J. Php. Chem Solrdr Vol. 47. No. I. pp. 89-97. 1986 0022-3697186 $3.00 + .

Xl
Printed in Great Britain. 0 1986 Pergamon Press Ltd.

DEFECT STUDIES OF DOPED AND UNDOPED

BARIUM TITANATE USING COMPUTER
SIMULATION TECHNIQUES

G. V. LEWIS and C. R. A. CATLOW

Department of Chemistry. University College London, 20 Gordon Street, London WC I H OAJ, UK

(Received 3 June 1985; accepted 17 August 1985)

Abstract-We present the results ofa computer simulation study of defect energies in BaTiOs. Our calculations
are used to propose a defect model consistent with experimental studies. Intrinsic disorder is masked by
oxygen vacancies which compensate accidental acceptor impurities. Holes are trapped by acceptors at high
po2 values whereas doubly ionised oxygen vacancies lead to n-type behavior at lower PO?. Whilst holes and
oxygen vacancies are weakly bound by barium vacancies, titanium vacancies act as deep traps for holes,
although negligible concentrations will be present in lightly doped BaTi03 samples. Three types ofcompeting
compensation mechanism are proposed for trivalent dopants, enabling donor ‘effectiveness’ to be predicted
in satisfactory agreement with experiment. Binding energies for electron and cation vacancy trapping by
donor dopants are generally calculated to be lower than those proposed previously to interpret conductivity
measurements.
Kqwords: barium titanate, defect energies, dopant, impurity compensation,

INTRODUCTION On moving towards higher ~02 values two charac-

teristic trends are observed. For ‘undoped’ and accep-
Although measurements of the Hall effect and Seebeck
tor-doped samples the conductivity passes through a
coefficients have determined the nature of the charge
minimum and then enters a ptype region in which
carriers in BaTiO, [ 11there is still no generally accepted
the conductivity increases with increasing poz. At room
defect model that is capable of interpreting all of the
temperature such samples exhibit insulating type be-
equilibrium conductivity measurements. Thus there
havior suggesting the energy of ionisation of the ac-
are conflicting discussions regarding the importance of
ceptors is high. There is also some doubt as to whether
intrinsic disorder, non-stoichiometry, accidental im-
acceptors are incorporated homogeneously or form
purities, charge trapping, compensation of dopants and
defect complexes since they are only partially effective
defect complexes. The construction of an acceptable
in modifying the electrical conductivity behavior of
defect model must be consistent with observed con-
undoped samples.
ductivity measurements throughout the whole range
In contrast donor dopants have a considerable effect
of experimental conditions (T = 25-13OO”C, poz
on the conductivity, resulting in n-type materials
= 10m20to 1 atm).
throughout the whole po2 range. On moving to higher
Above 500°C all experimental studies indicate that
po2 values several authors proposed that donors are
there is a region at low oxygen partial pressures where
increasingly compensated for by metal vacancies rather
the conductivity increases with decreasing po2. This is
than conduction electrons. Subbarro and Shirane [3]
characteristic of n-type conduction and it is generally
suggested that both barium and titanium vacancies
agreed that this is due to oxygen deficiency. Between
compensated the donors. More recently Jonker and
700°C and 900°C Daniels and HPrdtl [2] postulated
Havinga [4] proposed that La3+ is compensated for by
that singly ionised oxygen vacancies were created at
titanium vacancies whereas Daniels and Hiirdtl [2] fa-
low po2.
vor barium vacancy compensation.
There is further uncertainty concerning the behavior
0, (lattice) = V0 + i 02 (g) (1) of nominally undoped materials. Daniels and Hardtl
[2] attribute the observed conductivity to the presence
v, = V0 + P’. (2) of singly ionised barium and oxygen vacancies. Long
and Blumenthal [5. 61 proposed that with ‘undoped’
At higher temperatures they proposed that doubly BaTiO, at high oxygen partial pressures (poz = 1 atm)
ionised vacancies occurred in appreciable concentra- the neutrality condition
tions.
v, = VO’+ i”. (3) [A’] = 2[v,] (4)

However, other studies suggest that doubly ionised va- is valid, where A’ is an unknown acceptor impurity.
cancies dominate the defect chemistry in the n-type Seuter [7] proposed that excess barium vacancies pres-
region throughout the whole temperature range. ent in Ti02 deficient samples acted as an effective ac-

89
90 G. V. Lt.w~s and C. R. A. CATLOW

Table I. Potential parameters for barium titanite used in the calculation of defect energies

Interaction A(eV) & g(evF)

7+ 2-
Ba -0 12111.4 0.35220 ii.0
4+ ?-
l’i -Urn 077.2 0.38096 ‘~I. :)

Z--O:)- 22764. o 0.1490 4 3.0

Ion Y(e) k(eVir2)

2+
Ba I .848 29.1

Ti4+ -35.863 65974 .O

02- -2.389 18.41

ccptor concentration. Compensating barium and ox- by way of the shell model [IO], which represents each
ygen vacancies were believed to associate into vacancy ion in terms of a core with charge Y and a shell with
pairs. From the effects of additions of donor and ac- charge X. harmonically coupled by means of a spring
ccptor impurities Chan and Smyth [8] concluded that with force constant k, so that the electronic polarisa-
their undoped material contained 130 ppm of acci- bility of a free ion is given by
dental acceptor impurities. These acceptor impurities
may associate with charge compensating oxygen va- 01 = YZl!i. (7)
cancies to form defect pairs. At high po2 oxygen fills a
portion of the impurity related vacancies. Model parameters were derived by a least squares
fitting procedure to experimentally known crystal
properties and are given in Tables I and 2. Further
details of parameter derivation are given in [I I].
For the perfect lattice calculations the computer code
Electron holes are then trapped by the acceptor im-
purities. A recent investigation suggests that Al, a com-
Table 2. Short-range potential parameters for dopant
mon accidental acceptor impurity may be less than ion-oxygen ion interactions in barium titanate
5OV effective in creating acceptor levels [9]. The com-
pensating oxygen vacancies may contribute a small po2 Interaction .4 (eV) P (A)
independent conductivity component; that is. there
Li+_02- 292.3 0.3472
may be a significant ionic contribution to the observed
Na’-02- 61 I.1 0.3535
conductivity at gmln. K+_O*- 902.8 0.3698
The purpose of the present paper is to propose a Rb+-O’- 1010.8 0.3793
Mg*+_02m 1428.5 0.2945
defect model for BaTi03 based upon calculations using
Fe*+_@ 1207.6 0.3084
computer simulation techniques. The calculations are Mn2+_0*- 1007.4 0.3262
concentrated in four main areas. Ca2+_02e 1090.4 0.3437
(i) intrinsic defects SrZ+-02m 959. I 0.372 I
(ii) behaviour of impurities and dopants Al)+_@ 1474.4 0.3006
SC” _()2- 1299.4 0.3312
(iii) defect pair formation
Ti’+_@ 1715.7 0.3069
(iv) trapping of charge carriers V”_@ 790.2 0.306 I
Cr)‘_O’ 734. I 0.3010
C‘ompu~utionul techniques Mn3+-O2 I 257.9 0.3214
All of the calculations presented in this paper are Fe3+_02m 102.4 0.3300
y3+_y
based upon an ionic model description of the relevant 345. I 0.3491
Lg+_O’- I,439.7 0.365 1
oxides with integral ionic charges and pair-wise short- N&+-O*- I 379.9 0.360 I
range interactions represented by potentials of the form Eu3+_02- 358.0 0.3556
_ ^
Cd’+-OL 1336.8 0.355 I
V(r) = .4 exp(-r/p) - C./r6 H$+_@ 1350.2 0.3487
(6)
Yb3+-O2 1309.6 0.3462
L$+_o*- 1347. I 0.3430
where r is the distance between a given pair of ions Si4+_@ 913.2 0.3428
and the parametersn, p and C’were derived empirically Mn4+_(Jm 1396.4 0.3440
for each ion-ion potential. Ion polarisation is included ZS+-02m 1608. I 0.3509
 Defect studies of doped and undoped barium titanite
PLUTO [l2] was used. Summation of Coulomb in-
teractions between ions and summation of terms aris-
ing from the short-range potentials are included. There
is no Coulomb interaction between the core and shell
of the same ion and short-range interactions are spec-
ified between shells, since the interactions are consid-
ered to stem from overlap of electron density. The
short-range interaction includes intra-ionic core-shell
coupling. With a shell model potential the lattice energy
must be a minimum with respect to independent dis-
placements of cores and shells for an equilibrium con-
figuration. The minimisation is achieved using an it-
erative scheme: PLUTO incorporates a technique in-
volving first and second derivatives of the lattice energy
with respect to internal and bulk strains.
Once the minimum energy configuration ofthe per-
fect lattice is established defect energies are calculated
using a two region strategy in which the crystal im-
mediately surrounding the defect is simulated ato-
mistically, whilst more distant regions are approxi-
mated to a continuum. The inner region consisted of
approximately 150 ions and is equilibrated explicitly.
The polarisation energy of the outer regions is calcu-
lated using the Mott-Littleton approximation [ 131.The
computer code CASCADE [ 141is based upon this two
region approach and was used for all the defect cal-
culations presented in this paper.
RESULTS AND DI!ZXXJSSION
( 1) Behavior of undoped barium titanate
Assuming the conduction band is associated with
titanium (3d) orbitals and the valence band associated
with oxygen (2~) orbitals it is possible to calculate the
thermal band gap, I$ in barium titanate provided we
assume localised models for both hole and electron
states. Electron and hole formation energies are com-
bined with the intra-atomic energy terms, namely the
second electron affinity of oxygen and the fourth ion-
Table 3. Defect energies for undoped BaTi
(a) Schottky (eV per defect)
BaTiO3 2.29
Ti02 2.90
BaO 2.58
(c) Charge trapping energies (eV)
Iv0 + e’l -0.12
[“‘ha + 2K] -0.19
[“‘Qi + h'] -1.14
[v’ii + 4$1 -4.23
91
isation potential of titanium. By this procedure we cal-
culated a value of E& 3.05 eV which compares fa-
vourably with experimental values of 2.913, 3.1’ and
3.27 eV16 determined from Arrhenius plots.
A band gap of this magnitude would lead to insu-
lating materials at room temperature unless donor lev-
els are available close to the conduction band or ac-
ceptor levels are near the valence band.
Experimentally, materials equilibrated under low
oxygen partial pressures exhibit n-type conductivity at
room temperature whereas at higher oxygen partial
pressures insulating behaviour is observed. Daniels et
al. [IS] interpreted this behaviour in terms of Schottky
disorder on the barium and oxygen sublattice. Singly
and doubly ionised oxygen vacancies would result in
n-type conductivity whereas p-type behaviour would
not be observed if barium vacancies act as deep traps
for holes.
Our calculated trapping energies are presented in
Table 3. The results suggest oxygen vacancies are likely
to be doubly ionised, in agreement with the models of
Chan et al. [ 17, 181and Eror and Smyth [ 161. Daniels
et al. [ 151 have suggested that both singly and doubly
ionised oxygen and barium vacancies may be impor-
tant. Our calculated trapping energies also suggest that
holes will only be weakly bound at barium vacancies.
Indeed our results find that titanium vacancies must
be the majority cation vacancy if intrinsic disorder is
responsible for the lack of p-type conductivity at low
temperatures, since holes are predicted to be strongly
trapped at titanium vacancies.
Six types of intrinsic disorder that may influence the
defect properties of BaTi03 are given below (eqns (8
to 13)).
BaB. = VL, + Ba; (8)
TiTi = Vc + Tii”’ (9)
0, = vb’ + 0: (10)
(b) Frenkel (eV per defect)
Oxygen 4.49
Barium 5.94
Titanium 7.56
 92 G. V. LEWIS and C. R. A. CATI.OW

‘BaTiOj’ = Vi, + VI; + BaO (11) “r

‘BaTiOj’ = Vy: + 2V; + TiOz (12)

‘BaTiOJ’ = V’& + Vc + 3V;; + BaTiO,. ( 13)

3-

The calculated Schottky and Frenkel formation

energies per defect are summarised in Table 3. Since
Frenkel energies are considerably higher than Schottky
energies interstitial formation is unlikely. The more
energetically favourable Schottky energies are all sim- ‘Qln2+
ilar in energy. However the magnitude of the formation E/a’
\
energies suggests that low concentrations of vacancies \

are found in BaTi and hence extrinsic vacancies or

non-stoichiometry may be responsible for the observed
conductivity of ‘undoped’ BaTi03. Eror and Smyth
[ 161 postulated that vacancy pair formation occurs in
non-stoichiometric BaTiO, prepared with excess TiOz.
ot
‘BaTi03’ + Ti02 = Vi, + Vy + BaTi03 ( 14) Pb2+

V& + v, = (v&v;). (15)

-1’ ’ 1 I I I I I I I

04 0.6 08 10 12
For their proposal to be consistent with conductivity
Ionic Rodus/
measurements this vacancy complex must have a
binding energy in excess of 2 eV whereas our calculated Fig. 2. Calculated heats of solution plotted against radius for
binding energy is 0.4 eV. Moreover our energy of so- divalent dopant ions at barium sites.
lution from incorporation of titanium is 3.2 eV and
hence deviations from stoichiometry by this means are inates the conductivity behaviour of ‘undoped’ BaTiO,
unlikely. Thus our calculations for undoped BaTi03 with intrinsic disorder playing a minor role. Common
require further calculations to investigate the proposal impurity elements are Mg and Al whilst dopants such
of Chan et a/. [ 17, 181 in which extrinsic disorder, as La are often used to produce n-type materials.
caused by the presence of accidental impurities, dom-
(2) Effect of impurities and dopants
The effect of impurities and dopants upon conduc-
5’ aRb+ tivity will strongly depend upon valence state and ionic
radius. Solubility, site of incorporation, type of charge
I
compensation, tendency to defect pair formation and
I trapping of charge carriers also modify conductivity
4-
I
behaviour.
(a) Fucrors controlling d&ct compwzsution and thr
:
.\itc c~f’.sirhsritllrion. Monovalent ions are incorporated
K+ 1
Ql at barium sites and can be charge compensated by ox-
I
3- ‘1
ygen vacancy or hole formation.
I
\

E/N / MzO + ‘BaTiOj’ = 2M’,, + V, + 2BaO (16)

I
\
\
2- \ MzO + ‘BaTiO,’ = 2M’,, + 2h’ + 2BaO - i 02.
I
\
\ + /
\._g_ ,’
(17)
Vacancy formation is calculated to be 2.45 eV more
1 favorable than hole formation. A strong correlation
between ionic radius and heat of solution is found (see
Fig. I ). A similar trend is found for divalent ions sub-
t
stituting at barium sites and tetravalent ions substi-
0' tuting at titanium sites (Figs. 2 and 3). Such trends
0.6 1.0 14 16
have previously been observed for polycrystalline
Iomc Radius/n”
BaTiO, doped with lanthanides [ 191. The divalent ions
Fig. I. Calculated heats of solution plotted against ionic radius Mg2’ and Ni*’ are predicted to substitute. at least par-
for monovalent dopant ions at barium sites. tially, at titanium sites with charge compensation
 Defect studies of doped and undoped barium titanite 93

For titanium site substitution we find that oxygen

vacancy compensation is favoured over hole compen-
sation. Electron compensation is calculated to be fa-
voured over cation (titanium) vacancy compensation
Tl14+
for donor dopants e.g. M3+ at Ba sites. Only at high
“4+9
I PO2 or high dopant concentration is this titanium va-
cancy compensation mechanism likely to become
/ dominant. Electron compensation is 4.87 eV more fa-
Pb4’
0 /’ vourable than titanium vacancy compensation. which
is I .34 eV more favourable than barium vacancy com-
/ O&4+
/ pensation. Jonker and Havinga [4] estimate a value of
2.8 eV for the energy difference between the two cation
vacancy compensation reactions from the data of
Daniels d al. [ 151. Self-compensation occurs when tri-
valent dopants substitute at both barium and titanium
sites (eqn 23). Table 4 summarises the calculated ener-
gies of solution.
We note that for the oxides of the lighter metals
(A1203 to Fe203), the energies of solution are higher
than for those occurring later in the periodic table. For
these oxides, cation substitution at the titanium site is
energetically favoured over barium site substitution.
However, a more varied range of behavior is predicted
Fig. 3. Calculated heats of solution plotted against ionic radius when the ‘self-compensation’ reaction is considered.
for tetravalent dopant ions at titanium sites. Inspection of Table 5 indicates that there is a strong
correlation between ionic radius and the tendency to-
wards self-compensation for a particular dopant.
Scandium, with an ionic radius of 0.68 A, favours
MO + BaTiOj = M$ + Vi + TiOz. (18) self-compensation whereas Cr3+ (0.63 A) substitutes
predominantly at titanium sites. Thus, a criterion sim-
The ionic radii of Mg2+ (r = 0.65 A) and Ni*+ (r ply based on ionic radii would lead us to predict that
= 0.72 A) correspond closely with that of Ti4+ (r = 0.60 only cations whose radius was below 0.68 A would
A). Larger divalent ions are expected to substitute produce majority ‘acceptor’ behavior; that is, substi-
preferentially at barium sites and hence charge com- tution at a titanium site with oxygen vacancy com-
pensating defects are unnecessary. Generally, therefore, pensation. The only exception out ofthe cations under
divalent and tetravalent ions will have little influence consideration is T?*. Siege1 and Muller (1979) main-
upon the conductivity of BaTi03, although Mg2+ as tain that electronic effects also play a role and in the
an impurity may lead to larger oxygen vacancy con- case of Ti3+ it is possible that this electronic effect is
centrations in ‘undoped’ samples. Such behavior is in more important than that due to ion size factors.
agreement with the conductivity measurements of Sa- Turning now to the remainder of the oxides in table
buri [20] on magnesium doped polycrystalline BaTi03 4. (Y203 through to Lt12O3) we see that in every case.
samples. barium site substitution is preferred over titanium site
The dopants of most interest for practical applica- substitution. Hence, for all these dopants, electron
tions are trivalent ions. We find that at least five types compensation would be expected. Again, the situation
of charge compensating behavior may be expected is complicated by the ‘self-compensation’ reaction: that
(eqns 19 to 23). is. incorporation at both Ba and Ti sites. The effect of
the ‘lanthanide contraction’ can most clearly be seen
from Table 6. On moving along the lanthanide series,
M203 + BaTi03 = 2Mb. + VA, + 3BaO (19) a switch from majority Ba-site substitution to self-
compensation is observed.
= 2M’B, + 2e’ + 2BaO + i 02 (g) Hence. although in all cases donor-type behavior
is expected, the effectiveness of the later lanthanides
(20) should be reduced by self-compensation. The switch
= 2M;i + V;; + 2Ti02 occurs at a cation radius of between 0.89 A and 0.94 A.
(21)
At least two explanations for the dependence of re-
sistivity on donor dopant content in barium titanate
=2M$i+Zh.+ZTi02-~O~(g)
ceramics [ 19, 221 can now be proposed. On moving
to higher dopant concentrations, either self-compen-
(22)
sation becomes more effective or titanium vacancy
.
= M$i + Maa + BaTlO,. (23) compensation increases at the expense of electron
 94 G. V. LEWIS and C. R. A. CATLOW

Table 4. Ener~ic,.sc$So/uGon ./ill Oxides in BaTiOj. E& is energy required for substitution at Ba-sites with
electron compensation Ez, substitution at X-sites with oxygen vacancy compensation and Eslr is substitution
at both sites

..
vO
Oxide F;ri /ev EseldbV
7.35 14.92 9.55
*l2’3
3.92 5.61 3.16
sc2o3
Ti203 3.65 8.17 4.32

3.99 8.10 3.46

‘2’3
5.25 11.45 6.75
cr203
4.79 9.52 5.57
M”2°3
5.04 9.57 5.72
Fe203
3.97 1.04 0.92
v3
5.85 -1.20 0.74
L”2°3
Nd203 4.93 -0.60 o._%

E”203 4.43 0.02 0.64

Gd203 4.31 0.24 0.69

Iio203 3.96 1.05 0.92

Y-D20 3 3.79 1.88 1.25

L"203 3.76 2.13 1.35

compensation. It is also possible that both of these From Table 7 we note that there is good agreement.
mechanisms are in operation. For YzO,, a donor type material is produced under
To complete this section. the conductivity behavior normal conditions (TiOz excess). although acceptor-
‘predicted’ from our calculations is compared with the type behavior can be produced in TiOz deficient sam-
impurity behaviour observed experimentally [23]. ples. Our calculations suggest that for Y203. the energy

Table 5. Relation between ionic radius*’ and tendency towards Table 6. Dependence of compensation on ionic radius” for
self-compensation the lanthanides

..
Dopant (<y- E___)/eV Oxide (“;a - ESe,)/eV r(P)/2

*%*3 -2.20 ,-l (94 1.02

0.3 k2‘3
+0.74 0.68 Nd203 -1.18 1 .oo
"2'3
Ti203 -0.67 0.76 E”203 -0.62 O-95
+0.54 0.74 Cd20 3 -0.45 0.94
‘2’3
‘=2*3 -1 .s 0.63 Ho203 to.:3 0.89
Mn203 -0 -78 0.66 yb20 3 ,+0.63 0.86
Fe203 -0.68 0.64 L”20 3 +0.?7 0.85
 Defect studies of doped and undoped barium titanite 95
Table 7. 1mprrrii.rbehavior in BaTi03. A and D denote ac- namely the ionic radius and effective charge of the
ceptor and donor type behavior, respectively. Those given in dopant. The dependence of binding energy on ionic
parentheses indicate partially effective behavior
radius is clearly seen for the isovalent ions. As the ionic
radius increases, a rapid decrease in binding energy is
Oxide Behaviour noted. For the tetravalent ions, only Si4+ is expected
Predictedfrom
defect calculations Ekceriment to form dopant-vacancy associates. Results for mono-
valent dopants suggest that the degree of ion size ‘mis-
A A match’ with the host cation is an important factor is
*2'3
Ga2o3
(A) determining the binding energy. Both Li+ (r = 0.68 A)
(A) A and Rb+ (r = 1.47 A) are predicted to show a small
“2’3
A A degree of oxygen vacancy association whereas no as-
Mn203 sociation is predicted for Na+ (r = 0.98 A). A similar,
A A
Fe203 though more marked effect, was observed for fluorite
(D) D/A
‘2’3 oxides [27, 291.
D D Turning now to the influence of effective charge on
La2o3
D D the binding energies, we note that both Mg*+and Mn3+
Gd203
have the same ionic radius (r = 0.66 A) but the binding
energy for Mn3+ is smaller by 0.2 1 eV. On increasing
the effective charge, the binding energy is increased. A
difference for the three defect compensation reactions
comparison of the results for Mn3+ and Mn4+ suggests
is smaller than for any other dopant investigated. Con-
that the ionic radius effect is also an important factor.
sequently, one might expect unusual impurity behav-
For these ions there is a considerable difference in
iour from this dopant.
(b) D@ct pair,li,rmation. The idea of defect clus-
binding energy for a relatively small difference in ionic
radius.
tering in ionic crystals with the formation of defect
Further support for the idea that both the degree of
complexes is not a new one [24]. Many examples have
size ‘mismatch’ and effective charge are crucial factors
been investigated and as an example of the agreement
in the determination of binding energies, is found from
between theory and experiment, we consider fluorite
a comparison of the binding energies for Mg*+ ions at
structure oxides, made anion deficient by the intro-
Ba and Ti-sites. The effective charge increases from 0
duction of acceptor-dopants. In these oxides, associa-
to +2 and is accompanied by a significant decrease in
tion of the acceptor-impurities and resulting oxygen
the binding energy. Although the effective charge and
vacancies have been reported [25, 261. For the case of
Coulombic interaction increases, the degree of ion size
trivalent impurities, one half of the dopant ions were
‘mismatch’ is sufficient to outweigh this. The combined
found to form complexes with the oxygen vacancies.
effect of both factors is exemplified by the results for
Association energies in the 0.3 eV-0.5 eV range were
reported, in excellent agreement with the calculated
binding energies of Butler [27].
Table 8. Culcttlurc~I binding mrrgic~s .fiw dopunl-o.t-ygtw va-
The idea of acceptor-impurity oxygen vacancy as- t’uncy pairx (a) dopant at Ba-site. (b) dopant at Ti site. A
sociation in BaTi has been proposed by Eror and negative value for the binding energy indicates the system is
Balachandran [28] to explain the variation with tem- bound
perature of the change from ~0:‘~ to ~0:‘~ dependence
of the electrical conductivity. This is the transition Dopant BindLn~ enera/eV
z@
point for the change in the electroneutrality condition
from (a) Li+ 0.68 -0.06
Na+ 0.98 0.00
n’ = 2[V;;] (24)
x+ 1.33 -0.03
to Rb+ 1.47 -0.05
,
xA’ + -VA”= (2x + .v)[Vo] (25) MgL+ 0.66 -0.56
IWl% 0.80 -0.19
and the data was interpreted in terms of association ;?c
Ca 0.99 -0.03
between the acceptor impurities and oxygen vacancies. 2+
Sl? 1.12 +o.J8
From Arrhenius plots, a derived enthalpy value of I. 13
f 0.14 eV was obtained for the association reaction. (b) MS2+ 0.66 -0.39
Chan P/ a/. [ 181 have also suggested that the above Mn2+ 0.80 -0.X
temperature dependence observed for Al-doped
Al> 0.51 -0:s
BaTiOJ may indicate some small degree of defect as-
sociation of the type (AI$,VG)‘.
Mr?+ 0.66 -0.18
In Table 8. we present our calculated binding ener- Si 0.42 G1.43
gies for a range of dopant-oxygen vacancy pairs. PlnE 0.60 +0.&
k
At least two factors seem to be important in the Zr 0.79 +1.Jt3
determination ofthe magnitude ofthe binding energies;
 96 G. V. LEWISand C. R. A. CATLOW

Mn3+ and Mn4+ ions. The two factors reinforce each

other leading to a large difference in binding energy.
We can conclude from the above discussion that
Dopant E;i/eV
although Coulombic attraction contributes to the
binding energy of defect complexes, elastic forces (that 2+
Mg -0.76
is. relaxation of the ions surrounding the defect) play
a major and sometimes dominant role although in no MI-?+ -0.50
instance are the binding energies as large as those pro-
posed to explain conductivity measurements. MJ+ -0.52
Table 9 summarises results for dopant-cation va-
Fe*+ -0.64
cancy association.
A similar correlation between dopant radius and Fe3+ -0.84
binding energy to that observed for oxygen vacancy
complexes is noted for these neutral barium vacancy- A13+ -1.04
dopant complexes. For Y3+, the smallest cation, a large
d+ -0.58
binding energy is calculated. As the degree of ‘mis-
match’ increases there is a corresponding decrease in
the binding energy. However, conductivity measure-
ments are mainly concerned with lightly doped (< I %) have also been derived from thermogravimetric mea-
BaTi03 for which electron compensation dominates. surements [30]. These results suggest the Mn2+ and
Consequently. these complexes can be considered to Mn3’ levels are I .3 eV and I .9 eV respectively from
play a negligible role in the defect chemistry of samples the top of the valence band. Inspection on Table 10,
with low dopant and impurity concentrations. How- shows that our calculated energy difference for these
ever, at higher donor dopant concentrations, titanium two levels is 0.50 eV.
vacancy compensation is believed to occur [4]. Our However, the Mn3+ level is calculated to be only
calculations suggest a value of -0.90 eV for the binding 0.52 eV above the valence band edge whereas the ther-
energy of a [La’BaVz] complex and hence, vacancy- mogravimetrically determined value of EA is 1.3 eV.
dopant association may be important in more heavily These values are both consistent with the fact that p-
doped samples. type conductivity in BaTi is only observed at high
(c) Trapping qfchurge carriers. The oxygen vacancy temperatures. However, the latter value of 1.3 eV is
concentration of BaTiO3 doped with acceptors was de- larger than the activation energies found from electrical
termined gravimetrically by Hagemann and Hennings conductivity measurements [7].
[30] as a function of po2 for temperatures between In contrast, donor-doped crystals exhibit appreciable
700°C and 13OO’C. Their results were consistent with n-type conductivity even at low temperatures. At in-
compensation of acceptors by doubly ionised oxygen termediate po2 (- 12 < 1ogi0p02 < -5), the conductivity
vacancies, which accords with our calculated defect depends linearly on the concentration of donor dopant.
compensation reaction energies. We have attempted to estimate the trapping energy of
In order to obtain a more detailed understanding of electrons at donor centres assuming a small polaron
the defect chemistry of acceptor-doped BaTi03 spec- model for electron conduction (represented as Ti;, in
imens. it is necessary to determine the electronic energy our defect model) and then calculating the binding
levels of the acceptors within the BaTiO, band gap. energies for (Mi,Tir,) pairs. In all cases (M = La. Ce.
Nakahara and Murakami [31] determined the elec- Cr) the dopant-electron complexes were found to be
tronic states of Mn ions using ESR and optical ab- unbound: that is, conduction band electrons are pre-
sorption techniques. Their derived energy levels for dicted, in agreement with the experimental observation
MI? and Mn3’ were assigned above and below the of n-type semiconducting behaviour for donor-doped
Fermi level respectively since optical measurements BaTiOj.
showed that the absorption spectrum of oxidised crys-
tals contained a band at 22000 cm-~’ corresponding to
SUMMARY OF DEFECT MODEL
a transition greater than half the band gap. The elec-
tronic energy levels of Mn ions within the band gap For ‘undoped’ BaTiO, our calculations suggest that
intrinsic disorder is masked by oxygen vacancies which
compensate accidental acceptor impurities. At high
po2 holes are trapped at impurity sites and hence I>-
type insulating materials result at room temperature.
Specimens prepared at lower po2 values are rr-type
Dopant -r/x Binding Enerm/eV conducting with doubly ionised oxygen vacancies.
y3+ These observations have been contirmed by experi-
0.85 -0.73
> mental conductivity measurements. However. our
1,a3+ 1.02 -0.?7 calculations suggest that barium vacancies are weakly
c&3+ l.C? 4.2: bound by oxygen vacancies and will not act as deep
traps for holes. Titanium vacancies will act as deep
 Defect studies of doped and undoped barium titanite
traps for holes but negligible concentrations are ex-
pected in samples containing low concentrations of
impurities and donor dopants.
The varied behaviour of trivalent dopants can be
explained in terms of three competing compensation
mechanisms. Smaller ions (e.g. A13+) substitute pref-
erentially at titanium sites with predominantly oxygen
vacancy compensation whereas larger ions (e.g. La3+)
substitute at barium sites with predominantly electron
compensation. At high poz and high dopant concen-
trations titanium vacancy compensation becomes more
favourable. Trivalent ions of intermediate size (e.g.
Sc3+) tend to lend to ‘self-compensation’ and the ef-
fectiveness of donor and acceptor dopants may be
modified by this competing compensating reaction.
Hence many trivalent dopants may be only partially
effective in modifying the conductivity behaviour of
BaTiO,. It is predicted that the lanthanides will become
decreasingly effective as donor dopants on moving
across the lanthanide series. This is primarily due to
the ion size effect, the ‘lanthanide contraction’ fa-
vouring the ‘self-compensation’ mechanism. Binding
energies for charge trapping at dopants and dopant
vacancy pairs are generally calculated to be lower than
those proposed previously to interpret conductivity
measurements.
Acknowledgements-We would like to thank STC Compo-
nents Ltd and the SERC for supporting the work.
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