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S. B. Lee et al.: Dynamic observation of nanometer-sized island on SrTiO3
Sung Bo Lee, Mitsuhiro Saito, Fritz Phillipp
Max-Planck-Institut für Metallforschung, Stuttgart, Germany
Dynamic observation of nanometer-sized island
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formation on the SrTiO3(001) and (011) surfaces
by in situ high-resolution transmission electron
microscopy
Using in situ high-resolution transmission electron micros-
copy (HRTEM), we examine the formation and time evolu-
tion of the TiO islands on the SrTiO3(001) and (011) sur-
faces at 970 °C. Titanium monoxide (TiO) islands are
observed to form mainly on the SrTiO3(001) surface but
rarely on the (011) surface, which indicates an interface en-
ergy anisotropy with interface plane orientations.
Keywords: In situ high-resolution electron microscopy
(HRTEM); Annealing; Strontium titanate surface; Titanium
monoxide island
1. Introduction
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Recently, it has been reported that new phases appear on the
SrTiO3 (STO) (001) surface during annealing in oxidizing
or reducing atmospheres [1 – 6]. SrO is observed to appear
on the surface during annealing in oxidizing atmospheres
[1 – 4]. Under reducing conditions, Ti-rich phases (TiO and
Ti2O [3, 4], and Ti2O3 [5]) can form on and near the surface
[3 – 6]. However, the previous observations reveal their lim-
© 2005 Carl Hanser Verlag, Munich, Germany
itations in that they did not present observations of atomic-
ally-resolved structures of islands and island/STO inter-
faces. This is because in the previous reports islands were
observed in plan-view and ex situ after annealing by surface
topographical methods such as scanning tunneling micros-
copy (STM) or atomic force microscopy (AFM). To over-
come these limitations, recently, using in situ high-resolu-
tion transmission electron microscopy (HRTEM), Lee et
al. [7] investigated the edge surface of the TEM specimens
at a temperature of 970 °C by profile imaging in cross sec-
tion. They found that the edge surface is faceted into
{001} and {011} facet components and islands, identified
as TiO, form on the {001} surface facet. Through the in situ
HRTEM observation in cross-section, the exact surface
morphology of the islands and the interface between the is-
lands and the STO substrate were well characterized. In ad-
dition, we recently observed rare, but clear observations of
TiO island formation on the {011} surface facets. In the
present study we address and discuss why the TiO islands
form rarely on the STO(011) surface as compared with the
(001).
452
2. Experimental
As a raw material a single crystal STO wafer of 15 ×
10 × 2 mm3 (99.99 wt.% pure, small amounts (< 100 ppm)
of Ca, Ba, Cu, Ni, and Fe; Crystal GmbH, Berlin, Germany)
with a well-defined (± 0.1°) (100) orientation was used.
From the single crystal, 3 mm disks were cut, dimpled and
ion-milled for TEM specimens. In situ HRTEM observation
was made at a high temperature of 970 °C by the Stuttgart
JEOL JEM-ARM1250 operated at 1250 kV (0.12 nm
point-to-point resolution) equipped with a side-entry heat-
ing stage [8]. The base pressure in the specimen chamber
was 1.4–2 × 10 – 6 Pa. The specimens were tilted to the
[100] zone axis for HRTEM. Lattice parameter was
measured using the image processing technique package
LADIA (Lattice Distortion Analysis) [9]. Computer simu-
lations of the experimental high-resolution images were
performed with the EMS software package [10] and the
idim software package [11].
3. Results
Figure 1a shows a typical high-resolution microstructure
showing an island forming on the STO (001) surface which
was annealed for 140 min at 970 °C. The island exhibits a
distinct faceted shape composed of the {001} and {011}
surface facets. The spacing between two nearest dots of
the island is measured to be 2.07 Å ± 0.02 Å, which can be
explained by TiO out of many Ti and Sr oxides [12 – 14]. Ti-
tanium monoxide, TiO, has NaCl structure with a lattice
parameter of 4.18 Å [12, 14], which is about twice the
measured spacing of 2.07 Å. (For clarity, unit cell squares
are inserted on both the STO and the island, as exhibited
in Fig. 1a.) Thus the following orientation relationship is
found: (001)STO//(001)TiO. An interfacial dislocation was
observed, as indicated by a white arrow in Fig. 1a [7]. Fig-
ure 1b shows the high-resolution image of the same island
as shown in Fig. 1a after annealing for 228 min, exhibiting
a clear surface faceting. The interfacial dislocation is still
present at the interface between the STO and the island.
Using the idim software package [11] we performed a quan-
titative comparison of calculated images with the experi-
mental image of the island (Fig. 1b). From this we obtained
a best fit with a defocus value of – 31.6 nm (underfocus)
 Carl Hanser Verlag, München Z. Metallkd. 96 (2005) 5
Not for use in internet or intranet sites. Not for electronic distribution.
S. B. Lee et al.: Dynamic observation of nanometer-sized island on SrTiO3
(a)
(b)
Fig. 1. High-resolution images of (a) a TiO island formed on the
STO(001) surface after annealing (a) for 140 min and (b) for 228 min
at 970 °C. An extra lattice plane ending at the interface is indicated
by a white arrow (a, b). The inset in (b) is a simulation image (Df =
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– 31.6 nm, t = 1.3 nm).
and a specimen thickness of 1.3 nm (cross-correlation func-
tion (XCF) = 0.94). The simulation image is shown in the
inset of Fig. 1b. At variance with the frequent observations
of the islands on the (001) surface, only few islands appear
on the (011) surface, revealing an orientation relationship
of (011)STO//(011)TiO, as shown in Fig. 2. Also in this case,
© 2005 Carl Hanser Verlag, Munich, Germany
the island is polyhedral.
4. Discussion
The faceted shape of the TiO islands can be regarded as an
equilibrium shape because the faceted shape is maintained
even during their slow shrinkage [7], as clearly shown by
the island in Fig. 1b. Such faceted shape indicates a strong
surface energy anisotropy of the TiO island. The presence
of the interface dislocation shown in Fig. 1a is of course
due to the misfit between the STO lattice and the island lat-
tice. The lattice parameter of the STO is 3.905 Å and the
measured lattice parameter of the TiO is 4.14 Å, which re-
presents ~ 6 % compressive misfit strain for the TiO island
on the STO. The simulation image in Fig. 1b (inset) con-
firms that the experimental image contrast of the island
agrees with TiO.
Figure 2 shows the rare observation of the island forma-
tion on the STO(011) surface. The observed anisotropy in
the island formation between the (001) and (011) surfaces
is interpreted as arising from the interface energy anisotro-
Z. Metallkd. 96 (2005) 5
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Fig. 2. A high-resolution image of an island formed on the STO(011)
surface after annealing for 206 min at 970 °C.
py with respect to interface plane orientations (inclina-
tions). The island formation is explained in terms of Schott-
ky equilibrium according to the oxygen partial pressure in
the atmosphere [7]. Thus another possibility is that the
overall sublimation depends on the surface normal orienta-
tion and such an orientation dependence would explain the
observed anisotropy in the island formation.
The sublimation rate of each element (Sr, Ti, or O) during
annealing in vacuum (in the TEM) at 970 °C may be
strongly orientation-dependent. (That is, each element may
show a different sublimation rate according to surface nor-
mal orientations.) If so, islands on the (011) surface would
have a stoichiometry different from TiO observed on the
(001) surface. However, this is not the case, leading us to
the conclusion that the sublimation rate of each element is
not critically anisotropic.
So far no theoretical predictions have clarified the ther-
modynamic stability of TiO on STO in vacuum at such high
temperature and the interface energy between STO and TiO
or its anisotropy with respect to interface inclinations.
Therefore, the present experimental study motivates calcu-
lations of the interface energies with the changes of inter-
face inclinations and surface terminations of STO and TiO
sides adjoining the interface, and further, a theoretical ap-
proach for the thermodynamic stability of TiO on STO.
The help of Mr. Rainer Höschen at the ARM is appreciated.
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S. B. Lee et al.: Dynamic observation of nanometer-sized island on SrTiO3

[11] G. Möbus, M. Rühle: Ultramicroscopy 56 (1994) 54. Correspondence address

[12] R.W.G. Wyckoff: Crystal Structures, Vol. I, John Wiley & Sons,
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[14] W. Pies, A. Weiss, in: K.-H. Hellwege, A.M. Hellwege (Eds.),
Not for use in internet or intranet sites. Not for electronic distribution.
Sung Bo Lee, Research Professor
Department of Ceramic Engineering & Research Institute
of Information Display, Hanyang University
17 Haengdang-dong, Seongdong-gu, Seoul 133-791, South Korea
Tel.: +82 2 2220 0384

Landolt-Börnstein: Numerical Data and Functional Relationships Fax: +82 2 2220 1838
in Science and Technology, Vol. 7, Pt. b, Springer-Verlag, Berlin E-mail: bolee@hanyang.ac.kr
(1975).

(Received November 22, 2004; accepted February 14, 2005)

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454 Z. Metallkd. 96 (2005) 5