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Vibrational Spectroscopy 46 (2008) 100–106

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Raman spectroscopic characterization of RECa4O(BO3)3

(RE = La and Gd) crystals
G. Barros a, E.N. Silva a, A.P. Ayala a, I. Guedes a,*, C.-K. Loong b,
J. Wang c, X. Hu c, H. Zhang c
a
Departamento de Fı́sica, Universidade Federal do Ceará, Campus do Pici, CP 6030, Fortaleza CE 60455-760, Brazil
b
Intense Pulsed Neutron Source Division, Argonne National Laboratory, Argonne, IL 60439-4845, USA
c
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
Received 2 October 2007; accepted 5 November 2007
Available online 12 November 2007

Abstract
The phonon modes of the rare-earth calcium oxyborates [RECa4O(BO3)3, RE = La and Gd] were determined at room-temperature using Raman
scattering technique. The observed frequencies were assigned on the basis of the borate (BO3) vibrations and correlations with previous data
reported for other similar compounds. The influence of the RE ion substitution on the phonon distribution is discussed. Two main features were
observed when La3+ replaces for Gd3+: the frequency of most of the phonons shifts downwards and the frequency difference between the
components of the n1(BO3) doublet decreases. All these features result from the monoclinic lattice expansion.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Raman scattering; Nonlinear crystals; RECOB

1. Introduction [12]. The Raman and IR phonons of the GdCOB were also
reported by Maczka et al. [13]. They observed a significant LO–
The search for new nonlinear optical materials has led to the TO splitting of some modes, and based on the lattice dynamics
development of the rare-earth calcium oxyborate crystals model, they revised the mode assignment proposed in Ref. [11].
[RECa4O(BO3)3, hereafter RECOB] [1,2]. Good quality The Raman spectra of the Er3+:Yb3+:GdCOB, Nd3+:Yb3+:Gd-
crystals exhibiting a large transmission window, high damage COB and Er3+:Yb3+:YCOB have been reported in Refs. [7–9],
threshold and non-hygroscopicity can be grown by using the respectively. No appreciable changes in the phonon frequencies
Czochralski method [3]. At room-temperature RECOB have a were observed owing to the small difference in the interatomic
monoclinic structure belonging to the space group Cm (Cs3 ) distances upon replacing the RE3+ ion.
with two formula units per unit cell (Z = 2). Efficient second- The growth and the characterization of the LaCOB crystal
and third-harmonic generation has been reported for have been reported for several authors [14–19]. For instance,
YCa4O(BO3)3 (YCOB) and GdCa4O(BO3)3 (GdCOB) [4,5]. Jiang et al. [14] investigated its optical transmission window,
Spectroscopic studies of the isostructural RE-doped RECOB linear refractive indexes, specific heat and thermal expansion
[RE: RECOB] have also been reported [6–10]. coefficients. Shimizu et al. [17] investigated its room-
Raman and Infrared (IR) spectroscopies have been used to temperature dielectric, elastic and piezoelectric constants,
obtain the vibrational spectrum of several doped and pure and Adams et al. [19] characterized its nonlinear performance
RECOB crystals. For instance, Lorriaux-Rubbens et al. [11] as an efficient second-harmonic generator at 532 nm. Some of
reported the Raman phonons of GdCOB, YCOB and EuCOB. the optical properties of the RE:LaCOB are reported in Refs.
The Raman phonons of the SmCOB were reported by Xia et al. [20,21]. However, no information on the phonon spectrum of
the LaCOB is available yet. Therefore, in this work, we use
Raman spectroscopy to obtain the room-temperature phonon
* Corresponding author. Tel.: +55 85 3366 9920. spectra of the LaCOB. The mode assignment was given in
E-mail address: [email protected] (I. Guedes). correlation with previous works. We also recorded the Raman
0924-2031/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.vibspec.2007.11.002
 G. Barros et al. / Vibrational Spectroscopy 46 (2008) 100–106 101

spectrum of the GdCOB to investigate the effect of replacing Table 1

Summary of GdCOB and LaCOB technical specifications
Gd for La in the phonon distribution.
LaCOB GdCOB
2. Experimental Cristal structure Monoclinic, Monoclinic,
biaxial crystal biaxial crystal
Single crystals of LaCOB and GdCOB were grown Space group Cm Cm
successfully by the Czochralski method described elsewhere Z 2 2
Density (g cm3) 3.229 3.70
[15]. The phase identification and characterization of the
V (Å3) 468.3 449.7
samples were carried out by single crystal X-ray diffraction and a (Å) 8.183 8.078
is in accordance with the results previously shown in Refs. b (Å) 16.11 15.98
[2,18]. The results show that both the LaCOB and GdCOB have c (Å) 3.623 3.552
a monoclinic structure belonging to the space group Cm (C3s ) b (8) 101.36 101.26
(Z, a) (8) 24.8 26
with Z = 2. The RE3+ ions occupy the center of a distorted
(Y, b) (8) 0 0
oxygen octahedron with Cs symmetry. The Ca2+ ions occupy (X, c) (8) 13.4 15
two C1 symmetry sites: Ca2+(1) sixfold O2 coordinated and RE atomic number 57 64
Ca2+(2) eightfold O2 coordinated. The BO3 molecules occupy RE atomic weight (u) 138.91 157.25
two crystallographically distinct symmetry sites: B(1)O3, an RE average radius (Å) 1.95 1.88
isosceles triangle which is at the mirror plane with Cs site
symmetry, and B(2)O3, a scalene triangle which is rotated out of
the mirror plane with C1 site symmetry. The BO3 units form
rigid B–O triangles, which are connected to the distorted REO6
and CaO6 octahedra, forming a tri-dimensional network. It
should be noted that not all of the oxygen atoms are bounded to
boron ions. There is one oxygen, denoted for O(1), which is
bounded only to RE3+ and Ca2+ ions. The ionic radius of the
Ca2+ is similar to that of the RE3+, so an occupational disorder
between these ions at the symmetry sites can occur. The
distribution at the Cs site is 0.86 Gd + 0.14 Ca for GdCOB [2]
and 0.94 La + 0.06 Ca for LaCOB [18]. Throughout this work
we consider the RE3+ and Ca2+ ions mainly located at Cs and C1
symmetry sites, respectively. Since RECOB is a monoclinic
biaxial crystal, only the crystallographic b-axis coincides with Fig. 1. The orientation of the optical indicatrix axes (X, Z) relative to the
the optical Y-axis. Some structural data of GdCOb and LaCOB crystallographic axes (a, c) in the ac-plane. The values of w ((Z, a)) and f ((X, c))
are summarized in Table 1. for GdCOB and LaCOB are given in Table 1.
The samples for Raman measurements were cut and polished
into a rectangular block (8.7 mm  11.4 mm  8.7 mm for
GdCOB and 4.9 mm  4.6 mm  4.6 mm for LaCOB) and frequencies around 900–1000 cm1; (ii) the non-degenerate
oriented along the axes as shown in Fig. 1. Backscattered Raman out-of-plane B–O bending (n2) mode at frequencies around
spectra were collected with a Jobin-Yvon T64000 triple- 650–800 cm1; (iii) the doubly degenerated antisymmetrical
spectrometer equipped with a liquid N2-cooled CCD detector. stretching (n3) mode at frequencies around 1250–1450 cm1;
The slits were set to give a spectral resolution of 2 cm1. The
spectra were excited by a 514.5 nm radiation from an Ar-ion laser
Table 2
(Coherent-Innova 70) operating at 50 mW. Site symmetries of atoms and vibrational modes in the Cs3 space group

3. Results and discussions Ions Wyckoff Site Number vibrations

sites symmetry
A0 A00
Table 2 lists the site symmetries of the atoms and the RE(La, Y, Gd) 2a Cs 2 1
vibrational modes in the primitive cell of the Cs space group. Ca(1) 4b C1 3 3
The 18 atoms contained in the primitive cell give rise to 54 Ca(2) 4b C1 3 3
phonons which are distributed in terms of the irreducible O(1) 2a Cs 2 1
B(1) 2a Cs 2 1
representation of the Cs point group as 29A0 + 25A00 , where
O(2) 2a Cs 2 1
2A0 + A00 are acoustic modes. The structural rigidity of the O(6) 4b C1 3 3
crystal is mainly ascribed to the B–O bonds [6]. Information on B(2) 4b C1 3 3
the internal vibrations of the BO3 group can be obtained from O(3) 4b C1 3 3
the correlation diagrams shown in Table 3. O(4) 4b C1 3 3
O(5) 4b C1 3 3
The regular planar BO3 group with D3h symmetry has four
internal modes: (i) the symmetrical stretching (n1) mode at GTOTAL = 29A0 + 25A00 . GACOUSTIC = 2A0 + A00 . GIR,RAMAN = 27A0 + 24A00 .
102 G. Barros et al. / Vibrational Spectroscopy 46 (2008) 100–106

Table 3
Correlation diagram for the BO3 internal vibrations

and (iv) the doubly degenerated in-plane O–B–O bending (n4) which implies that the frequencies of the internal vibrations of the
mode at frequencies around 590–680 cm1 [13]. From Table 3, B(1)O3 triangle should be higher than those of the B(2)O3
the internal modes of the BO3 units occupying Cs and C1 triangle [2]. The vibration at 1236 was assigned to A00 symmetry,
symmetries sites are distributed in terms of the A0 and A00 while the others were assigned to A0 symmetry.
representations as: 4A0 (n1, n2, n3, n4) + 2A00 (n3, n4) and 6A0 (n1, In Ref. [13], 3 n3(TO) Raman modes with A0 symmetry at
n2, 2n3, 2n4) + 6A00 (n1, n2, 2n3, 2n4), respectively. So, 1206, 1255 and 1286 cm1 and one n3(TO) modes with A00
10A0 + 8A00 are internal modes and the remaining 17A0 + 16A00 symmetry at 1253 cm1 were observed for GdCOB. The modes
16A00 are external modes. Table 4 displays the factor group at 1206, 1253 and 1255 cm1 correspond to the vibrations of
analysis for the RECOB crystal. Polar phonons with A0 and A00 the B(2)O3 triangle, while that at 1286 cm1 to the vibration of
symmetries are both Raman- and infrared-active. In this case, a the B(1)O3 one. The two modes missing in the spectra are: the
TO–LO splitting may occur, what would lead to the observation n3(B(1)O3) with A00 symmetry at 1299 cm1 and the
of twice as many phonons as those predicted by the Group n3(B(2)O3) with A00 symmetry at 1236 cm1. In that work
Theory. the high-frequency modes are correctly assigned to the
Fig. 2(a) displays phonons with A0 (TO) symmetry, while n3(B(1)O3) vibrations. Also, the authors observed that the A0
Fig. 2(b) and (c) display phonons with A0 (TO + LO)  A00 (TO) modes exhibit a significant LO–TO splitting. The frequencies
symmetries. The low-intensity modes appearing in the highest- of the A0 modes shift upwards from 1206, 1255 and 1286 cm1
frequency part of the spectra (1100–1400 cm1) are assigned to for q/Y (TO) to 1251, 1302 and 1352 cm1 for q/Z (TO + LO),
the n3(BO3) vibrations. According to Table 3, 3A0 + 3A00 modes respectively. Six IR bands were observed: 3 A0 modes centered
are expected to be observed. In Ref. [11], 4 modes were observed at 1215, 1271 and 1314 cm1, and 3 A00 modes centered at
at 1206, 1236, 1296 and 1354 cm1 for GdCOB. The first two 1240, 1267 and 1295 cm1. The bands appearing in the
modes were assigned to the vibrations of the B(1)O3 triangle, reflectance spectra are broad, indicating a significant TO–LO
while the remaining two to the vibrations of the B(2)O3 one. mode splitting. Based on lattice dynamics calculations, the
However this assignment, as also observed by Maczka et al. [13], authors assigned the vibrations near to 1300 cm1 to the
seems to be not correct. The B–O bond lengths of the B(1)O3 n3(B(1)O3) and those in the range 1210–1270 cm1 to the
triangle are slightly shorter than those of the B(2)O3 triangle, n3(B(2)O3). However, it should be noted that the highest-
Table 4
Factor group analysis for RECOB (RE = Gd and La)a
Symmetry Cs n(N) n(A) n(R) n(T) n(O1) n(i) IR R
A0 29 2 4 13 2 10 x, y xx, zz, yy, xy
A00 25 1 5 11 1 8 z xz, yz
a
n(N), overall degrees of freedom; n(A), acoustic modes; n(T), translational lattice modes; n(R), rotational lattice modes; n(O1), vibrations of the O1 atoms not
bonded to the boron; n(i), internal vibrations. R and IR denote Raman and IR activities.
 G. Barros et al. / Vibrational Spectroscopy 46 (2008) 100–106 103

Fig. 2. Room-temperature Raman spectra of the GdCOB (bottom) and LaCOB (top). (a) Displays phonons with A0 (TO) symmetry, while (b) and (c) display phonons
with A0 (TO + LO)  A00 (TO) symmetries.

frequency part (n > 1000 cm1) of the polarized Raman makes difficult a reliable assignment. From the polarized (E//
spectra shown in Refs. [11,13] is quite noisy and the XZ(A0 ) and E//Y(A00 )) IR spectra, the authors reported 3
n3(BO3) vibrations are barely seen. From Fig. 2(a)–(c) we n2(BO3) bands: (i) the n2(B(1)O3) mode with A0 symmetry at
observed 6 n3(BO3) vibrations for both the LaCOB and GdCOB 793 cm1, (ii) the n2(B(2)O3) mode with A0 symmetry at
compounds. For GdCOB they are at 1208, 1219, 1228, 1253, 760 cm1, and (iii) the n2(B(2)O3) mode with A00 symmetry at
1304 and 1345 cm1, while for LaCOB they are at 1198, 1203, 742 cm1. Two of them are narrow (742 and 793 cm1)
1222, 1251, 1291 and 1334 cm1. These vibrations either indicating that the TO–LO splitting is small. The one at around
correspond to the predicted 3A0 + 3A00 modes or result from the 760 cm1 is broad and clearly indicates a considerable TO–LO
TO–LO mode splitting of the polar modes. splitting. From Fig. 2(a)–(c) we observed 4 n2(BO3) vibrations
The n1(BO3) modes appears as a very intense doublet at 935 for both the LaCOB and GdCOB compounds. For GdBO3 the
and 947 cm1 for GdCOB and at 929 and 937 cm1 for vibrations appear at 743, 753, 772 and 797 cm1. Since the
LaCOB. References [11,13] report this doublet for the GdCOB Group Theory analysis predicts only three, 2A0 + 1A00 modes, it
at 932–944 cm1 and at 933–945 cm1, respectively. This indicates that two of these modes may result from the TO–LO
doublet appears as narrow and very weak bands at 930 and splitting of the polar mode. For LaCOB the n2(BO3) vibrations
942 cm1 in the IR spectrum [13], indicating a negligible LO– appear at 745, 755, 775 and 798 cm1.
TO splitting of the n1(BO3) modes. Three n1(BO3) modes are Six 3A0 + 3A00 n4(BO3) modes are expected in the range 590–
predicted by the Group Theory: 1A0 mode corresponding to the 680 cm1. In Ref. [11] the authors observed all of the 6 n4(BO3)
B(1)O3 group, and A0 + A00 corresponding to the B(2)O3 modes. Three A0 symmetry modes at 607, 617 and 638 cm1,
triangle. The highest frequency mode is assigned to the B(1)O3 and three A00 symmetry modes at 590, 603 and 623 cm1. The
triangle, while the lowest frequency should correspond to the high-frequencies vibrations at 623 and 638 cm1 correspond to
A0 + A00 vibrations of the B(2)O3 triangle. Polarized measure- the n4(B(1)O3) modes with A00 and A0 symmetries, respectively.
ments reveal that these vibrations are either degenerated [13] or Only three Raman modes were reported in Ref. [13]: two A0
the A00 mode is missing [11]. modes at 601 and 611 cm1, and one A00 mode at 591 cm1.
The spectral region 740–800 cm1 comprises the n2(BO3) These modes correspond to the vibrations of the B(2)O3
modes. Three (2A0 + 1A00 ) modes are predicted. In Ref. [11], 2 triangle. However, the polycrystalline IR spectrum shows five
Raman modes were observed for GdCOB: the mode at bands at 594, 601, 615, 620 and 635 cm1, while the polarized
737 cm1 with A00 symmetry corresponding to the vibration of (E//Y) IR spectrum shows three A0 modes at 598, 612 and
the B(1)O3 triangle, and the mode at 749 cm1 with A0 633 cm1. This indicates that the TO–LO splitting of the
symmetry corresponding to the vibration of the B(2)O3 triangle. n4(BO3) modes is small. For GdCOB, we observed three out of
In Ref. [13], 3 Raman-active phonons were observed: (i) one the six modes at 617, 620 and 640 cm1, while for LaCOB
mode with A0 symmetry at 747 cm1, and (ii) two modes at 773 these modes were observed at 612, 615, and 635 cm1. Of the
and 751 cm1 with intermediate A0 (TO–LO) symmetry. The 16 internal modes observed for GdCOB, 14 and 13 modes
intensity of the n2(BO3) vibrations appearing in the polarized coincide (10 cm1) to those reported in Refs. [11,13],
Raman spectra reported in Refs. [11,13] is very weak, what respectively.
104 G. Barros et al. / Vibrational Spectroscopy 46 (2008) 100–106

The spectral region n < 550 cm1 contains the external from the behavior of the n1(BO3) modes. Besides the downshift,
modes corresponding to the translational (T) and rotational (R) the frequency difference between the components of the
motions of the BO3 groups, and translational motion of the n1(BO3) doublet of the LaCOB (Dn = 8 cm1) becomes smaller
O(1), Ca2+ and RE3+ ions. According to Table 4, 3 (2A0 + 1A00 ) than that of the GdCOB (Dn = 12 cm1). Inspection of Table 6,
modes correspond to the T-like Gd3+ modes; 12 (6A0 + 6A00 ) shows that the average distances of the B–O bonds in the
modes correspond to the T-like Ca2+ modes; 9 (5A0 + 4A00 ) and B(1)O3 and B(2)O3 triangles are almost the same for both the
9 (4A0 + 5A00 ) modes correspond to the T- and R-like BO3
modes, respectively. Based on previous analysis of other borate Table 5
systems [22,23], Dominiak-Dzik et al. [8] proposed the Frequencies (cm1) and possible assignment of the vibrations measured in
RECOB (RE = Gd and La)
following mode assignment for the GdCOB: (i) T-like Gd3+
modes appear in the ranges 90–150 cm1 and 210–265 cm1; GdCOB LaCOB Assignment
(ii) R-like BO3 modes appear in the range 154–200 cm1; (iii) 97 vw 101 vw Lattice
T-like BO3 modes appear in the range 280–340 cm1, and (iv) 117 m 115 m Lattice
T-like Ca2+ modes appear in the range 340–525 cm1. They 129 m 133 m Lattice
145 vw Lattice
observed three R-like BO3 modes at 154, 171 and 200 cm1;
153 vw Lattice
two T-like Gd3+ modes at 245 and 261 cm1; one T-like BO3 176 sh Lattice
mode at 294 cm1; and three T-like Ca2+ modes at 367, 375 and 181 w 181 w Lattice
464 cm1. In Ref. [11], the authors assigned the low-frequency 184 w Lattice
modes not only in terms of the T- and R-like BO3 modes, but 192 vw Lattice
238 w Lattice
also in terms of the internal and external modes of the GdxOy
245 m 241 m Lattice
and CaaOb groups. However, as discussed in Ref. [13], this 248 sh Lattice
assignment is not precise and the assignment proposed in Ref. 262 w 256 w Lattice
[8] is not supported by the lattice dynamics calculations. The 269 m Lattice
following assignment was therefore proposed by Maczka et al. 294 w Lattice
299 m 287 m Lattice
[13]: (i) T-like Gd3+ modes appear in the region n < 120 cm1;
299 vw Lattice
(ii) T-like Ca2+ modes appear in the range 120–300 cm1; (iii) 307 w Lattice
R-like BO3 modes appear in the range 120–200 cm1; (iv) T- 316 m 308 m Lattice
like BO3 modes appear in the range 200–400 cm1; and (v) the 321 sh 328 sh Lattice
frequencies appearing at 334, 451 and 461 cm1 correspond to 337 w 355 sh Lattice
359 m Lattice
T-like modes of the unbounded O(1) atom. From Raman and IR
372 m Lattice
measurements, they observed 28 (15A0 + 13A00 ) out of the 33 381 m 364 m Lattice
modes (17A0 + 16A00 ) expected. Inspection of the IR spectra 400 sh Lattice
indicates a negligible TO–LO splitting of the external modes. 425 w 392 m Lattice
The modes were grouped into four regions: (i) n < 120 cm1, 428 w Lattice
437 w Lattice
containing the T-like Gd3+ modes; (ii) 120 < n < 200 cm1
439 vw Lattice
containing both the T-like Ca2+ and R-like BO3 modes; (iii) 462 vw 457 w Lattice
200 < n < 300 cm1 containing both the T-like Ca2+ and T-like 460 m Lattice
BO3 modes; and (iv) 300 < n < 400 cm1 containing the T-like 487 vw 471 w Lattice
BO3 modes. Since the assignment of the external modes 492 m 494 sh Lattice
512 sh 500 sh Lattice
presented in Ref. [13] is not unequivocal and no further
508 m Lattice
information can be obtained from our results, we will assign all 605 vw 599 sh n4(BO3)
the modes with n < 550 cm1 as lattice modes. Our results 617 vw 612 vw n4(BO3)
indicate that 25 and 26 lattice modes are observed for GdCOB 620 vw 615 vw n4(BO3)
and LaCOB, respectively. Of the 25 modes observed for 629 sh n4(BO3)
640 vw 635 vw n4(BO3)
GdCOB, 20 and 17 modes coincide (Dn  10 cm1) to those
743 vw 745 vw n2(BO3)
reported in Refs. [11,13], respectively. Table 5 lists the 753 vw 755 vw n2(BO3)
frequencies observed and their tentative assignments. 772 vw 775 vw n2(BO3)
Let us consider the effect of replacing the RE3+ ion on the 797 vw 798 vw n2(BO3)
phonon spectra of the RECOB compounds. From Fig. 2(a)–(c), 935 vs 929 vs n1(BO3)
947 vs 937 s n1(BO3)
we observed that most of the frequencies shift downwards when
1208 m 1198 sh n3(BO3)
La replaces for Gd. This results from the lattice expansion (see 1203 vw n3(BO3)
Table 1) which occurs due to the size difference between the 1219 m n3(BO3)
La3+ and Gd3+ ions. The volume of the unit cell increases from 1228 w 1222 vw n3(BO3)
449.7 to 468.3 Å3 when La3+ replaces for Gd3+, increasing the 1253 w 1251 sh n3(BO3)
1304 w 1291 w n3(BO3)
average distances between the atoms as shown in Table 6. This
1345 w 1334 w n3(BO3)
increase of the interatomic distances leads to the observed
frequency downshift. Another interesting feature is observed s: strong; vs: very strong; m: medium; w: weak; vw : very weak; sh: shoulder.
 G. Barros et al. / Vibrational Spectroscopy 46 (2008) 100–106 105

Table 6 observed. For GdCOB and LaCOB we observed 25 and 26

Selected average interatomic distances (d(Å)) in the RECOB structure
external vibrations out of the 33 (17A0 + 16A00 ) modes
Bonds Distances (d(Å)) predicted by the Group Theory analysis, respectively. For
GdCOB LaCOB GdCOB, Lorriaux-Rubbens et al. [11] and Maczka et al. [13]
observed 30 and 28 external vibrations, respectively. The
B(1)–O(2) 1.369  2 1.382  2
B(1)–O(6) 1.378 1.395
second corresponds to the region of the BO3 internal modes. For
B(2)–O(3) 1.366 1.384 GdCOB and LaCOB we observed 16 and 17 internal vibrations
B(2)–O(4) 1.381 1.397 out of the 18 (10A0 + 8A00 ) modes predicted, respectively.
B(2)–O(5) 1.365 1.379 However, some of them may result from the TO–LO splitting of
Ca(1)–O(1) 2.319 2.345 the polar modes. This is likely to occur for the n3(BO3) and
hRE–O(1)i 2.249 2.288
RE–O(4) 2.389  2 2.409  2
n2(BO3) modes. The only modes having negligible TO–LO
hRE–O(6)i 2.393 2.433 splitting are the n1(BO3) vibrations, which are unequivocally
assigned. For GdCOB, Lorriaux-Rubbens et al. [11] and
The symbol h i denotes for average distances.
Maczka et al. [13] observed 15 and 16 internal vibrations,
respectively. The phonon distribution shows two features when
Gd3+ is replaced by La3+. Most of the frequencies observed
shifts downwards, and the frequency difference between the
components of the n1(BO3) doublet at around 950 cm1
decreases. The frequency softening observed results from the
monoclinic lattice expansion (4%). For instance, the modes at
372 and 245 cm1 for GdCOB appear at 364 and 241 cm1 for
LaCOB, which corresponds to a frequency downshift of 2 %.
The decrease of the frequency difference between the
components of the n1(BO3) doublet results from the increase
of the RE–O bond-lengths, since the B–O bond-lengths are the
same for both the B(1)O3 and B(2)O3 triangles.

Acknowledgements

Financial support from the Brazilian agencies CNPq,

CAPES, FUNCAP and FINEP is gratefully acknowledged.
Work performed at Argonne National Laboratory is supported
by the US DOE-BES under contracts No. W-31-109-ENG-38.
The work at Shandong University is supported by a grant for
Fig. 3. Schematically simplified fragment of the RECOB structure. State Key Program of China.

compounds. In the unit cell of the RECOB, the REO6 References

octahedron shares the oxygen O(4) and the oxygen O(6) with
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[2] A.B. Ilyukin, B.F. Dzhurinskii, Russ. J. Inorg. Chem. 38 (1993) 847.
When Gd is replaced by La, the RE–O(4) bond length increases [3] G. Aka, A. Khan-Harari, F. Mougel, D. Vivien, F. Salin, P. Coquelin, P.
from 2.389 to 2.409 Å (0.8%) and the RE–O(6) bond lengths Colin, D. Pelenc, J.P. Damelet, J. Opt. Soc. Am. B 14 (1997) 2238.
increase (on average) from 2.393 to 2.433 Å (1.6%). This [4] M. Iwai, T. Kobayashi, H. Furuya, Y. Miro, T. Sasaki, Jpn. J. Appl. Phys.
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