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Acta Materialia 56 (2008) 4993–4997

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Grain-boundary plane orientation dependence of electrical barriers

at R5 boundaries in SrTiO3
Sung Bo Lee a,*, Jong-Heun Lee b, Yoon-Ho Cho b, Doh-Yeon Kim a, Wilfried Sigle c,
Fritz Phillipp c, Peter A. van Aken c
a
School of Materials Science and Engineering, Seoul National University, Seoul 151-744, South Korea
b
Department of Materials Science and Engineering, Korea University, Seoul 136-713, South Korea
c
Max-Planck-Institut für Metallforschung, Heisenbergstrasse 3, 70569 Stuttgart, Germany

Received 20 February 2008; received in revised form 14 June 2008; accepted 16 June 2008
Available online 19 July 2008

Abstract

Dependence of the electrical properties on grain-boundary plane orientation is examined by a combination of high-resolution trans-
mission electron microscopy, impedance spectroscopy, and electron energy-loss spectrometry using two kinds of SrTiO3 R5 ([1 0 0]/36.8°)
bicrystalline grain boundaries: symmetric (3 1 0) (18.4°/18.4°) and asymmetric (8.4°/28.4°). While the symmetric grain boundary is
observed to be straight with the symmetric (3 1 0)//(3 1 0) plane orientation, the asymmetric grain boundary is faceted into symmetric
(3 1 0)//(3 1 0) and (2 1 0)//(2 1 0), and asymmetric (1 0 0)//(4 3 0). Grain-boundary impedance is observed only in the asymmetric grain
boundary, and the electron energy-loss spectrometry quantification indicates that the asymmetric (1 0 0)//(4 3 0) facets are more oxy-
gen-deficient than the symmetric ones. The results suggest that the asymmetric (1 0 0)//(4 3 0) facets are the most resistive among the three
different facets.
Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Annealing; Electron energy-loss spectroscopy; Transmission electron microscopy; Strontium titanate; Grain-boundary structure

1. Introduction ous high- and low-angle grain boundaries in undoped

Strontium titanate (SrTiO3) is widely used as grain-
boundary barrier-layer devices, such as capacitors and
varistors [1], and thus knowledge of the electrical proper-
ties of grain boundaries is imperative. The electrical behav-
ior is known to depend on the double-Schottky barrier
established by the grain-boundary charge and the associ-
ated space charge across the grain boundary [2,3]. It has
been suggested that, for undoped SrTiO3, oxygen defi-
ciency, that is, an excess of oxygen vacancies, causes a
net positive charge at the grain-boundary core with a neg-
ative space charge, creating a double-Schottky electrical
barrier [4–6]. According to the electron energy-loss spec-
trometry (EELS) measurements by Kim et al. [4], for vari-
*
Corresponding author. Tel.: +82 2 880 8970; fax: +82 2 884 1413.
E-mail address: bolee@snu.ac.kr (S.B. Lee).
SrTiO3, the Ti-to-O atomic concentration ratio is higher
than in the bulk, indicating that the grain boundaries are
segregated by Ti or deficient in O. An atomic resolution
study using the combination of Z-contrast imaging and
EELS by Browning et al. [5] indicated that an undoped
R5 grain boundary is oxygen-deficient, which leads to a
positive grain-boundary charge.
A grain boundary is described by five macroscopic
degrees of freedom: three for grain misorientation and
two for grain-boundary plane orientation (also referred
to as grain-boundary inclination) [7]. The charge carrier
transport has been observed to change with grain-bound-
ary misorientation angle. In a study using a SrTiO3 low-
angle grain boundary (5.4°/[0 0 1] tilt), De Souza et al. [8]
showed that cores of dislocations are charged. Resistance
of low-angle grain boundaries increases with increasing tilt
angle, because the dislocation spacing decreases [9]. At a

1359-6454/$34.00 Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2008.06.019
4994 S.B. Lee et al. / Acta Materialia 56 (2008) 4993–4997
fixed misorientation relationship, furthermore, the electri-
cal property is expected to depend also on grain-boundary
inclination. However, its effect has been rarely studied.
In the present study, to explore the effect of grain-
boundary inclination, two kinds of nominally undoped
R5 grain boundaries in SrTiO3 were used: one was a sym-
metric (3 1 0)1//(3 1 0)2 grain boundary and the other an
asymmetric one. These grain boundaries were annealed at
1100 °C for 36 h in air. While the symmetric grain bound-
ary was observed to be flat with the symmetric boundary
plane orientation, the asymmetric grain boundary revealed
two kinds of symmetric facets and one kind of asymmetric
facet. Their electrical properties were investigated by
impedance spectroscopy and were then linked to the depen-
dence of oxygen deficiency on grain-boundary inclination,
which was determined by EELS. Our work suggests that
the charge carrier transport characteristics strongly depend
on grain-boundary plane orientations even at a fixed mis-
orientation relationship, in contrast to the popular view.
2. Experimental
As depicted in Fig. 1, we used two kinds of nominally
undoped SrTiO3 bicrystals (Crystal GmbH, Berlin) con-
taining a 36.8° [0 0 1] tilt (R5) grain boundary with different
macroscopic grain-boundary plane orientations. One was a
symmetric (3 1 0)1//(3 1 0)2 bicrystal (18.4°/18.4°) and the
other was asymmetric (8.4°/28.4°), where (h k l) is the index
Fig. 1. Plan view of: (a) the symmetric (3 1 0)1//(3 1 0)2 bicrystal (18.4°/
18.4°), and (b) the asymmetric (8.4°/28.4°) bicrystal. The geometrical
notations are explained in the text.
of the grain-boundary plane with respect to the adjoining
grain 1 or 2 and (a1/a2) indicates the smallest angles
between the grain-boundary plane and a principal axis of
the grains adjoining the boundary (i.e., [1 0 0]), as depicted
in Fig. 1. The sum of the two angles, i.e., 36.8°, corresponds
to the misorientation angle. The dimensions of the bicrystal
were 10  5  0.5 mm3. The as-received bicrystals were
measured by X-ray fluorescence, atomic absorption spec-
trometry and inductively coupled plasma-mass spectrome-
try to contain small amounts of Ba (19 ppm), Ca (14 ppm),
Al (10 ppm), K (2 ppm), Na (<2 ppm), Si (<2 ppm) and Fe
(<2 ppm). These symmetric and asymmetric bicrystals were
annealed in air at 1100 °C for 36 h to get the near-equilib-
rium grain-boundary structure. They were heated at a rate
of 10 K min 1, and after annealing, were cooled in the fur-
nace to room temperature.
The impedance measurements were performed in a
dielectric/impedance analyzer (Model Alpha-N, Novocon-
trol, Germany) at 450 °C in air at frequencies between 0.1
and 107 Hz. (Details about the position and the size of the
electrodes for the impedance measurements can be found
elsewhere [10].) For transmission electron microscopy
(TEM), disks of 3 mm in diameter were cut from the
bicrystals. The disks were mechanically polished, dimpled
and finally ion milled to perforation by a Baltec RES010
ion-milling system at an angle of 13° at 3 kV. The high-res-
olution transmission electron microscopy (HRTEM) was
done using the Stuttgart JEOL JEM-ARM1250 at
1.25 MeV (point-to-point resolution: 0.12 nm). Electron
energy-loss spectrometry (EELS) for the local electronic
structure of the grain boundary was done with the Gatan
UHV ENFINA 766 system attached to a VG HB501 UX
dedicated STEM operated at 100 keV (Vacuum Genera-
tors, Inc., UK). During the EELS measurements, an area
of 3  4 nm2 was illuminated, containing either the grain
boundary or bulk area adjacent to the grain boundary.
The energy resolution was about 0.8 eV. Electron energy-
loss spectra were obtained at a dispersion of 0.1 eV per
channel.
3. Results
The HRTEM results performed in the [0 0 1] projection
of the grain boundaries are given in Fig. 2. The symmetric
grain boundary was straight and indexed to be (–1 –3 0)1//
(–1 3 0)2 (henceforth, symmetric (3 1 0)) as shown in Fig.
2a). On the other hand, the asymmetric grain boundary
was faceted into three kinds of facet components: symmet-
ric (3 1 0) and (1 –2 0)1//(–2 1 0)2 (briefly, symmetric (2 1 0))
and asymmetric (0 –1 0)1//(–3 4 0)2 facets (hereafter, asym-
metric (1 0 0)//(4 3 0)) as shown in Fig. 2b. No second phase
was observed in the grain boundaries. The impedance spec-
tra obtained from the grain boundaries examined are pre-
sented in Fig. 3. For the symmetric grain boundary, only
one semicircle ascribed to the impedance of the bulk
appeared. However, for the asymmetric grain boundary,
in addition to the bulk impedance, a semicircle correspond-
 S.B. Lee et al. / Acta Materialia 56 (2008) 4993–4997
Fig. 2. HRTEM images of: (a) the annealed symmetric grain boundary,
and (b) the annealed asymmetric grain boundaries. The asymmetric grain
boundary (b) was faceted into two kinds of symmetric facet components,
(3 1 0) and (2 1 0), and an asymmetric (1 0 0)//(4 3 0) facet component.
ing to the impedance response of the grain boundary
appeared in the lower frequency range, as shown in Fig. 3b.
To explore the correlation between the boundary struc-
ture and its impedance characteristics, we measured by
EELS Ti:O intensity ratios and the crystal-field splitting
in the bulk and at the facets of the asymmetric grain
boundary. Fig. 4a shows EELS spectra from a (1 0 0)//
(4 3 0) facet and from the bulk off the facet. Both Ti L3
and L2 edges are split into eg and t2g peaks by the crys-
tal-field effect [11]. (The concept of crystal-field splitting
will be noted below.) The symmetric (3 1 0) and (2 1 0) facets
and asymmetric facets revealed reduction in crystal-field
splitting by 0.09 ± 0.01 eV (6 data points), 0.06 ± 0.01 eV
(4 points) and 0.1 ± 0.02 eV (5 points), respectively, as
compared with the measured bulk value (2.26 ± 0.01 eV).
(All the errors are standard errors.) Of the three kinds of
facets the Ti:O atomic concentration ratio is the highest
in the asymmetric (1 0 0)//(4 3 0) facet followed by the sym-
metric (2 1 0) facets and the symmetric (3 1 0) facets, as
shown in Fig. 4b. The symmetric (3 1 0) and (2 1 0) facets
showed increases in Ti:O intensity ratio by 2.8% and
4.0% on average, respectively, as compared with the bulk.
4995
Fig. 3. Impedance spectra at 450 °C in air measured from (a) the annealed
symmetric grain boundary (18.4°/18.4°) and (b) the annealed asymmetric
grain boundary (8.4°/28.4°).
On the other hand, the Ti:O ratio at the (1 0 0)//(4 3 0) facets
was increased by about 8.3% as against that in the bulk
(Fig. 4b).
4. Discussion
Grain-boundary faceting, as observed in Fig. 2b, is due
to anisotropy in the grain-boundary energy at a fixed mis-
orientation relationship [12–14]. Singular points, such as
cusps, in the polar plot of the grain-boundary energy versus
grain-boundary plane normal orientation (c-plot) corre-
spond to a singular plane in the equilibrium shape and pro-
duce Herring torque terms [12]. Any local grain-boundary
plane normal orientation which happens to lie between the
cusp orientations will be unstable and be faceted into these
orientations according to a lever rule [12–16]. Grain-
boundary faceting is observed to occur by temperature
decrease [17–19] or composition change [18,20]. Indeed,
asymmetric facet planes ((1 0 0)//(4 3 0)) observed in Fig.
2b can be energetically favorable, even compared with sym-
metric ones, as demonstrated by Merkle and Wolf [21].
The previous results [10,19] suggest that the symmetric
(3 1 0) and asymmetric (1 0 0)//(4 3 0) facet components are
stable at 1100 °C. Since the average plane normal orienta-
tion of the asymmetric grain boundary (8.4°/28.4°) lies
between the symmetric (3 1 0) and asymmetric (1 0 0)//
(4 3 0) facet normal orientations (Fig. 1b), the macroscopic
plane is expected to be faceted into these orientations. The
average grain-boundary plane normal orientation of the
asymmetric grain boundary is nearer to the asymmetric
facet normal orientation ((1 0 0)//(4 3 0)) than to the sym-
4996 S.B. Lee et al. / Acta Materialia 56 (2008) 4993–4997
Fig. 4. (a) EELS spectra from an (1 0 0)//(4 3 0) facet and the bulk off from
the facet of the asymmetric grain boundary showing the Ti–L and O–K
edges. (b) Increase in Ti:O intensity ratios at the symmetric (3 1 0) (10 data
points), asymmetric (1 0 0)//(4 3 0) (8 points) and symmetric (2 1 0) facets (8
points) with respect to the bulk. (The error bar shown is the standard
error.)
metric (3 1 0) one (8.4° vs. 10°, as depicted in Fig. 1b). We
can thus expect that the asymmetric facets have a higher
area fraction. As shown in Fig. 2b, after annealing at
1100 °C, the asymmetric (1 0 0)//(4 3 0) facets apparently
occupied a larger area than the (3 1 0) symmetric facets.
The appearance of the (2 1 0) facets in the asymmetric
grain boundary (8.4°/28.4°) is attributed to our belief that
after diffusion bonding the grain-boundary plane was not
perfectly flat across the whole bicrystal. Parts of the plane
normal orientation of the asymmetric grain boundary
might have larger inclination than nominally expected,
which would make the symmetric (2 1 0) facets appear in
equilibrium. After prolonged annealing at 1100 °C for
more than 36 h, the (2 1 0) symmetric facets are expected
to eventually disappear, as shown in the previous result
[10].
The facets revealed different EELS characteristics. The
mean Ti:O intensity ratio of the asymmetric (1 0 0)//(4 3 0)
facets is the highest, followed by those of the symmetric
(2 1 0) and (3 1 0) facets. However, owing to the small num-
ber of data points the error bars (standard errors of the
mean) in Fig. 4b overlap. In order to judge the statistical
significance, we calculated confidence intervals for the
Ti:O ratio data at the three grain-boundary facets. Com-
paring the (3 1 0) and (1 0 0) facets, these intervals touch
each other at a confidence value of 70%, i.e., there is a
probability of 0.7 that the Ti:O ratios measured at these
two facets are really different. For the (3 1 0) and (2 1 0) fac-
ets this probability is 0.25, and for the (2 1 0) and (1 0 0) fac-
ets 0.5. We interpret these probabilities as a strong
indication that the asymmetric (1 0 0) facets are more oxy-
gen-deficient than the (2 1 0) and (3 1 0) facets.
In the cubic perovskite structure, such as SrTiO3, Ti
atoms are octahedrally coordinated by six oxygen atoms.
Ti L edges arise from electron transitions from the Ti
2p3/2 and Ti 2p1/2 levels to the unoccupied d (and s) states.
Because of the ligand field of the six nearest neighbor oxy-
gen atoms, the unoccupied Ti d levels split into eg and t2g
bands (crystal-field splitting) and thus both the Ti L3 and
L2 edges split into two peaks corresponding to the transi-
tions to eg and t2g bands [11,22]. Due to missing oxygen
atoms, the symmetry in the TiO bonds at the grain bound-
ary will be lost and the electrostatic field imposed onto the
central Ti atom by nearest neighbor oxygen atoms will be
reduced, causing the crystal-field splitting to be decreased.
As noted earlier, though not so different from those at the
symmetric facets, the reduction in crystal-field splitting at
the asymmetric facets was the most significant, well corre-
sponding to the highest degree of oxygen deficiency there.
The O–K edge from a (1 0 0)//(4 3 0) facet in Fig. 4a showed
a slight decrease in intensity of the second peak (indicated
by an arrow) relative to the first peak, as compared with
that from the bulk, which is also a signature of distortion
of the symmetry in the Ti–O bonds, as described by Bryd-
son et al. [22]. Crystal-field splitting can be also affected by
the Jahn–Teller effect, which is a geometrical distortion of a
non-linear molecule with degenerate electronic states, such
as the octahedral TiO6 complex, which removes the degen-
eracy and decreases the energy of the complex. In the pres-
ent study, however, we believe that the main reason for the
geometrical distortion of the octahedral complex is the
oxygen depletion and this depletion is likely to originate
from geometrical constraints in the GB region.
Merkle and Wolf [21,23] suggested that the grain-
boundary planar unit-cell area is correlated with the
grain-boundary energy to some degree, a smaller unit-cell
area generally leading to a shorter repeat unit distance at
the grain boundary on an atomic scale and hence to
grain-boundary energy minima in the c-plot, though scatter
was found. The planar unit-cell area is defined as the
atomic volume divided by the interplanar spacing of the
(h k l) planes of the grains lying perpendicular to the bound-
ary plane normal [21,23]. For SrTiO3, instead of the atomic
volume, the unit-cell volume, a3, is used, where a is the lat-
tice parameter of SrTiO3 (3.905 Å). The planar unit-cell
areas on both sides of the symmetric (3 1 0) facet are
 S.B. Lee et al. / Acta Materialia 56 (2008) 4993–4997
3.16a2 and those of the symmetric (2 1 0) facet 2.24a2. Note
that, for the asymmetric facet, the planar unit-cell area of
(1 0 0) side is a2, but that of (4 3 0) side is 5a2, which repre-
sents the actual unit-cell area of the asymmetric facet.
Because of its more disordered and incoherent structure,
the asymmetric facet is thus expected to accommodate
more oxygen vacancies than the symmetric ones. Oxygen
deficiency (that is, oxygen vacancy formation) at the
boundary facets means that the facets are positively
charged, which form a double-Schottky barrier, and will
block the charge carrier transport across the facets, as sug-
gested previously [4–6,8–10]. Higher degree of oxygen defi-
ciency leads to a higher blocking effect. Thus, the
asymmetric facet is likely to be the most resistive among
the three kinds of facets, which explains why the asymmet-
ric grain boundary containing the asymmetric (1 0 0)//(4 3 0)
facets showed distinct grain-boundary impedance as shown
in Fig. 3.
5. Concluding remarks
We have shown the correlation between the structures of
SrTiO3 R5 ([1 0 0]/36.8°) grain boundaries and their macro-
scopic electrical properties. Different from the symmetric
grain boundary (18.4°/18.4°), the asymmetric grain bound-
ary exhibited clear grain-boundary impedance. As charac-
terized by EELS, of the three kinds of the facets the
asymmetric (1 0 0)//(4 3 0) facet exhibited the highest degree
of oxygen deficiency. This explains the appearance of the
grain-boundary impedance of the asymmetric grain bound-
ary. Our study clearly suggests that the charge carrier
transport characteristics strongly depend on grain-bound-
ary inclination.
Acknowledgements
We thank Mrs. Ute Salzberger for the TEM specimen
preparation. The help at the ARM of Mr. Rainer Höschen
is acknowledged. This work was supported by the Korea
4997
Research Foundation Grant funded by the Korean Gov-
ernment (MOEHRD) (KRF-2007-314-D00107).
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