separated that there is negligible interaction
between them. For both oxygen and titanium, the most stable
Frenkel defect is comprised of the intrinsic defects with the
highest charge, jq 2j in the case of oxygen (Ef 6.1 eV)
and jq 4j in the case of titanium (Ef 6.7 eV). These
results are comparable to previous results obtained using the
PBE functional.68 Importantly, in the presence of a non-
equilibrium electric field, the stability of Frenkel defects
comprised of oppositely charged interstitial and vacancy
defects would be enhanced and could provide a driving force
for defect generation in films under electrical bias.
While the calculations above are helpful for identifying
the most likely Frenkel defects to form in TiO2, they do not
allow us to say, anything about the mechanism of defect
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J. Appl. Phys. 118, 134103 (2015)
formation. To address this, we consider the stability of meta-
stable configurations involving closely separated vacancy
and interstitial defects and characterize the activation ener-
gies associated with defect generation. First, we perform a
systematic search of possible vacancy-interstitial configura-
tions in order to determine the metastable configurations
with the lowest formation energy. For oxygen Frenkel
defects, we consider as initial geometries the optimized
structures of the q 0, q  1, and q 2 oxygen intersti-
tial with an oxygen vacancy created in lattice sites up to the
seventh nearest neighbor. For the titanium Frenkel defects,
we consider the optimized structure of the q 4 and
q 3 titanium interstitial with Ti vacancies created in lat-
tice sites up to the second nearest neighbor. Following struc-
tural optimization, many of these initial geometries relax
to the bulk crystal structure, indicating the lack of any nearby
potential energy minimum; however, a number of metastable
configurations are obtained.
Following our search, we find that the most stable oxy-
gen Frenkel defect involves a q 2 oxygen interstitial and
a q 2 oxygen vacancy located at the fourth nearest neigh-
bor lattice site (Ef 5.97 eV). The most stable titanium
Frenkel defect consists of a q 4 interstitial and a q 4
vacancy at the neighboring lattice site (Ef 3.15 eV). The
structures of both defects are shown in Fig. 3. The fact that
the most stable defects involve vacancies and interstitials
with the highest charge is consistent with the result obtained
(4) for isolated defects above. However, the formation energies
are in both cases lower as a result of mutual electrostatic and
(5) elastic interactions between the vacancy and interstitial. The
(6)
(7)
(8)
FIG. 3. (a) Structure of the most stable oxygen Frenkel defect and (b) the
most stable titanium Frenkel defect in rutile TiO2. Red and green spheres
represent oxygen and titanium ions, respectively. The ion which is displaced
out of its lattice site in highlighted in blue. The arrows indicate the displace-
ment of ions associated with defect formation.
 134103-5 S. Abdelouahed and K. P. McKenna
binding of the interstitial to the vacancy is small for oxygen
but high for the titanium defect due to the smaller distance
versus 3.85 A ).
between the vacancy and interstitial (1.82 A
With the most stable oxygen and titanium Frenkel
defect configurations identified, we calculate the activation
barriers associated with the initial stage of defect formation
using the constrained minimization procedure outlined in
Sec. II. Fig. 4 shows the potential energy surface for both
defects from which we estimate activation energies of 7.3
and 3.3 eV for oxygen and titanium, respectively. As noted
above, the binding energy of the titanium interstitial to the
vacancy is higher than for oxygen and further separation of
the vacancy and interstitial requires overcoming an addi-
tional activation barrier of 3.4 eV. To assess the possible
role of a non-equilibrium electric field in assisting the
defect formation process, we calculate the corresponding
induced dipole moment jpj (Fig. 4). The dipole moment
increases in a monotonous fashion to about 5.3 eA and 4.0
eA for the oxygen and titanium defect, respectively. In the
presence of an electric field, these induced dipole moments
will reduce both the defect formation energy and barrier to
formation. For example, for both the O and Ti Frenkel
defects shown in Fig. 4, the dipole moment close to the
transition state is about 3 eA , and for electric fields of 1, 5,
and 10 MV/cm, the expected reductions in the activation
energy (E.p) are 0.03, 0.15, and 0.30 eV, respectively. We
return to discuss this point in more detail in Sec. IV.
FIG. 4. (a) Potential energy surface associated with generation of an oxygen
Frenkel defect and (b) a titanium Frenkel defect in rutile TiO2. The corre-
sponding induced dipole moment jpj is also shown.
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C. Role of charge trapping
We now extend the calculations above to consider
whether the trapping of electrons or holes which may be
injected under a non-equilibrium bias can assist the forma-
tion of defects. This is an issue that has seen considerable
speculation, but there is little quantitative known. Modeling
the non-equilibrium injection and trapping of charge directly
is an extremely challenging problem requiring approaches
that can bridge the timescales associated with electron trans-
fer and ionic motion.69 However, to provide some insight,
we consider a simpler model where we assess the formation
energies associated with creating Frenkel defects in the pres-
ence of an additional electron or hole. In particular, in
Kroger-Vink notation
OXO e ! Oi VO ; (9)
OXO h ! Oi VO ; (10)
TiXTi e ! Tii VTi ; (11)
TiXTi h ! Tii VTi : (12)
On the left hand side of the reactions above, the electron ini-
tially occupies a state at the conduction band minimum and
the hole occupies a state at the valence band maximum.
As in Sec. III B, for each of the reactions above, we
have identified the most stable defect involving a vacancy
and interstitial at close separation. For titanium, we find little
reduction in defect formation energy by addition of electrons
or holes. However, for oxygen defects, addition of a hole
leads to a significant reduction in formation energy. In par-
ticular, we identify the following reaction as the most stable:
OXO h ! OXI VO ; (13)
with a formation energy of 4.70 eV. The defect is qualita-
tively different to the one formed in the absence of a hole as
it involves a neutral oxygen interstitial and a positively
charged vacancy (Fig. 5(a)). The much lower formation
energy (4.70 eV compared to 5.97 eV) can be understood in
terms of the energy gained by localization of the hole.
The potential energy surface associated with defect for-
mation is calculated in the same was as described previously
(Fig. 5(b)). The estimated activation energy is 4.9 eV, con-
siderably lower than the 7.3 eV obtained without the hole
present. This is explained by the fact that in the latter case the
displaced oxygen carries a 2 charge and therefore experien-
ces stronger electrostatic repulsion with surrounding lattice ox-
ygen ions during the transition, whereas in the former case, it is
neutral. Again, we also calculate the corresponding induced
dipole moment jpj, which reaches a maximum of 2.3 eA .
IV. DISCUSSION AND CONCLUSIONS
We start with a discussion of some of the factors which
may affect the accuracy of the calculations presented in this
article. The approximations used in the DFT implementation,
in particular, the use the DFT U approach, may leave
residual self-interaction error which will affect the formation
 134103-6 S. Abdelouahed and K. P. McKenna
FIG. 5. (a) Structure of the oxygen Frenkel defect formed in the presence of
a hole. Red and green spheres represent oxygen and titanium ions, respec-
tively. The ion which is displaced out of its lattice site in highlighted in blue.
The arrows indicate the displacement of ions associated with defect forma-
tion. (b) Potential energy surface associated with defect generation. The cor-
responding induced dipole moment jpj is also shown.
energy of defects and the nature of charge localization. The
band gap is also underestimated using this approach.
However, the properties of intrinsic defects calculated in Sec.
III A are in very good agreement with a range of alternative
self-interaction corrected methods suggesting the approxima-
tions employed are reasonable. Another potential source of
error is the use of periodic boundary conditions which leads
to artificial interactions between the defect and its periodic
images. To limit these effects, we have used a relatively large
supercell (216 atoms) and the high dielectric constant of rutile
TiO2 means electrostatic interactions are screened effectively.
Finally, another possible source of error is the constrained
minimization approach employed to characterize the potential
energy surface associated with defect formation. This
approach provides a reliable upper estimate of the activation
barrier but cannot exclude lower energy pathways involving
more complex ionic displacements (although we were unable
to find any after a thorough search).
We now turn to discussion of some of the potential
implications of our results. Considering the possibility of
electric field assisted defect generation in TiO2, we have
identified that the initial step in the formation of a charged
vacancy and interstitial pair is associated with activation bar-
riers of 7.3 eV (oxygen) and 3.3 eV (titanium). The dipole
moment associated with these defects is about 4 to 5 eA ; ally, the results are relevant to a far wider range of TiO2
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J. Appl. Phys. 118, 134103 (2015)
therefore, under an electric field, effective activation ener-
gies may be reduced. Considering the electric fields that may
realistically exist in devices (130 MVcm1), this field effect
can only offer a reduction of the order 1 eV at most. After
activation, the binding between the vacancy and interstitial is
relatively weak in the case of oxygen, and so the charged in-
terstitial would be free to diffuse away driven by the electric
field. For the titanium defect, the binding is stronger and a
subsequent barrier of 3.4 eV must be overcome before the Ti
ion is free to diffuse away. Typical activation energies asso-
ciated with oxygen vacancy diffusion in TiO2 are of the
order 2.6 eV.5154 Even considering the effect of hole trap-
ping which can reduce the activation energy to oxygen
vacancy generation, these results suggest that diffusion of
pre-existing oxygen vacancies is always much more facile
than defect generation in bulk TiO2. However, activation
energies near the electrode interface7072 or at grain bounda-
ries12,73,74 may be considerably lower. Of the defect genera-
tion processes considered, Ti Frenkel formation appears as
the most favorable. This is especially true in the presence of
a high local electric field, suggesting this process may play a
role in the set process where a high field may exist between
the filament apex and the electrode.
One of the reasons the results presented in this article
are useful is that there is little experimental information
available on defect generation process which may take place
under electrical bias in TiO2 and oxides more generally. On
the other hand, this makes direct validation of the predicted
defect creation pathways and activation energies extremely
difficult. One of the few examples where an activation
energy for Frenkel defect generation has been extracted
experimentally is in a study of forming in HfO2 films.11 In
this work, the temperature dependence of the forming pro-
cess was investigated and fitted to a trap-assisted-tunneling
simulation including field enhanced Frenkel defect genera-
tion. An activation energy attributed to oxygen Frenkel
defect formation of 4.4 eV was obtained. Although HfO2 is a
quite different material with a much wider gap, we note that
this activation energy is broadly similar to the energies
obtained for TiO2 (4.9 eV and 7.3 eV).
In summary, we have performed a first principles theoret-
ical investigation into non-equilibrium defect generation proc-
esses in TiO2. We have identified atomistic pathways for the
initial step in the generation of oxygen and titanium Frenkel
defects and have characterized the corresponding activation
energies. Our key conclusions are that the formation of both
oxygen and titanium Frenkel defects induces a net dipole
moment, and therefore, their formation can be assisted by an
electric field. In the case of oxygen, we also find that trapping
of holes can further reduce the barrier to defect formation.
However, the activation energies remain relatively high. The
lower barrier to formation of titanium defects and the larger
associated dipole moment suggests such processes may be rel-
evant in very high local electric fields (for example, as may be
present during a set operation). These results provide much
needed atomistic models of defect generation processes in
metal oxide materials and provide key parameters needed to
assess the role they play in resistive switching.28 More gener-
 134103-7 S. Abdelouahed and K. P. McKenna J. Appl. Phys. 118, 134103 (2015)

28
applications where non-equilibrium electric field driven defect D. Li, M. Li, F. Zahid, J. Wang, and H. Guo, J. Appl. Phys. 112, 073512
generation may contribute to material degradation, for exam- (2012).
29
Y. Guo and J. Robertson, Microelectron. Eng. 147, 339 (2015).
ple, in photocatalysts, dye-sensitized solar cells and electrodes 30
A. Fujishima and K. Honda, Nature 238, 37 (1972).
in rechargeable batteries.3032 31
B. ORegan and M. Gratzel, Nature 353, 737 (1991).
32
K. Schierbaum, U. Kirner, J. Geiger, and W. G opel, Sens. Actuators B 4,
ACKNOWLEDGMENTS 87 (1991).
33
N. Yu and J. W. Halley, Phys. Rev. B 51, 4768 (1995).
34
K.P.M. acknowledges support from EPSRC (EP/ J. Chen, L.-B. Lin, and F.-Q. Jing, J. Phys. Chem. Solids 62, 1257 (2001).
35
E. Cho, S. Han, H.-S. Ahn, K.-R. Lee, S. K. Kim, and C. S. Hwang, Phys.
K003151) and COST Action CM1104. This work made use
Rev. B 73, 193202 (2006).
of the facilities of Archer, the UKs national high- 36
N. A. Deskins and M. Dupuis, Phys. Rev. B 75, 195212 (2007).
37
performance computing service, via our membership in the M. M. Islam, T. Bredow, and A. Gerson, Phys. Rev. B 76, 045217 (2007).
38
UK HPC Materials Chemistry Consortium, which is funded E. Finazzi, C. Di Valentin, G. Pacchioni, and A. Selloni, J. Chem. Phys.
129, 154113 (2008).
by EPSRC (EP/L000202). All data created during this 39
B. J. Morgan and G. W. Watson, J. Phys. Chem. C 113, 7322 (2009).
research are available by request from the University of York 40
S.-G. Park, B. Magyari-K ope, and Y. Nishi, Phys. Rev. B 82, 115109
Research database http://dx.doi.org/10.15124/0bede454-b78e- (2010).
41
474c-8d93-38b9911700f5. B. J. Morgan and G. W. Watson, J. Phys. Chem. C 114, 2321 (2010).
42
A. Janotti, J. B. Varley, P. Rinke, N. Umezawa, G. Kresse, and C. G. Van
1 de Walle, Phys. Rev. B 81, 085212 (2010).
R. Waser and M. Aono, Nat. Mater. 6, 833 (2007). 43
2 G. Mattioli, P. Alippi, F. Filippone, R. Caminiti, and A. Amore Bonapasta,
A. Sawa, Mater. Today 11, 28 (2008).
3 J. Phys. Chem. C 114, 21694 (2010).
D.-H. Kwon, K. M. Kim, J. H. Jang, J. M. Jeon, M. H. Lee, G. H. Kim, 44
P. Deak, B. Aradi, and T. Frauenheim, Phys. Rev. B 86, 195206 (2012).
X.-S. Li, G.-S. Park, B. Lee, S. Han, M. Kim, and C. S. Hwang, Nat. 45
H.-Y. Lee, S. J. Clark, and J. Robertson, Phys. Rev. B 86, 075209 (2012).
Nanotechnol. 5, 148 (2010). 46
4 T. S. Bjrheim, A. Kuwabara, and T. Norby, J. Phys. Chem. C 117, 5919
H. Akinaga and H. Shima, Proc. IEEE 98, 2237 (2010).
5 (2013).
F. Pan, S. Gao, C. Chen, C. Song, and F. Zeng, Mat. Sci. Eng. R 83, 1 47
A. Janotti, C. Franchini, J. B. Varley, G. Kresse, and C. G. de Walle, Phys.
(2014).
6 Status Solidi-RRL 7, 199 (2013).
T. W. Hickmott, J. Appl. Phys. 33, 2669 (1962). 48
7 M. Setvin, C. Franchini, X. Hao, M. Schmid, A. Janotti, M. Kaltak, C. G.
J. Gibbons and W. Beadle, Solid State Electron. 7, 785 (1964).
8 Van de Walle, G. Kresse, and U. Diebold, Phys. Rev. Lett. 113, 086402
F. Argall, Solid State Electron. 11, 535 (1968).
9
G. Dearnaley, A. M. Stoneham, and D. V. Morgan, Rep. Prog. Phys. 33, (2014).
49
1129 (1970). A. Malashevich, M. Jain, and S. G. Louie, Phys. Rev. B 89, 075205
10
M. D. Pickett, D. B. Strukov, J. L. Borghetti, J. J. Yang, G. S. Snider, D. (2014).
50
R. Stewart, and R. S. Williams, J. Appl. Phys. 106, 074508 (2009). C. Lin, D. Shin, and A. A. Demkov, J. Appl. Phys. 117, 225703 (2015).
51
11
G. Bersuker, D. C. Gilmer, D. Veksler, P. Kirsch, L. Vandelli, A. M. Arita, M. Hosoya, M. Kobayashi, and M. Someno, J. Am. Ceram. Soc.
Padovani, L. Larcher, K. P. McKenna, A. Shluger, V. Iglesias, M. Porti, 62, 443 (1979).
52
and M. Nafra, J. Appl. Phys. 110, 124518 (2011). D. Derry, D. Lees, and J. Calvert, J. Phys. Chem. Solids 42, 57 (1981).
53
12
K. Szot, W. Speier, G. Bihlmayer, and R. Waser, Nat. Mater. 5, 312 (2006). D.-K. Lee and H.-I. Yoo, Solid State Ionics 177, 1 (2006).
54
13
D. Choi, D. Lee, H. Sim, M. Chang, and H. Hwang, Appl. Phys. Lett. 88, A. G. Hollister, P. Gorai, and E. G. Seebauer, Appl. Phys. Lett. 102,
082904 (2006). 231601 (2013).
55
14
K. Yang, Y. Dai, B. Huang, and Y. P. Feng, Phys. Rev. B 81, 033202 (2010). G. Kresse and J. Furthm uller, Phys. Rev. B. 54, 11169 (1996).
56
15
A. C. Torrezan, J. P. Strachan, G. Medeiros-Ribeiro, and R. S. Williams, G. Kresse and J. Furthm uller, Comput. Mater. Sci. 6, 15 (1996).
57
Nanotechnology 22, 485203 (2011). J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865
16
L. Liborio and N. Harrison, Phys. Rev. B 77, 104104 (2008). (1996).
58
17
J. P. Strachan, G. Medeiros-Ribeiro, J. J. Yang, M.-X. Zhang, F. Miao, I. S. L. Dudarev, G. A. Botton, S. Y. Savrasov, C. J. Humphreys, and A. P.
Goldfarb, M. Holt, V. Rose, and R. S. Williams, Appl. Phys. Lett. 98, Sutton, Phys. Rev. B 57, 1505 (1998).
59
242114 (2011). B. Morgan and G. Watson, Phys. Rev. B 80, 233102 (2009).
60
18
K. Kamiya, M. Y. Yang, S.-G. Park, B. Magyari-K ope, Y. Nishi, M. D. C. Cronemeyer, Phys. Rev. 87, 876 (1952).
61
Niwa, and K. Shiraishi, Appl. Phys. Lett. 100, 073502 (2012). Z.-W. Lu, D. Singh, and H. Krakauer, Phys. Rev. B 51, 6842 (1995).
62
19
D. Ielmini, F. Nardi, and C. Cagli, Nanotechnology 22, 254022 (2011). S. Lany and A. Zunger, Model. Simul. Mater. Sci. Eng. 17, 084002
20
B. J. Choi, D. S. Jeong, S. K. Kim, C. Rohde, S. Choi, J. H. Oh, H. J. Kim, (2009).
63
C. S. Hwang, K. Szot, R. Waser, B. Reichenberg, and S. Tiedke, J. Appl. G. Henkelman and H. J onsson, J. Chem. Phys. 113, 9978 (2000).
64
Phys. 98, 033715 (2005). G. Henkelman, A. Arnaldsson, and H. J onsson, Comput. Mater. Sci. 36,
21
J. Yang, F. Miao, M. Pickett, D. A. A. Ohlberg, D. R. Stewart, C. N. Lau, 354 (2006).
65
and R. S. Williams, Nanotechnology 20, 215201 (2009). A. T. Brant, E. M. Golden, N. C. Giles, S. Yang, M. A. R. Sarker, S.
22 Watauchi, M. Nagao, I. Tanaka, D. A. Tryk, A. Manivannan, and L. E.
L. Goux, P. Czarnecki, Y. Y. Chen, L. Pantisano, X. P. Wang, R.
Degraeve, B. Govoreanu, M. Jurczak, D. J. Wouters, and L. Altimime, Halliburton, Phys. Rev. B 89, 115206 (2014).
66
Appl. Phys. Lett. 97, 243509 (2010). H. Kamisaka and K. Yamashita, J. Phys. Chem. C 115, 8265 (2011).
23 67
P. Huang, X. Liu, B. Chen, H. Li, and Y. Wang, IEEE Trans. Electron S. Na-Phattalung, M. Smith, K. Kim, M.-H. Du, S.-H. Wei, S. Zhang, and
Devices 60, 4090 (2013). S. Limpijumnong, Phys. Rev. B 73, 125205 (2006).
24 68
K.-H. Xue, B. Traore, P. Blaise, L. R. C. Fonseca, E. Vianello, G. Molas, J. He, R. Behera, M. Finnis, X. Li, E. Dickey, S. Phillpot, and S. Sinnott,
B. De Salvo, G. Ghibaudo, B. Magyari-K ope, and Y. Nishi, IEEE Trans. Acta Mater. 55, 4325 (2007).
69
Electron Devices 61, 1394 (2014). L. G. C. Rego and V. S. Batista, J. Am. Chem. Soc. 125, 7989 (2003).
25 70
B. Traore, P. Blaise, E. Vianello, E. Jalaguier, G. Molas, J. F. Nodin, L. O. Sharia, K. Tse, J. Robertson, and A. A. Demkov, Phys. Rev. B 79,
Perniola, B. D. Salvo, and Y. Nishi, in International Reliability Physics 125305 (2009).
71
Symposium Proceedings (IEEE, 2014), p. 5E.2.1. D. Jeong, H. Schroeder, and R. Waser, Phys. Rev. B 79, 195317 (2009).
26 72
R. Ottking, S. Kupke, E. Nadimi, R. Leitsmann, F. Lazarevic, P. Planitz, S. R. Bradley, K. P. McKenna, and A. L. Shluger, Microelectron. Eng.
G. Roll, S. Slesazeck, M. Trentzsch, and T. Mikolajick, Phys. Status Solidi 109, 346 (2013).
73
212, 547 (2015). K. P. McKenna, A. Shluger, V. Iglesias, M. Porti, M. Nafra, M. Lanza,
27
S. Clima, Y. Y. Chen, R. Degraeve, M. Mees, K. Sankaran, B. Govoreanu, and G. Bersuker, Microelectron. Eng. 88, 1272 (2011).
74
M. Jurczak, S. De Gendt, and G. Pourtois, Appl. Phys. Lett. 100, 133102 S. K. Wallace and K. P. McKenna, Adv. Mater. Interfaces 1, 1400078
(2012). (2014).

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