J O U R N A L O F M AT E R I A L S S C I E N C E L E T T E R S 1 7 ( 1 9 9 8 ) 1 0 6 3 1 0 6 5
Second harmonic generation in BaTiO3 lm crystallized on tellurite
glass surface
K. TANAKA, H. KURODA, A. NARAZAKI, K. HIRAO, N. SOGA
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-01,
Japan
E-mail: ktanaka@collon1.kuic.kyoto-u.ac.jp
Transparent glass-ceramics containing ferroelectric
crystalline phases have been successfully prepared
by many investigators [110]. Non-linear optical
properties and electro-optical properties of those
materials can be utilized for optoelectronic devices
such as an optical switch, an optical shutter,
frequency upconversion, and so forth. Borrelli and
Layton [3] determined quadratic electro-optic coef-
cients of transparent glass-ceramics containing
ferroelectric crystals such as NaNbO3 and LiTaO3 .
They also revealed that a linear electro-optic effect,
i.e., Pockels effect is observed in poled transparent
glass-ceramics providing the size of the crystalline
phase included is at least 0:2 m in size. Kao et al.
[6] prepared transparent glass-ceramics containing
-BaB2 O4 crystalline phase and revealed that the
resultant materials exhibit second harmonic genera-
tion. Ding et al. [7, 8] utilized ultrasonic treatments
to prepare transparent glass-ceramics where crystal-
line thin lms of -BaB2 O4 and LiNbO3 are formed
on the glass surfaces. These glass-ceramic materials
manifested efcient optical second harmonic gen-
eration. Komatsu et al. [9, 10] reported preparation
of transparent tellurite glass-ceramics containing
dielectric crystals such as LiNbO3 and BaTiO3 . In
these glass-ceramics, one can increase the crystallite
size while keeping the material transparent to visible
light, because the refractive index of the tellurite
glass matrix is close to those of LiNbO3 and BaTiO3
crystals. Recently, we reported second harmonic
generation in transparent tellurite glass-ceramic
material where BaTiO3 crystalline phase is precipi-
tated [11]. However, the origin of the second
harmonic generation in this glass-ceramic still
remains unclear. In the present investigation, we
further examine this transparent glass-ceramic to
characterize the BaTiO3 phase and to clarify the
origin of second harmonic generation.
Glass was prepared using reagent-grade BaCO3 ,
TiO2 and TeO2 as starting materials. The raw
materials were weighed to make 15BaO
15TiO2 :70TeO2 (in mol %) composition, and mixed
thoroughly. The mixture was melted in a platinum
crucible at 1000 8C for 40 min in air. The melt was
poured onto a stainless steel plate and cooled in air.
The as-prepared glass was annealed for 30 min at
around the glass transition temperature determined
by means of differential thermal analysis (DTA). The
annealed glass was cut into a plate of about 7 mm 3
7 mm 3 1 mm, and both sides were polished with
0261-8028 # 1998 Kluwer Academic Publishers
CeO2 powders. The resultant glass specimens were
heat-treated at elevated temperatures to fabricate
glass-ceramics. X-ray diffraction analysis with CuK
radiation (Rigaku, RAD-C) was carried out to
ascertain that the as-prepared specimen was amor-
phous and to identify crystalline phases in the heat-
treated specimens.
The second harmonic intensity was measured at
room temperature using the Maker fringe method
[12]. The fundamental wave of a pulsed Nd:YAG
laser (Spectra-Physics, GCR-11) with a wavelength
of 1064 nm was used as incident light. The situation
of polarization was p-excitation and p-detection. The
second harmonic wave generated from the specimen
was detected using a monochromator (SPEX, 270M)
equipped with a photomultiplier (SPEX, 1424M).
The intensity of the second harmonic wave was
determined using a digital oscilloscope (Hewlett
Packard, 54522A). Details of the measurements of
optical second harmonic intensity were described
elsewhere [13].
Fig. 1 shows X-ray diffraction patterns of the
pulverized glass-ceramic specimen (lower gure) and
the surface state of the bulk glass-ceramic specimen
(upper gure) heat-treated at 420 8C for 5 h. These
two patterns are evidently different from each other.
The diffraction line at around 2 31:48 in the
lower diffraction pattern is attributable to BaTiO3 .
Intensity, (arbitrary units)
10 20 30 40 50 60 70
2, (deg)
Figure 1 X-ray diffraction patterns of pulverized specimen (lower)
and surface of bulk specimen of glass-ceramics (upper) with
15BaO:15TiO2 :70TeO2 composition heat-treated at 420 8C for 5 h.
(s) BaTiO3, (4) Ba2 Te3 O8.
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The diffraction lines at around 2 31:4 and 65.38
in the upper diffraction pattern are due to reections
from (1 0 1) or (1 1 0) and (2 0 2) or (2 2 0) planes of
BaTiO3, respectively. On the other hand, the
diffraction lines at around 2 23:5 and 47.88 are
close to those due to (1 0 0) or (0 0 1) and (2 0 0) or
(0 0 2) planes of BaTiO3 , respectively, but the
discrepancy is rather large; the diffraction line at
around 2 23:58 leads to the spacing of lattice
planes d 0:379 nm, whereas d 0:404 and
0.399 nm for the (1 0 0) plane of cubic and
tetragonal BaTiO3 , respectively, and d 0:403 nm
for the (0 0 1) plane of tetragonal BaTiO3 . A
comparison between these two diffraction patterns
in Fig. 1 reveals that BaTiO3 precipitates on the
surface of the glass-ceramic with (1 0 1) or (1 1 0)
plane oriented. Hence, our previous estimation [11]
that lattice planes of BaTiO3 crystals are randomly
oriented is not correct, but the (1 0 1)- or (1 1 0)-
oriented BaTiO3 crystals are present only at the
surface region of the glass-ceramic.
Fig. 2 shows X-ray diffraction patterns of surface
states of glass-ceramic specimens heat-treated at
several temperatures indicated in the gure. The
position, linewidth, and intensity ratio of diffraction
lines are almost independent of the heat treatment
temperature. The spacing of lattice planes for
BaTiO3 precipitated was evaluated from the diffrac-
tion line corresponding to the (1 0 1) or (1 1 0) plane,
and summarized in Table I along with the spacing of
lattice planes for cubic and tetragonal BaTiO3 cited
from the JCPDS cards. The spacing of lattice planes
for BaTiO3 phase precipitated in the transparent
glass-ceramic is rather closer to the spacing of lattice
planes for cubic BaTiO3 than that for tetragonal
phase.
It is known that the cubic phase is present even at
room temperature when the size of BaTiO3 particles
is small. Uchino et al. [14] examined the particle
423 8C
Intensity, (arbitrary units)
420 8C
418 8C
415 8C
10 20 30 40 50 60
2, (deg)
Figure 2 X-ray diffraction patterns of surface of bulk glass-ceramics
with 15BaO:15TiO2 :70TeO2 composition heat-treated at 415, 418,
420, and 423 8C.
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TA B L E I Spacing of lattice planes, d, for (1 0 1) or (1 1 0) plane
of BaTiO3 precipitated in the glass-ceramics derived from
15BaO15TiO2 70TeO2 glass. The spacing of lattice planes for
cubic and tetragonal BaTiO3 cited from JCPDS cards are also given
Heat treatment temperature d
(8C) (nm)
415 0.2848
418 0.2845
420 0.2847
423 0.2855
cubic BaTiO3 (1 1 0) 0.285
tetragonal BaTiO3 (1 0 1) 0.2838
(1 1 0) 0.2825
 Cited from JCPDS cards.
size dependence of crystal structure and Curie
temperature of BaTiO3 particles. They found that a
BaTiO3 particle of 0:12 m is composed of only the
cubic phase even at room temperature. Takeuchi et
al. [15] calculated the volume fraction of cubic
phase in BaTiO3 particles with different diameters
by means of careful X-ray diffraction measurements
at room temperature. They revealed that the fraction
of cubic phase increases monotonically with a
decrease in the average diameter of BaTiO3 particles
and about 5% of BaTiO3 phase still remains as the
cubic phase even when the particle size is 0:5 m.
Lynch and Shelby [16] examined PbTiO3 phases
precipitated in glass-ceramics of the PbO-BaO-
TiO2 -B2 O3 system and revealed that the ratio of
lattice parameters, c=a, deviates from that of pure
PbTiO3 crystal and approaches 1 when the glass
transition temperature of the glass matrix exceeds
the Curie temperature of PbTiO3 , i.e., 490 8C. They
argued that the transition from paraelectric (cubic) to
ferroelectric (tetragonal) phases is hindered by the
glass matrix when the glass transition temperature is
above the Curie temperature because the change in
unit cell dimensions at the Curie temperature
scarcely takes place due to the high viscosity of
the glass matrix at the Curie temperature. This
situation is applicable to the present case. The glass
transition temperatures of not only the 15BaO:
15TiO2 :70TeO2 glass but barium titanium tellurite
glasses with other compositions, which can be a
composition of the glass matrix after the precipita-
tion of BaTiO3 and Ba2 Te3 O8, lie in the region of
340 to 470 8C [10], which is higher than the Curie
temperature of BaTiO3 , i.e., 120 8C. In addition, it
was suggested that internal stresses arise in sintered
BaTiO3 ceramics composed of ne grains of 1 m
or less and are apt to force the grains toward the
cubic phases [17, 18]. We anticipate that such an
internal stress arises at the interface between BaTiO3
grains and glass matrix in the present glass-ceramic
material and makes the cubic phase stable even at
room temperature.
Based on the above-mentioned previous studies
70 concerning the stability of paraelectric (cubic) phase
below the Curie temperature, it is not unreasonable
that cubic BaTiO3 phases are present in the trans-
parent glass-ceramic derived from the 15BaO:
15TiO2 :70TeO2 glass. Nonetheless, these specimens
exhibit second harmonic generation. Fig. 3 shows the
dependence of second harmonic intensity on angle of
incidence for the transparent glass-ceramics heat-
treated at several temperatures indicated in the
gure. It should be noted that the X-ray diffraction
lines due to BaTiO3 disappeared when the surfaces
of the glass-ceramic specimens were mechanically
etched, and the second harmonic generation was not
observed for specimens after etching. Hence, it is
obvious that the second harmonic wave is generated
from the BaTiO3 phase. We suppose that a small
tetragonal deviation from cubic structure of the
BaTiO3 crystals precipitated on the surface of glass-
ceramics contributes to the second harmonic gen-
eration [19, 20]. Fig. 3 also indicates that the
variation of second harmonic intensity with angle
of incidence depends on the heat treatment tem-
perature. The reason for such a phenomenon is
unclear at this moment, but it may be ascribed to the
difference in microstructure of BaTiO3 lm. Further
investigation is in progress to analyse the angle of
incidence dependence of the second harmonic
intensity.
Second harmonic intenstiy, (arbitrary units)
250
Angle of incidence, (deg)
Figure 3 Dependence of optical second harmonic intensity on angle of
incidence for the transparent glass-ceramics derived from the
15BaO:15TiO2 :70TeO2 glass. The heat treatment temperatures are
indicated in the gure.
Acknowledgments
The authors would like to thank Professor T.
Kokubo, Graduate School of Engineering, Kyoto
University, for X-ray diffraction measurements. The
authors are also indebted to Professor T. Komatsu,
Nagaoka University of Technology, and Professor T.
Yoko, Institute for Chemical Research, Kyoto Uni-
versity, for suggestions on many aspects of the
present work.
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Received 23 December 1997
and accepted 1 May 1998
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