JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2007; 38: 142146

Published online 4 October 2006 in Wiley InterScience
(www.interscience.wiley.com) DOI: 10.1002/jrs.1600

Effect of lanthanum substitution on the Raman spectra

of barium titanate thin films
P. S. Dobal, A. Dixit and R. S. Katiyar
Department of Physics, University of Puerto Rico, San Juan, PR 00931-3343, USA

Received 24 February 2006; Accepted 17 June 2006

Thin films of Ba1x Lax TiO3 on platinum substrates were synthesized using the solgel method for x values
of 0.0, 0.03, 0.05, and 0.10, and the effect of trivalent La3+ substitution on the structural and dielectric
properties was studied. Using X-ray diffraction, structural analysis of these compositions revealed a slight
increase in the tetragonal distortion of the unit cell with increase in La content. Accordingly, an increase
in the tetragonal to cubic transition temperature TT/C was detected by temperature-dependent Raman
spectroscopy in the range of 70500 K. Unlike the results from Raman scattering for the La-doped BaTiO3
films, the dielectric measurements showed broad and diffused dielectric maxima, making the estimation
of the transition temperature merely qualitative. Copyright 2006 John Wiley & Sons, Ltd.

KEYWORDS: Barium titanate thin films; lanthanum substitution; solgel method; phase transition; perovskite

INTRODUCTION that alter the crystal symmetry at submicron level and to

The perovskite family consists of many titanates used
in a variety of electroceramic thin film applications.1
Among these, barium titanate BaTiO3 (BTO) has become
a very important material with widespread use in the
electronic industry owing to its high dielectric constant and
piezoelectric, electrostrictive, and ferroelectric properties.2 5
Most of the useful properties of BTO can be improved
and tailored by modifying its stoichiometry. This can be
achieved by incorporating appropriate dopants in its lattice,
which is possible because of the intrinsic capability of
the perovskite structure to host ions of different sizes.
Numerous studies have been attempted to establish a
relationship between the doping concentration and the
static/dynamic properties of the resulting composition.6 9
However, an exact correlation is difficult to establish, since
the electrical properties of doped compositions depend
on various process-dependent parameters, such as the
substitution sites, charge compensating defects, vacancies
or defect pairs, etc. On the other hand, the average structural
properties of such compositions do not necessarily depend
on all these parameters.
As a novel nondestructive technique, Raman spec-
troscopy has extensively been used to study the structural
properties of a wide variety of materials. It has been of major
interest owing to its ability to detect any structural changes
Correspondence
to: R. S. Katiyar, Department of Physics,
University of Puerto Rico, P.O. Box 23343, San Juan, Puerto Rico
00931-3343, USA. E-mail: rkatiyar@upracd.upr.clu.edu
provide an estimation of the factors responsible for such
structural changes. The ABO3 type perovskite family is one
of the classes of materials in which Raman spectroscopy has
been very useful in elucidating the phase transitions,10 15
as well as to study other aspects like substitution,11 16
stress/strain,17,18 size effect,18 20 etc. In this study, La3C was
incorporated on Ba2C sites of the perovskite BTO lattice
to produce Ba1
x Lax TiO3 (BLT) compositions. Results from
temperature-dependent Raman spectroscopy of these com-
positions are discussed.
EXPERIMENTAL
Thin films of BLT for x values of 0.0, 0.03, 0.05, and 0.10 were
prepared by the solgel technique on platinum substrates.
Barium acetate, lanthanum 2-methoxyethaoxide, and Ti-
isopropoxide were used as precursor materials. For initial
crystallization and removal of organics, each coating was
dried at 600 C for 5 min. The coating and firing sequence
was repeated several times to obtain the desired thickness.
Finally, the films were annealed at 1000 C for 2 h in air.
Cu K radiation of 1.5405 A was employed for recording
the X-ray diffraction patterns in the resulting films using a
Siemens D5000 X-ray diffractometer.
Raman spectra of BLT films were recorded using a triple
spectrometer, T64000 from JY Horiba. An optical microscope
with 80 objective was used to focus the 514.5-nm radiation
from a Coherent Innova 99 ArC laser on the sample surface,
over a circular area less than 2 m in diameter. The same

Copyright 2006 John Wiley & Sons, Ltd.

 Effect of lanthanum substitution on the Raman spectra of barium titanate thin films 143

microscope objective was used to collect the backscattered

radiation. The scattered light dispersed by the spectrometer
was detected by a charge-coupled device (CCD). With a
25 mm CCD and 1800 grooves/mm grating, the spectral
resolution was typically less than 1 cm
1 . A microscope-
compatible thermal stage from MMR Technology was used
while recording the temperature-dependent Raman spectra
in the range 70500 K.

RESULTS AND DISCUSSION

Structural determination by X-ray diffraction
X-ray diffraction (XRD) patterns of BLT films with La content
x D 0.0, 0.03, 0.05, and 0.10 are shown in Fig. 1(a). The
inset shows the splitting of 001 and 100 reflections in
these compositions. The diffraction pattern obtained from
powdered BTO (x D 0.0) is also presented by dotted
curve. The comparison of powder and film XRD patterns
clearly indicates that the films were entirely crystallized into
perovskite structures. Except the substrate Pt peaks at about
39.8 and 46.2 degree 2
values, no other impurity/constituent
phases were detected. The splitting of diffraction peaks in
all BLT compositions confirmed the tetragonal structure of
the films. Compared with the films, splitting was more
clearly observed for the stress-free powder samples. The
lattice parameters obtained from the powder and thin film
compositions, however, showed the same trend of a marginal
increase in the tetragonal distortion (c/a ratio) with increase
in La content (Fig. 1(b)). Considering the radii of La3C ,
Ba2C , and Ti4C ions, 1.36, 1.44, and 0.74 A0 , respectively,
substitution of Ba2C by La3C was expected to occur more
on the A-sites of the BTO. Therefore, the similar crystal Figure 1. (a) X-ray diffraction patterns of BLT films with La
structure of undoped and lanthanum-doped barium titanate content x D 0.0, 0.03, 0.05, and 0.10. Inset shows the splitting
was attributed to the low concentration of the dopant on the of 001 and 100 reflections, (b) variation in tetragonal distortion
A-sites of the BTO lattice. at different La concentrations in BLT.

Raman scattering from BLT films
BTO is a well-known classic ferroelectric material that is
cubic above 393408 K and belongs to the space group
Pm3m (O1h ). At temperatures below 393 K, it is ferroelectric
with a P4mm (C14v ) structure, which further transforms
to orthorhombic and rhombohedral structures at 278 and
183 K, respectively.21 Optical modes of cubic phase of
BTO transform according to the 3F1u C 1F2u irreducible
representation. The F1u modes are infrared-active and the
F2u mode is the so called silent mode since it is neither
infrared- nor Raman-active.22 Each triply degenerate F1u
mode splits into A1 C E phonons in the tetragonal phase
whereas F2u splits into an E C B1 mode. These modes further
split into longitudinal (LO) and transverse (TO) components
because of the long-range electrostatic forces associated with
lattice ionicity.22 24 The E C B1 modes derived from the cubic
F2u mode are essentially degenerate. For other modes of
tetragonal phase, the assignment of phonons as LO or TO
is valid as long as the phonon wave vector lies along one
of the principal symmetry directions of the crystal. For the
phonons propagating in between the principal axes, mixing
of the A1 and E modes occurs and quasi modes appear in the
spectra.25
Room temperature-measured Raman spectra of BLT films
are displayed in Fig. 2. The top dotted curve is the Raman
spectrum of the BaTiO3 x D 0.0 powder sample. The
spectra of x D 0.0 compositions, obtained from both powder
and thin film, contain one overdamped E1 (TO) mode and
other E1 and A1 modes. Accurate assignment of these peaks
required the phonons to be propagating along a principal
axis. For oblique angles, phonon dispersion made it difficult
to isolate different E(TO) modes from the corresponding
A1 (TO) modes.25 Since our BLT films did not reflect any
preferential growth direction in their X-ray reflections, an
approximate assignment was done. The coupling of a sharp
A1 TO1  mode at about 180 cm
1 with a broad A1 TO2  mode
at about 267 cm
1 resulted25,26 in an anti-resonance effect at
about 180 cm
1 . A third asymmetric A1 TO3  mode appeared

Copyright 2006 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2007; 38: 142146
DOI: 10.1002/jrs
144 P. S. Dobal, A. Dixit and R. S. Katiyar
at about 525 cm
1 . The E(TO) mode that has been associated
with the tetragonalcubic phase transition27 was observed at
about 306 cm
1 . The A1 LO3  mode, which appeared at about
727 cm
1 in tetragonal BTO for phonons propagating along
c-axis, transformed to the 715 cm
1 ELO3  mode for phonons
propagating in ab plane. Owing to the polycrystalline nature
of our films, the mode around 715 cm
1 in BTO was assigned
as ELO3  mode. All of the features observed in the tetragonal
phase have been reported and discussed in the literature.23 27
Because of the random orientations of grains in the film,
the directions of the phonon wave vectors were randomly
distributed with respect to the crystallographic axes. As a
result, the Raman peaks resulting from the mode mixing and
long-range electrostatic force effects were broader than those
reported for BTO single crystals. Also, the wavenumbers of
the ETO2  modes in BTO films were found to be slightly
lower compared to bulk BTO, indicating stresses in the
films.28 Such stresses in thin films could originate from
differences in lattice parameters and thermal expansion
coefficients of the film and substrate material. However,
because of their similar thickness (400 nm) the stress/size
effects in BLT films were ignored.
Raman spectra produced from La-substituted BTO did
not show any remarkable shift of the anti-resonance effect at
about 180 cm
1 because of the similar masses of La and Ba
ions. However, the coupling between the sharp A1 TO1  and
broad A1 TO2  modes weakened as the intensity of A1 TO2 
mode decreased with increase in La content. All other Raman
modes also weaken and broaden with increase in La content
in BLT (Fig. 2). The breakdown of long-range order can
allow off-Brillioun-zone-center (k 6D 0) phonons and lead to
a change in the spectral distribution of the Raman modes.
Figure 2. Room temperature Raman spectra of the BLT films.
The dotted curve is the Raman spectrum of x D 0.00 powder
sample. Inset shows the energy and half-width variation of the
ETO1  mode.
Copyright 2006 John Wiley & Sons, Ltd.
However, no extra Raman lines were observed for any of the
BLT films in this study. The ETO1  mode, which appeared as
a small hump at about 40 cm
1 in the spectra of x D 0.0, 0.03,
and 0.05 composition films, was downshifted and broadened
in the spectrum of x D 0.10 composition film. The energy
and half-width variation for this mode is shown in the inset
of Fig. 2, after fitting the Raman data with damped harmonic
oscillator type phonon functions. The 267 cm
1 mode, which
was found to be most sensitive to the lattice distortion,
showed a small decrease in its energy. Other modes also
displayed a marginal change in their wavenumbers with
increase in La content.
To understand the phase transition behavior of BLT
films, Raman spectra were recorded in the temperature
range 70500 K with an interval of 1020 K. The depolarized
Raman spectra of BLT films at 70 K are shown in Fig. 3. The
disappearance of the overdamped E1 (TO) mode as well as
the strong appearance of the ETO3  mode at about 485 cm
1
in these compositions clearly indicate a different phase at
70 K. The appearance of extra bands at about 640 cm
1 was
interpreted as being caused by the distortions of TiOTi
bonds in the low-temperature phase.
Raman spectra recorded in the rhombohedral phase of
BTO film (below 200 K) could not be distinguished from those
in the orthorhombic phase (200290 K). The disappearance
of the 306 cm
1 E(TO) mode clearly suggested a tetragonal
to cubic phase transition at about 410 K. Two very broad
bands centered at about 288 and 516 cm
1 characterized the
cubic paraelectric phase. The ETO3  mode, which appeared
at 485 cm
1 in the 70-K Raman spectra (Fig. 3), was found to
lose its intensity with increase in temperature. Earlier studies
have revealed that the observation of this mode depends
on the excitation geometries utilized.23 26 Therefore, the
appearance of the 485 cm
1 ETO3  mode in the 70-K Raman
Figure 3. Depolarized Raman spectra of BLT films recorded at
70 K.
J. Raman Spectrosc. 2007; 38: 142146
DOI: 10.1002/jrs
 Effect of lanthanum substitution on the Raman spectra of barium titanate thin films
spectra could have been due to lattice orientations in the films
that allowed this mode in backscattering geometry. With
increase in temperature, as the material rearranged itself,
this mode lost its intensity and disappeared in the phase,
which appeared above 390 K. Since this mode disappeared
at 390 K in BTO Raman spectra, which is the orthorhombic to
tetragonal transition temperature of BTO, the disappearance
temperature was termed as TO/T . Similarly, the notation
TT/C was used to represent the tetragonal to cubic transition
temperature.
Like BTO, Raman spectra recorded in the rhombohedral
phases of BLT films could not be distinguished from those
in the orthorhombic phases. However, an increase in the
orthorhombic to tetragonal transition temperature (TO/T ),
as well as a marginal increase in the tetragonal to cubic
transition temperature (TT/C ), was observed with increase in
La content. The tetragonal to cubic transformation in these
films was observed at about 410, 420, 430, and 440 K for
x D 0.00, 0.03, 0.05, and 0.10 compositions, respectively.
The transition temperature variation with La content in BLT
is plotted in Fig. 4. This increase is in line with the XRD
observations of marginal increase in the c/a ratio with La
addition in BTO. Similar results of increasing TT/C have been
observed for Pb2C substitution at Ba sites of BTO.3
The 267 cm
1 mode has been found to display a dis-
continuous behavior at the phase transition temperatures in
BTO crystals.10 The temperature variation of the wavenum-
ber of this mode is plotted in Fig. 5 after fitting the Raman
data to phonon functions corrected for the temperature fac-
tor. The bottommost data is the measured energy of this
mode, while all other data points for undoped as well as
La-doped compositions are the phonon wavenumbers fitted
to the Raman data. The discontinuity in both the measured
as well as in the fitted energy values clearly indicated the
Figure 4. Variation of orthorhombic to tetragonal (TO/T ) and
tetragonal to cubic transition temperature (TT/C ) with La
content.
Copyright 2006 John Wiley & Sons, Ltd.
145
phase transition temperatures TO/T and TT/C for each com-
position. All the transition temperatures obtained from the
267 cm
1 mode behavior were in good agreement with those
derived from the disappearance of the 306 cm
1 E(TO) and
485 cm
1 ETO3  modes.
Dielectric properties
The phase transition behavior of BLT thin films was also
studied from the temperature-dependent dielectric constant.
Temperature variation of the dielectric constant for BLT
films, which was measured at 100 KHz, is shown in Fig. 6.
The undoped BaTiO3 x D 0.0 showed three distinct phase
transitions as reported in the literature.29,30 A dielectric maxi-
mum max of 543 at about 410 K characterized the tetragonal
to cubic transition TT/C . The orthorhombic to tetragonal tran-
sition TO/T appeared as a small hump at about 310 K and
the rhombohedral to orthorhombic phase transition TR/O
was observed at 218 K. However, with increase in La con-
tent in the films, the transition temperatures TR/O , TO/T ,
and TT/C could not be isolated and a very broad dielectric
response was observed for x D 0.10 BLT film. Morrison and
coworkers31 33 have extensively studied the electric prop-
erties of BLT films and observed a systematic variation of
sharp dielectric peaks with La substitution. It is therefore
very unlikely that La-doping caused the broadening of the
dielectric peaks in the BLT films. Such broadening might
be associated with electrically active surface/grain bound-
ary defects, which are Raman inactive but contribute to the
broadening and smearing of dielectric peaks.34,35
CONCLUSIONS
Raman spectroscopy was utilized to study the effect of
trivalent La3C substitution on the structural properties of
Figure 5. Variation of the energy of the 267 cm
1 mode with
temperature. Squares show the measured energy whereas the
open circles represent the fitted wavenumber.
J. Raman Spectrosc. 2007; 38: 142146
DOI: 10.1002/jrs
146 P. S. Dobal, A. Dixit and R. S. Katiyar

5. Setter N, Cross LE. J. Appl. Phys. 1980; 51: 4356.

6. Yu Z, Ang C, Guo R, Bhalla AS. Appl. Phys. Lett. 2002; 81: 1285.
7. Samara GA. J. Phys.: Condens. Matter 2003; 15: R367.
8. Chen MS, Shen ZX, Tang SH, Shi WS, Cui DF, Chen ZH. J. Phys.:
Condens. Matter 2000; 12: 7013.
9. Pontes FM. J. Appl. Phys. 2002; 91: 5972.
10. Perry CH, Hall DB. Phys. Rev. Lett. 1965; 15: 700.
11. Dobal PS, Katiyar RS. J. Raman Spectrosc. 2002; 33: 405.
12. Kojima S, Ikeuchi Y, Zhunchang H, Qingrui Y. Jpn. J. Appl. Phys.
1996; 35: 5192.
13. Kojima S. J. Phys.: Condens. Matter 1998; 10: L327.
14. Dobal PS, Dixit A, Katiyar RS, Bhalla AS. Proc. SPIE 2001; 4333:
111.
15. Dixit A, Majumder SB, Dobal PS, Katiyar RS, Bhalla AS. Thin
Solid Films 2004; 447448: 284.
16. Aparna M, Bhimasankaram T, Suryanatrayan SV, Prasad G,
Kumar GS. Bull. Mater. Sci. 2001; 24: 497.
17. Dobal PS, Bhaskar S, Majumder SB, Katiyar RS. J. Appl. Phys.
1999; 86: 828.
Figure 6. Temperature variation of the dielectric constant of 18. Park Y, Cho K, Kim HG. J. Am. Ceram. Soc. 1998; 81: 1893.
BLT films measured at 100 kHz. 19. Schlag S, Eicke HF. Solid State Commun. 1994; 91: 883.
20. Ahmad T, Kavitha G, Narayan C, Ganguli AK. J. Mater. Res.
2005; 20: 1415.
BTO thin films. Structural analysis of the films using X ray 21. Jaffe B, Cook W, Jaffe H. Piezoelectric Ceramics. Academic Press:
revealed a slight increase in the tetragonal distortion of the London, 1971.
unit cell with increase in La content. Accordingly, an increase 22. Loudon R. Adv. Phys. 1964; 13: 423.
23. Pinczuk A, Taylor W, Burstein E. Solid State Commun. 1967; 5:
in the ferroelectric transition temperature Tc was detected by
429.
temperature-dependent Raman spectroscopy. Temperature- 24. Domenico MD Jr, Wemple SH, Porto SPS, Buman RP. Phys. Rev.
dependent dielectric measurements were performed to 1968; 174: 522.
verify the phase transitions observed in Raman scattering. 25. Scalabrin A, Chaves AS, Shim DS, Porto SPS. Phys. Status Solidi
Unlike Raman scattering, the La-doped BTO films showed a B 1977; 79: 731.
26. Chaves A, Katiyar RS, Porto SPS. Phys. Rev. B 1974; 10: 3522.
broad dielectric response, making estimation of the transition
27. Begg BD, Finnie KS, Vance ER. J. Am. Ceram. Soc. 1996; 79: 2666.
temperature difficult. 28. Rossetti GA Jr, Cross LE, Kushida K. Appl. Phys. Lett. 1991; 59:
2524.
Acknowledgements 29. Yu Z, Guo R, Bhalla AS. J. Appl. Phys. 2000; 88: 410.
This work was supported in part by the NSF-INT-0097018 and 30. Hennings D, Schnell H, Simon G. J. Am. Ceram. Soc. 1982; 65: 539.
NASA-NCC3-1034 grants. 31. Morrison FD, Sinclair DC, West RA. J. Appl. Phys. 1999; 86: 6355.
32. West RA, Adams TB, Morrison FD, Sinclair DC. J. Eur. Ceram.
Soc. 2004; 24: 1439.
REFERENCES 33. Morrison FD, Coats AM, Sinclair DC, West RA. J. Electroceramics
1. Smolenskii GA. Ferroelectric and Related Materials. Gordan and 2001; 6: 2139.
Breach Science Publishers: London, 1993. 34. Bratkovsky AM, Levanyuk AP. Phys. Rev. Lett. 2005; 94: 107 601.
2. Ramesh R, Aggrawal S, Auciello O. Mater. Sci. Eng. 2001; 32: 191. 35. Lookman A, Bowman RA, Gregg JM, Kut J, Rios S, Dawber M,
3. Jona F, Shirane G. Ferroelectric Crystals. Pergamon: New York, Ruediger A, Scott JF. J. Appl. Phys. 2004; 96: 555.
1962.
4. Cross LE. Ferroelectrics 1987; 76: 241.

Copyright 2006 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2007; 38: 142146
DOI: 10.1002/jrs