Materials Science and Engineering, B1 (1988) 193-201 193

The Influence of Ionic Radii on the Incorporation of Trivalent Dopants into

BaTiO 3

L. A. XUE*, Y. CHENt and R. J. BROOK~

Department of Ceramics, The University of Leeds, Leeds LS2 9JT (U.K.)
(Received June 10, 1988 )

Abstract ceramics. In this respect, the effects of donor

The form of incorporation of different lantha-
nide ions into BaTiO 3 has been investigated as a
function of the dopant concentration (0.15-3.0
at. %) and of the A-to-B site ratio (0.99-1.01); mic-
rostructural examination and electrical conduc-
tivity measurements have been used to assess the
incorporation mode. The ionic radii of the dopants
are significant in determining the form of incorpor-
ation. La 3+ to Ho 3+ substitutefor Ba 2+ and hence
act as donors, while Tm ~+ to Lu 3. replace Ti 4÷
and thus behave as acceptors. Er ~÷ can be forced
into either the barium or the titanium sublattice by
adjustment of the A-to-B ratio (it is a donor for an
A-to-B ratio less than unity, an acceptor for an
A-to-B ratio greater than unity and self-compen-
sated for an A-to-B ratio equal to unity). Similar
features are found in a parallel study of group llIb
dopants (Sc 3+, Y~+ and La3+). Sc ~+ is a typical
acceptor, while Y-~+ is analogous to Er 3+. The
group Illa trivalent cations are all acceptors (B site
occupancy for size reasons). On similar grounds,
Bi ~+ is always an A site donor. A phenomenon of
"barium site preference" is found for ions of inter-
mediate sizes. This is discussed in terms both of the
"tolerance factor" t and of the relative strengths of
the valence bonds.
1. Introduction
Aliovalent dopants can have a profound influ-
ence on the microstructural development and
resultant electrical properties of BaTiO3-based
*Present address: Department of Materials Science and
Engineering, Comell University, Ithaca, NY 14853, U.S.A.
tPresent address: Department of Civil Engineering, The
University of Leeds, Leeds LS2 9JT, U.K.
-~Present address: Max Planek Institut fiir Metallforschung,
7000 Stuttgart 80, ER.G.
dopants and of acceptor dopants are remarkably
different. For instance, acceptor-doped BaTiO3 is
an insulator at room temperature. Donor-doped
BaTiO 3 is a semiconductor at relatively low
doping levels (up to a concentration of around
0.3-0.5 at.%), higher donor contents giving rise to
restored insulating behaviour; this "conductivity
anomaly" [1-3] has been interpreted either as a
grain size effect arising from kinetic processes
during firing and cooling [1] or as a change in the
mode of donor compensation from electrons to
cation vacancies [3, 4]. It has also been found that
all donor dopants can inhibit grain growth in
BaTiO 3 once their concentrations are beyond a
common threshold of 0.3-0.5 at.%, whilst only
certain acceptors can act in this way [5].
Because of the large difference between the
ion sizes of Ba 2+ and Ti 4+ (1.47 A and 0.68 A
respectively), the ionic radius is a rather critical
factor in determining the lattice site which a par-
ticular dopant will occupy. As a result, relatively
small ions go to the six-coordinated titanium site
while large ions go to the 12-coordinated barium
site. Ionic radii for dopants of interest are listed in
Table 1.
Trivalent dopants in BaTiO 3 raise an interest-
ing situation for they can behave as donors or as
acceptors, depending on the site occupied. These
ions are also among the dopants of most interest
for practical applications. Thus the resulting
microstructures and electrical properties will be
strongly dopant size dependent. For example,
La 3+ has a 12-coordinated size of 1.23 A and has
been recognized as a typical donor and as an
effective grain growth inhibitor in BaTiO 3 [1, 5],
while the opposite is true for AI 3 + which has a
six-coordinated radius of 0.51 A [5, 7]. Roten-
berg et al. have also suggested that the site occu-
pied by rare earth cations (Sm3+, Er 3+ and Lu 3+)

0921-5093/88/$3.50 © Elsevier Sequoia/Printed in The Netherlands

194

TABLE 1 lonic radii of Ba 2 +, Ti 4 + and the relevant standing of the differences in behaviour
trivalent dopants (data from ref. 6)
associated with the changing ionic size would
Ion Ionic radius (A) assist efforts to improve the performance of these
devices. Smyth and coworkers [10] have
Six 12
coordinated coordinated
examined the incorporation of some lanthanides,
namely neodymium, samarium, dysprosium,
Ti Iv 0.68 erbium and ytterbium into BaTiO 3 as a function
Bam 1.47
La m 1.14 1.23 of the barium-to-titanium ratio, using measure-
Ce m 1.07 I. 15 ments of the oxygen-pressure-dependent conduc-
Pr m 1.06 1.14 tivity. They found a gradual shift in the site
Nd m 1.04 1.12
Sm m 0,98 1.06 occupied as the ionic size changed and a signifi-
Eu m 0.98 1.06 cant effect of the barium-to-titanium ratio on the
Gd m 0.97 1.04 distribution of the dopant. Er 3" is found to be an
Tb m 0.93 1.00
Dy m 0.92 0.99 intermediate case and occupies either the barium
Hom 0.91 0,98 site when there is an excess of TiO:, or the tita-
Er m 0.89 0.96
nium site when there is an excess of BaO.
Tm M 0.87 0.94
Yb m 0.86 0.93 However, their study is limited to a low doping
Lum 0.85 0.92 content of 1200 ppm, and the effect on micro-
ym 0.92 0.99 structure development and grain growth has not
Sc m 0.81 0.87 been examined.
K~ 1.33 1.44 It has been shown that the combined study of
AI m 0.51 the degree of grain growth inhibition and the
Ga l~j 0.62
In m 0,81 extent of the conductivity anomaly exhibited in
Bi m 0.96 1,03 donor-doped BaTiO 3 [1-3] can be employed as a
Tav 0.68 fairly sensitive and reliable method for the inves-
tigation of the behaviour of the dopant [5].
Previous work has shown that the grain growth
depends on the ionic radii and concentrations [8].
inhibition varies greatly as a consequence of
The work of Lee and Smyth [9] on the series
lanthanide contraction [5]i In this paper, we
La 3+, y3 +, Sc 3+ and A13 + has shown by means of
report results obtained by using these two tech-
conductivity measurement made as a function of
niques to study the incorporation of trivalent ions
oxygen partial pressure that La 3÷ behaves as a
into BaTiO3 as a function of the dopant concen-
donor while Sc 3÷ and AI 3+ behave as acceptors;
tration and of the barium-to-titanium ratio. The
y3+ acts as a donor in the presence of excess
lanthanide series is taken as the model system.
TiO2 and as an acceptor in the presence of excess
BaO. This is consistent with the finding that, with
2. Experimentalprocedures
the addition of excess BaO, yttrium-doped
BaTiO3 no longer shows semiconducting behav- All elements in the lanthanide series except
iour at low doping levels [5]. Thus y3 +, having an promethium were investigated. Trivalent cations
intermediate ionic radius (0.92 A for the Ti 4 ÷ site of the group III series (Sc 3t, y 3+ A13., Ga 3 ~ and
and 0.99 ,/k for the Ba 2+ site), can be accommo- In 3+) and Bi 3+ were also included for compari-
dated in either of the cation sites in the BaTiO3 son. The concentration of the additives studied
lattice. was normally in the range 0.15-3.0 at.%. All
The lanthanide series represents a group of chemical reagents involved were of high purity
progressively smalled trivalent ions, the largest (greater than 99.9%). A commercial high purity
ionic radius being 1.23 A (La 3+ , 12 coordinated) BaTiO 3 (Ticon HPB, TAM Ceramics, lots 708
and the smallest radius being 0.85/~ (Lu 3+, six and 717) was employed in the experiments. The
coordinated). Therefore, they are an ideal choice A-to-B site ratios of the as-received HPB powder
for studies of the influence of the dopant size on were 0.9926 (lot 708) and 0.9901 (lot 717),
site occupancy and on the ensuing microstruc- which were adjusted to desired values by addition
tures and electrical properties. Lanthanide-doped of either Ba(NO3) z or Ti(C4HgO)4 solution. Here
BaTiO 3 has found wide application in the manu- A and B represent the total of all species occupy-
facture of positive temperature coefficient ther- ing the 12-coordinated A sites (barium sites) and
mistors and of barrier layer caPacitors. An under- the six-coordinated B sites (titanium sites)

respectively. The dopants were introduced in the
form of either ethanol solution or aqueous solu-
tion to an ethanol suspension of the HPB powder
which had been ultrasonically agitated; they were
then precipitated using ammonia solution. Drying
was achieved by a combination of infrared
heating above and a hot plate below, the suspen-
sions being continually stirred. After calcination
at 1100 °C for 5 h, the powders were die pressed
at a pressure of about 60 MPa into pellets 1 cm in
diameter which were then sintered in air at
1310-1350 °C for 1 h and furnace cooled. The
densities of the final specimens were in the range
91%-96% of the theoretical density, as deter-
mined by the mercury immersion method. The
microstructures were examined by scanning
electron microscopy on both polished-and-
etched sections and on fracture surfaces. The
room temperature conductivity was measured by
the d.c. two-probe method.
Fig. 1. Scanning electron photographs of polished-and-etched sections of (a) undoped, (b) BaTiO~ doped with 0.4 at.% Ho and
(c) BaTiO 3 doped with 0.7 at.% Ho.
195
3. Results and discussion
The overall effect of the doping and of the
A-to-B ratio, in terms of the resulting microstruc-
ture and room temperature electrical conduc-
tivity, is briefly summarized for the different
dopants in Table 2. Typical microstructures of
both highly donor-doped fine-grained BaTiO 3
and of undoped or low level donor-doped
coarse-grained materials are shown in Fig. 1.
From there, the grain growth inhibition function
of the donor is clear. As noted before, the com-
mon feature of different donor-doped BaTiO3
compositions, i.e. the fact that the materials
become semiconducting at relatively low dopant
content (less than 0.3-0.5 at.°) but insulating
again at higher donor concentrations [1-3], is a
simple means of determining whether a particular
dopant under given conditions is acting as a
donor or not. It can be immediately seen from
i
.=
~ , ~ ~"-~_~ ~:~'~ ~ , ,. ~. . . . ~-,~4~ ~'~4~ ,~"~
VA V A V A V A VA V A VAVA VAVA VAVA VAVA VAVA VAVA VAVA VA~VA VA~VA VAVAVA
i
4-
II
"It
II
~ ~°° ....
 197

TABLE 2--continued

Dopant A -to-B Assumed Dopant Micro - ~oom

ratio site content structure temperature
occupation (at.%) (C or F) electrical
conductivity
(3"or/)
Lu 0.99 A < 0.35 C I
Lu 0.99 A > 0.45 F I
Lu 0.994 A < 0.40 C I
Lu 0.994 A > 0.50 F l
Lu 1.01 B < 0.70 C l
Lu 1.01 B > 0.80 F l
Sc 0.994 A U p to 0.80 C 1
Sc 1.01 B < 0.30 C I
Sc 1.01 B >0.35 F I
Y 0.99 A <0.50 C S
Y 0.99 A > 0.55 F I
Y 0.994 A <0.45 C S
Y 0.994 A >0.50 F I
Y 1.00 A+B <0.45 C S
Y 1.00 A+ B > 0.50 F I
Y 1.01 B < 0.35 C 1
Y 1.01 B >0.40 F I
Bi 0.994 A <0.25 C S
Bi 0.994 A > 0.30 F 1
Bi 1.01 B < 0.20 C S
Bi 1.01 B >0.25 F 1
AI 0.994 B U p to 1.2 C I
AI 0.99 A U p to 1.0 C l
Ga 0.994 B U p to 0.80 C 1
Ga 0.99 A U p to 1.0 C 1
In 0.99 A U p to 0.50 -- I
In 0.994 B < 0.22 C 1
> 0.25 F I

C, coarse grained; F, fine grained; S, semiconducting; I, insulating; (SS), slightly semiconducting.

Table 2 that, in the lanthanum series, the ions Donor G.G.LT. of Ln-Doped BaTiO3

from La 3+ to Ho 3÷ are all donors, regardless of 3.0-

the A-to-B site ratio, while Tm 3+, Yb 3+ and
Lu 3+ are A-to-B-ratio-independent acceptors as .-e- A/B = 0.994
= ,

indicated by the absence of the conductivity

anomaly. Er 3÷ behaves rather differently in acting 2.0
as a weak donor at an A-to-B ratio of less than
unity but as an acceptor when the A-to-B ratio is q
greater than unity. o
These results are generally in agreement with ~
c
1.0
the previous findings of Smyth and coworkers QO
[10], in that Er 3÷ occupies either the A site or the
B site, depending on the actual A-to-B ratio.
0.0
However, Smyth and coworkers describe a i , r • i • i • i , T , w , r * ~ , I , ~

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er
gradual shift in donor-acceptor character in the
lanthanide series and suggest that, as the ionic Lanthanides (111)
radius increases, the behaviour becomes increas- Fig. 2. G G I T values for lanthanide donors in BaTiO 3.
ingly donor type with an increasing fractional A
site occupation of the dopant. In the present required to produce grain growth inhibition (the
study, such a gradual shift in donor character has donor grain growth inhibition threshold (GGIT);
not been observed. This can be shown by a close these data are plotted in Fig. 2. The GG1T has a
examination of the donor concentrations relatively constant value, varying around 0.3-0.5
198
at.%, for all lanthanide donors except for Er 3÷
where there is a sharp increase to 2.5 at.%. A sud-
den change in the mode of dopant incorporation
is indicated. At the dopant concentrations studied
in this work, Er 3+ is the only lanthanide which
can be forced into either the Ba 2+ or the Ti 4+ site
by changing the A-to-B ratio. The somewhat
lower GGIT value for cerium may imply the
existence of Ce 4- on the barium sublattice.
The dopant concentration investigated in the
present work is higher than those studied by
Rotenberg et al. [8] and by Smyth and coworkers
[9, 101. The homogeneity of our materials has
been checked with energy-dispersive X-ray
analysis (EDXA) on polished sections of speci-
mens, and with X-ray diffraction (XRD) analysis
on powders made of crushed and ground sintered
pellets. No noticeable variation in the concentra-
tion of the dopants has been observed by EDXA.
Although microstructure examination revealed in
some samples the presence of a small amount of
grain boundary phase which has been identified
by EDXA as either titanium-rich or barium-rich
barium titanate phases, XRD studies performed
on these specimens did not detect any second
phases. These results suggest a fairly homo-
geneous distribution of the lanthanide dopants in
the materials. This is consistent with the high
solid solubility limits of lanthanides in BaTiO~
reported in the literature. For example, a solid
solubility of 13 at.% for lanthanum in BaTiO~ has
been found by, Jonker and Havinga [11], and a
similar value (12 at.%) for neodymium by Shaikh
and Vest [12].
The possible modes for incorporating a triva-
lent ion (M ~+ ) into the BaTiO3 lattice are of the
following types.
(a) A site, electron compensation, is given by
M203 + 2TiO_, -+ 2MB," + 2Ti-vi + 6 0 o + 2e' + !0~
~1)
(b) A site, barium vacancy compensation, is
given by
M203 + 3TiO~ + 2Mu~" + 3TiT~+ 9 0 o + VB~(" (2)
(c) A site, titanium vacancy compensation, is
given by
2M,O~_ + 3TiO~_ -~ 4MB," + 3Tiv~ + 120o + VT i ....
(.3)
(d) B site, hole compensation, is given by
M203 + 2BaO + ½02 ~ 2MT~' + 2BaB, + 6 0 o + 2h"
(4)
(e) B site, oxygen vacancy compensation, is
given by
M,()~ + 2BaO ~ 2M-ri' + 2Ba~< + 5 0 o + Vo'" (5)
i i' A+ B sites, sell-compensation, is given by
MeO~ ~ M~," + MTi'+ 30(~ (6)
Modes involving interstitial lattice defects have
been discarded as being very unlikely in the
perovskite structure t 13-1 5 t.
At low concentrations, La ~~ to Ho ~* and also
Er ?'+ at A-to-B ratios less than unity incorporate
into the BaTiO 3 lattice according to mode (a); this
produces a semiconducting material and abnor-
mal grain growth is not inhibited. At high con-
centrations, these donors substitute for Ba 2+
through mechanism (c) [4, 5], giving rise to a fine-
grained microstructure and an insulating material.
The remaining three lanthanides, i.e. Tm 3+, Yb 3+
and Lu 3+. go to the titanium sublattice and act as
acceptors. Their actual incorporating modes are
based on either eqn. (4) (at low concentrations) or
eqn. (5)(at high concentrations)[5]. The same
mechanisms apply to Er 3~ at A-to-B ratios
greater than unity, which then becomes an
acceptor and behaves similarly to these last three
lanthanides. The wide disparity observed among
the acceptors in their effects on grain growth is
consistent with previous findings on acceptor
behaviour [5 ].
For Er -~+, there is a strong tendency to adopt
a self-compensation mechanism as illustrated
in mode (f); evidence comes from the observation
that Er 3+ loses its ability to retard grain growth at
an A-to-B ratio of unity and produces materials
that are almost insulating. The slightly semicon-
ducting behaviour measured may stem from a
small deviation of the actual A-to-B ratio from
unity.
To evaluate fully the effect of ion size on the
dopant site occupation, it is helpful to look at the
relation between the lanthanide contraction and
the deviation in size from either Ba e+ or Ti 4÷.
Use is made of the ionic radius data from ref. 6 as
listed in Table 1. The relative differences in ionic
radii thus obtained are plotted in Fig. 3, where r 0
represents the ionic radius of either Ti 4+ (six
coordinated) or Ba: + (12 coordinated), and r the
ionic radius of the lanthanide on the correspond-
ing site. As shown in the diagram, the two traces
which represent the relative deviation of the sizes
of the lanthanides from the sizes of either Ba 2+ or
Ti 4. cross at a point lying between Ho 3÷ and

Relative Difference in Ionic Radii for Lanthanides to Ti(IV) & Ba(ll)
0,7"
-~ ro = Ti(IV)
0.6
0.5
,o
~" 0.4
b smaller than unity, there is less than the ideal
L,.
0.3
(I.2
ka Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
L a n t h a n i d e s (111)
Fig. 3. Relative difference between the ionic radii of lantha-
nide ions and the host cations in BaTiO~.
a b
@ © • from the ionic radius set of Ahrens [17], which
A~÷ O ~- B.÷
Fig. 4. Two different ways of viewing the cubic perovskite
structure: (a) cubic close-packed arrangement of A and
oxygen ions, with the B ions filling the interstitial positions~
(b) framework of BO~, octahedra, with the A ions occupying
the holes, Oxygen ions are at the corners of octahedra.
Er 3+. Thus there is a quite good correlation
between the calculated transfer ion size and the
experimental results. The diagram suggests that
Ho 3+ is closer to the ideal intermediate size than
is Er 3+, whilst the experimental observations
indicate that only Er 3+ behaves as a mixed site
ion. This implies that factors other than simple
ion size influence the site occupation of a dopant,
somewhat favouring the barium site selection.
If the actual geometrical packing of the ions in
the BaTiO 3 lattice is taken into account, this devi-
ation may be understood. The perovskite struc-
ture which BaTiO 3 displays can be regarded as a
cubic close-packed arrangement of A (here
barium) and oxygen ions, with the B (here tita-
nium) ions filling the interstitial octahedral posi-
tions (Fig. 4(a)). The packing of this structure can
be characterized by a "tolerance factor" t which is
199
defined in the following way[16]:
rA+ro
t= 2]/Z(r~ + ro) (7)
where r A, r B and r o are the ionic radii of the A, B
and oxygen ions respectively• When t is exactly
equal to unity, the packing is "ideal". When t is
space available for the B ion. The situation will
become worse if a larger dopant ion then comes
to substitute for the host B ion. This is the case in
BaTiO3, as is shown by calculation using the ionic
radii from ref. 6 (ro = 1.40 A); a value of 0.976 is
yielded for the tolerance factor t. This value pre-
dicts a relative preference for a dopant ion of
intermediate size to go to the Ba 2+ site. In the
present study, therefore, the lanthanides have a
slight bias to replace Ba 2+ rather than Ti 4 +, shift-
ing the switch-over point from donor to acceptor
behaviour to a smaller ionic radius. It should be
pointed out that the t value for BaTiO3 as calcu-
lated by Megaw [16], who used the Goldschmidt
radii (modified for Ba2+), was 1.02. This value
would yield the opposite effect. The data suggest,
therefore, that the values for ionic radius
employed in this study are more appropriate. The
data are also in agreement with the prediction
would give an even smaller t value than that
attained in this work.
The perovskite structure can also be visualized
as a three-dimensional framework of BO~ (here
TiO6) octahedra as shown in Fig. 4(b). The
dimensions of the structure will be essentially
determined by the T i - O octahedra, where the
strong valence bond of value ~ keeps the octa-
hedra as relatively rigid units. The electrical
neutrality requirement is fulfilled by occupation
of the central position in the structure with an A
cation• Since the valence bond to this ion has the
low value of 4, the size of A will have relatively
less effect on the structure, as long as it is small
enough to fit in the hole• This may also contrib-
ute to the observed phenomenon of barium site
preference.
A parallel study has been done on the group
IIIb ions (Sc 3+, y3+ and La ~ ) . Although much
shorter, this series provides a good comparison.
La 3+ is known as a perfect donor. Sc 3+, as can be
seen from Table 2, is a typical acceptor. The Y3 +
ion, like Er 3+, can either be a donor (for an
A-to-B ratio less than unity) or an acceptor (for an
A-to-B ratio greater than unity). This finding is in
20{J
Relative Difference in Ionic Radii
0.7
/ two lanthanides, Dy s+ and Ho ~~, are also below
-o- ro = Ti(IV) /J
0.6 =
0.5"
o 0.4
i
0.3
0.2
0A ,
Sc Y La
Trivalent I o n s
Fig. 5. Relative difference in ionic radii between group lllb
series ions and the host cations in B a T i O >
line with that of Lee and Smyth [9]. However, Y-~"
is a much more effective d o n o r than E r 3+. This is
immediately apparent when the G G I T values of
the two are compared at an A-to-B ratio of 0.994
(0.5 at.% and 2.5 at.% for y3+ and E r 3+ respec-
tively). Moreover, at an A-to-B ratio of unity, Y~+
still shows a clear d o n o r character, while Er s+
exhibits predominantly self-compensating behav-
iour. T h e strong d o n o r behaviour of y 3 + can be
attributed to its larger ionic radii (0.92 A in six-
coordination and 0.99 A in 12-coordination as
against 0.89 A and 0.96 A for Er ~+). If the rela-
tive differences in ionic radii are plotted for L a ~+,
y 3 * and Sc 3+, as in Fig. 5, it is seen that Y~- is
located at the d o n o r side of the "ideal" inter-
mediate ion size.
Two critical values (0.92 A and 0.96 A) for
dopant ionic radii may be set up to estimate
which site a given dopant will go to. If an ion has a
six-coordinated radius smaller than 0.92 A, it
most probably substitutes for Ti 4 +. In contrast, if
its 12-coordinated radius is over 0.96 A, then the
behaviour of the dopant is most probably of
donor type. T h e chance for an ion to satisfy both
criteria is rare (only E r ~+, Y~+, Dy 3÷ and H o ~+
do). T h e group IIIa ions studied ( A P - , Ga 3 + and
In 3 +) are all acceptors with six-coordinated radii
much smaller than the critical value. Bi 3+ has a
12-coordinated radius larger than the critical
value and is always incorporated into the barium
sublattice as a donor, T h e other established triva-
lent ions in the BaTiO3 lattice, i.e. Cr 3+ and Fe 3+,
and indeed most of the cation dopants known for
BaTiO3 observe this size rule. T h e r e are some
exceptions, i.e. Ca ~-+ is known to be able to
replace Ti 4 + [5, 18], although its six-coordinated
radius is 0.99 A [61; the six-coordinated sizes of
the critical value, but they do not substitute for
Ti a~ in a noticeable manner, at least in the
concentration range studied.
It is interesting to see flom these results h o ~
significant the influence of a small variation
(about 0.02 A) in dopant size can be for the
ensuing microstructures and electrical properties
of the material.
A question remains in respect of the ability of
Y ~ to occupy either A or B sites while its coun-
terpart in the lanthanide series, i.e. Dy ~ , cannot;
both ions have the same ionic radii and bear the
same electrical charge. Ho :+, which is even
smaller than Y~+, also behaves as Dy -~, This
certainly means that other factors such as polar-
izability and the character of the bonding also
play a role. In this regard, Y~ ~ seems to differ
distinctly from the rare earths.
4. Conclusion
T h e lanthanide contraction has a notable effect
on the way in which a lanthanide ion incorporates
into the BaTiO~ lattice. La 3 ~ to H o -~* substitute
for Ba 2 + and hence act as donors, while Tm 3+ to
Lu ~" replace Ti 4+ and behave as acceptors. Er 3-
can be forced into either the barium or titanium
sublattices by alteration of the A-Io-B ratio (it is a
d o n o r for an A-to-B ratio less than unity, an
acceptor for an A-to-B ratio gre-~ter than unity
and self-compensated for an A-to-B ratio equal to
unity). These occupancies lead to very different
results in terms of the microstructures and elec-
trical properties of the materials produced.
A parallel study on the group IIIb dopants
(Sc 3-, Y-~- and La 3+ arrives at a similar conclu-
sion Sc -~+ is found to be a typical acceptor. Y-~*.
although being much stronger in donor character
than Er ~ , can also be either a d o n o r or an
acceptor, depending on the A-to-B rauo.
These results are explained in terms of the
influence of ionic radius on doping character.
A degree of barium site preference is observed
for dopants of intermediate size. This can be
interpreted in terms of either a "tolerance factor"
t or the relative strengths of the valence bonds of
T i - O and B a - O in the BaTiO~ structure.
Acknowledgment
One of the authors (L. A. Xue would like to
thank Professor R. Raj for providing him oppor-

tunities to complete a part of this work at Cornell
University.
References
1 R. Wernicke, Phys. Status Solidi A, 47(1978) 139-144.
2 T. Murakami et al., J. Am. Ceram. Soc., 56 (1973)
294-297.
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