Chapter 6

Studies on n=2 Aurivillius Phases:

Structure of the Series Bi3-xLaxTiNbO9
(0.0x1.0)

126

127

6.1 Introduction
The Aurivillius family of layered Bi oxides has been a subject of considerable interest
since they display ferroelectric properties that might lead to the generation of useful
technical devices [121]. These oxides have the general formula [Bi 2O2] [An-1BnO3n+3]
(n=1,2,3,4) where the [Bi2O2]2+ layers are interleaved with n perovskite-type layers having
the composition [An-1 Bn O3n+1] [106,143]. Crystallographic studies in recent years have
brought out the role of cation disorder specially for higher members in the series (>n=3).
The subtle interplay of electronic and steric factors in the packing of [Bi 2O2]2+ layers with
perovskite layers bring about interesting consequences like modulations as demonstrated
by detailed single crystal studies by Thompson and coworkers [115,116]. It has been
demonstrated [123] that the ferroelectric properties of the solutions starting from the x=0
member depend largely on the size and charge carried by the substituting element. It is
observed that the Tc is lowered with increasing lanthanum substitution and the value of
the dielectric constant reduces drastically near the transition [122].
Substitution has been found to be feasible at the perovskite A-site by both divalent ions
such as Sr2+, Ba2+, Ca2+ as well as trivalent ions such as La 3+ [144]. Combined X-ray and
neutron diffraction studies by Lightfoots group on the n=3 member with divalent Sr and
trivalent La ions have clearly demonstrated that the cations display disorder with the
incorporation of non-lone pair cations in the [Bi2O2]2+ layers [148]. We have recently
demonstrated that similar disorder occurs in the n=4 layers by abinitio powder X-ray
diffraction studies [149]. It is therefore interesting to investigate the behavior of the La 3+
ions in Bi3TiNbO9.

6.2 Experimental
Bi3-xLaxTiNbO9 at x=0.2, 0.4, 0.6, 0.8 and 1 were synthesized by the solid state reaction
of stoichiometric amounts of La2O3, Bi2O3 and TiO2 at 1223K for 15 hours, then at 1323K
for 24 hours with intermittent grinding after each heating step. Quantitative elemental
analyses on all samples were carried out on a JEOL JSM-840 SEM/EDAX machine in
order to confirm the composition of the metal ions. The ratio of the metal ions thus
calculated from the EDAX analyses correspond to that of the ions taken initially for
syntheses. Preliminary powder X-ray diffraction data revealed that the compounds were
128

formed without any impurity phases. Electron diffraction studies were carried out using a
JEOLJEM 200CX microscope.
High resolution room temperature X-ray diffraction data on all the three compounds were
collected on a STOE STADI/P X-ray powder diffractometer with germanium
monochromated CuK1 ( = 1.54056) radiation in the transmission mode. The samples
were rotated during data collection to reduce orientation effects, if any and the data were
recorded using a linear PSD. The X-ray data were measured in the range 2=3 to 89.48
for x=0.2, 0.4, 0.6, 0.8 and 1 and 2=3 to 79.48 for x=0 composition at steps of 0.02
with exposure time of 6 seconds per step.

6.3 Results and Discussion

6.3.1 Structure refinement in space group A21am
The powder X-ray diffraction patterns of all but x=1.0 compositions suggest
isostructurality with the parent Bi3TiNbO9. The model suggested by Lightfoot et. al [144]
in the space group A21am fits all these compositions as indicated by the Rietveld
refinement results (table 6.1). The presence of a 2 1 screw axis along the a axis is shown
in the (100) zone axis orientation selected area electron diffraction pattern (SAD) (figures
6.1(a)-(b)). The 2a cell (a=3.9) in the ab plane is evident from figure 6.1(a). The
A-lattice centering is clear from the (001) zone axis SAD pattern (figure 6.1(b)). Further,
the electron diffraction patterns of Bi2LaTiNbO9 (x=1) clearly suggest the absence of Acentering in the lattice as shown in figures 6.1(c) and (d). These figures show that the
lattice is primitive with the appearance of spots in the intermediate space as compared to
figures 6.1(c)-(d). Indeed, the absence of lattice centering and the drastic drop in
dielectric constant suggest the choice of a centrosymmetric, primitive space group [122].
Rietveld refinements of all except x=1 composition, were carried out in the space group
A21am using the GSAS program [37]. The profiles were fitted using a pseudo-Voigt
function after accounting for the background with a Chebyshev polynomial consisting of
15-20 coefficients. No cation disorder was assumed and the La atoms were confined to
the Wyckoff 4a (perovskite Bi) sites. The possibility of existence of cation disorder

129

Figure 6.1: Selected area electron diffraction patterns of

(a) (001) orientation for x=0
(b) (100) orientation for x=0
(c) (001) orientation for x=1
(d) (100) orientation of x=1

130

however, was tested by varying the occupancies of the possible Bi sites. It was clear from
subsequent refinements that cation disorder does not exist in the n=2 phase. The
occupancies and thermal parameters of titanium and niobium atoms were also refined
alternately keeping the overall occupancy of the respective sites constrained to 1.0. The
details of the crystal data and refinements are given in table 6.1. The observed, difference
and calculated patterns of the x=0.0 and 0.4 compositions are shown as representative
patterns in figures 6.2 and 6.3. The atomic coordinates and the bond distances are listed
in tables 6.2 and 6.4.
Table 6.1
Crystal data and refinement results of Bi2-xLaxTiNbO9 (0 x 1)
Composition
Formula
weight
Color
Space group
Z
()
Cu(K1)
2 ()
Profile
function
a ()
b ()
c ()
V (3)
Rwp (%)
Rp (%)
R(I, hkl) (%)
Number of
data points

x=0.0

x=0.2

x=0.4

x=0.6

x=0.8

x=1.0

911.77
yellow
A21am
4

897.74
yellow
A21am
4

883.74
yellow
A21am
4

868.53
yellow
A21am
4

855.71
yellow
A21am
4

841.70
yellow
Pmcb
4

1.54056

1.54056

1.54056

1.54056

1.54056

1.54056

3-79.48
pseudoVoigt
5.4248(2)
5.3864(2)
25.0392(9)
731.67(7)
17.29
11.79
8.35

3-89.48
pseudoVoigt
5.4364(2)
5.4106(3)
25.0787(11)
737.96(5)
10.29
5.57
12.67

3-89.48
pseudoVoigt
5.4392(2)
5.4145(2)
25.0705(11)
738.32(5)
12.57
7.65
9.8

3-89.48
pseudoVoigt
5.4449(2)
5.4277(2)
25.0677(9)
740.82(6)
12.8
6.86
11.33

3-89.48
pseudoVoigt
5.4455(3)
5.4382(2)
25.0398(10)
741.47(5)
14.53
7.52
12.60

3-89.98
pseudoVoigt
5.4340(3)
5.4420(3)
25.0040(11)
739.59(5)
13.89
8.69
12.57

3850

4300

4300

4300

4300

4300

131

Figure 6.2: Observed, calculated and difference X-ray patterns of Bi3TiNbO9 (x=0)
(space group A21am)

132

Figure 6.3: Observed, calculated and difference X-ray patterns of Bi2.6 La0.4TiNbO9
(x=0.4) (space group A21am)

133

Table 6.2
(a) Final structural parameters from powder X-ray data at 298K for
Bi3TiNbO9
atom
site
x
y
z
occupancy
Uiso(2)
Bi(1)
4a 0.0235(21)
0.2385(12)
0.0000
1.00
0.0268(14)
Bi(2)
8b 0.5156(19)
0.7296(6)
0.1989(1)
1.00
0.0238(14)
Ti(1)
8b 0.4677(14)
0.7292(6)
0.4121(2)
0.45(1)
0.0194(26)
Nb(1)
8b 0.4677(14)
0.7292(6)
0.4121(2)
0.55(1)
0.0194(26)
O(1)
4a 0.459(11)
0.182(10)
0.0000
1.00
0.0176(56)
O(2)
8b 0.471(8)
0.775(8)
0.3411(12)
1.00
0.0176(56)
O(3)
8b 0.784(19)
0.008(37)
0.2568(18)
1.00
0.0176(56)
O(4)
8b 0.633(7)
0.936(7)
0.0923(14)
1.00
0.0176(56)
O(5)
8b 0 .755(9)
1.007(17)
0.5678(12)
1.00
0.0176(56)

atom
Bi(1)
La(1)
Bi(2)
Ti(1)
Nb(1)
O(1)
O(2)
O(3)
O(4)
O(5)

(b) Final structural parameters from powder X-ray data at 298K for
Bi2.8 La0.2TiNbO9
site
x
y
z
occupancy
Uiso(2)
4a 0.0142(27)
0.2232(12)
0.0
0.79(2)
0.0067(13)
4a 0.0142(27)
0.2232(12)
0.0
0.21(2)
0.0067(13)
8b 0.5003(25)
0.7339(8)
0.1990(1)
1.00
0.0075(5)
8b 0.4638(18)
0.7630(28)
0.4114(2)
0.46(2)
0.0092(28)
8b 0.4638(18)
0.7630(28)
0.4114(2)
0.54(2)
0.0092(28)
4a 0.448(17)
0.169(13)
0.0
1.00
0.0173(48)
8b 0.471(16)
0.668(9)
0.3381(12)
1.00
0.0173(48)
8b 0.765(23)
-0.003(36)
0.2599(17)
1.00
0.0173(48)
8b 0.649(9)
1.040(9)
0.0710(12)
1.00
0.0173(48)
8b 0.773(9)
1.018(23)
0.5673(14)
1.00
0.0173(48)

atom
Bi(1)
La (1)
Bi(2)
Ti(1)
Nb(1)
O(1)
O(2)
O(3)
O(4)
O(5)

(c) Final structural parameters from powder X-ray data at 298K for
Bi2.6 La0.4TiNbO9
site
x
y
z
occupancy
Uiso(2)
4a
-0.0074(20) 0.2353(9)
0.0
0.58(1)
0.0164(1)
4a
-0.0074(20) 0.2353(9)
0.0
0.42(1)
0.0164(1)
8b
0.4816(19) 0.7294(1)
0.1988(1)
1.00
0.0269(8)
8b
0.4516(16) 0.7576(19)
0.4124(1)
0.38(2)
0.0236(21)
8b
0.4516(16) 0.7576(19)
0.4124(1)
0.62(2)
0.0236(21)
4a
0.441(17)
0.187(9)
0.0000
1.00
0.0230(43)
8b
0.420(7)
0.684(7)
0.3387(9)
1.00
0.0230(43)
8b
0.739(16)
0.003(26)
0.2586(15)
1.00
0.0230(43)
8b
0.635(8)
0.941(7)
0.0763(11)
1.00
0.0230(43)
8b
0.667(8)
1.005(8)
0.5686(10)
1.00
0.0230(43)
(d) Final structural parameters from powder X-ray data at 298K for
134

atom
Bi(1)
La(1)
Bi(2)
Ti(1)
Nb(1)
O(1)
O(2)
O(3)
O(4)
O(5)

atom
Bi(1)
La(1)
Bi(2)
Ti(1)
Nb(1)
O(1)
O(2)
O(3)
O(4)
O(5)

site
4a
4a
8b
8b
8b
4a
8b
8b
8b
8b

x
-0.0001(25)
-0.0001(25)
0.4963(19)
0.4631(17)
0.4631(17)
0.563(13)
0.468(16)
0.755(20)
0.711(14)
0.682(10)

Bi2.4La0.6TiNbO9
y
z
0.2340(11)
0.0
0.2340(11)
0.0
0.7307(6)
0.1987(1)
0.7634(24)
0.4126(2)
0.7634(24)
0.4126(2)
0.198(13)
0.0000
0.669(7)
0.3356(10)
0.005(41)
0.2599(15)
0.926(10)
0.0652(13)
1.024(10)
0.5737(12)

occupancy
0.58(1)
0.42(1)
1.00
0.54(2)
0.46(2)
1.00
1.00
1.00
1.00
1.00

Uiso(2)
0.0102(11)
0.0102(11)
0.0206(8)
0.0175(23)
0.0175(23)
0.0147(47)
0.0147(47)
0.0147(47)
0.0147(47)
0.0147(47)

(e) Final structural parameters from powder X-ray data at 298K for
Bi2.2La0.8TiNbO9
site
x
y
z
occupancy
Uiso(2)
4a
-0.0100(30) 0.2308(14)
0.0
0.35(1)
0.0111(14)
4a
-0.0100(30) 0.2308(14)
0.0
0.75(1)
0.0111(14)
8b
0.4749(24) 0.7331(8)
0.1988(1)
1.00
0.0226(9)
8b
0.4587(29) 0.7649(30)
0.4122(2)
0.54(2)
0.0125(23)
8b
0.4587(29) 0.7649(30)
0.4122(2)
0.46(2)
0.0125(23)
4a
0.518(18)
0.233(16)
0.0000
1.00
0.0198(50)
8b
0.432(16)
0.677(11)
0.3351(11)
1.00
0.0198(50)
8b
0.730(22)
0.003(37)
0.2593(19)
1.00
0.0198(50)
8b
0.714(14)
0.925(11)
0.068(14)
1.00
0.0198(50)
8b
0.687(20)
1.026(17)
0.5727(13)
1.00
0.0198(50)

6.3.2 Structure determination in Pmcb

The composition Bi2LaTiNbO9 (x=1.0) was assigned a primitive orthorhombic cell and
the structure determination was attempted. Initial full pattern fitting and peak
135

decomposition using EXTRA [52] suggested the space group Pmcb uniquely for 33
extracted reflections. SIRPOW92 [145] was then used to locate the heavy atom positions
(La, Bi, Nb/Ti atoms). Refinements of these atoms using the GSAS program followed by
a subsequent difference Fourier map resulted in the location of all oxygen atoms. The
strategy followed for the refinement of the earlier compositions was followed and the
results are given in table 6.1. The observed, difference and calculated patterns of the
x=1.0 composition is shown in figure 6.4. The atomic coordinates and bond distances are
listed in tables 6.3 and 6.5.

Figure 6.4: Observed, calculated and difference X-ray patterns of Bi2LaTiNbO9 (x=1)
(space group Pmcb)

136

Table 6.3
Final structural parameters from powder X-ray data at 298K for
Bi2LaTiNbO9
atom
La(1)
La(1)
Bi(2)
Bi(3)
Ti(1)
Nb(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)

site
2d
2a
4h
4g
4g
4h
8i
4g
2b
8i
2c
8i
4g

x
0.0
0.5
0.5
1.0
0.5
0.0
0.215(9)
0.0
0.5
0.2699(6)
0.0
0.269(11)
0.5

y
0.0
-0.5
-0.5042(29)
-0.5034(28)
0.0475(8)
-0.4886(6)
0.277(9)
0.490(3)
0.0
0.648(6)
0.5
0.325(9)
0.008(36)

z
0.0
0.0
0.2015(1)
0.3041(2)
0.0957(9)
0.0835(4)
0.2451(17)
0.1746(24)
0.0
0.0773(11)
0.0
0.0722(17)
0.1600(20)

occupancy
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00

Uiso (2)
0.0266(25)
0.0206(35)
0.0164(16)
0.0240(17)
0.0160(26)
0.0160(26)
0.0156(49)
0.0156(49)
0.0156(49)
0.0156(49)
0.0156(49)
0.0156(49)
0.0156(49)

The structure of the end members of Bi3-xLaxTiNbO9 (x=0 & x=1) respectively are shown
in figures 6.5 and 6.6. The Ti/Nb atoms occupy the M position of the MO 6 octahedra in
the perovskite layer with the inter-leaving of the O-Ti/Nb-O chain along the c axis by
the [Bi2O2 ]2+ layers. It is of interest to note that upon La substitution the volume of the
137

unit cell steadily increases up to x=0.8 but drops to an intermediate volume for x=1 (table
6.1). Indeed, the c axis contracts at full lanthanum substitution. The Ti-O distances in all
the compositions range from 1.63(5) to 2.45(11) with alternate bonds being long and
short resulting in a zigzag arrangement of Ti/NbO6 octahedra. The Ti-O distance
variations though large are in reasonable agreement with those observed in n=3 system
from neutron studies (Ti-O range 1.72(1)- 2.32(1)). Considering that the size of Bi3+ and
La3+ ions being similar, the variations seen in Bi-O distances (table 6.5) also appear
reasonable.
It is noteworthy that in the n=3 series [148], the La cations are disordered over both the
perovskite A sites and [Bi2O2 ]2+ B sites. The crystal system goes to the tetragonal
symmetry (I4/mmm) with the inherent strain present in this compound relieved due to the
La atom being distributed over both sites. It appears that no such cation (La 3+) disorder is
observed in the current study and for the x=1 composition, the strain may be relieved due
to the octahedral tilting, with the retention of the orthorhombic symmetry (Pmcb). The
selected area electron diffraction patterns unequivocally confirm the retention of the
orthorhombic symmetry with the absence of the A centering in the x=1 composition.

138

Figure 6.5: Crystal structure of Bi3-xLaxTiNbO9 (0x0.8), viewed along [110] direction
(space group A21am)
139

Table 6.4
Bond lengths () in Bi2-xLaxTiNbO9 (0x0.8)
Parameter
Ti/Nb-O(2)
Ti/Nb-O(5)
Ti/Nb-O(5)
Ti/Nb-O(1)
Ti/Nb-O(4)
Ti/Nb-O(4)

Parameter
Bi(1)-O(1)
Bi(1)-O(1)
Bi(1)-O(1)
Bi(1)-O(1)
(Bi(1)-O(4)x2
(Bi(1)-O(4)x2
(Bi(1)-O(5)x2
(Bi(1)-O(5)x2

Parameter
Bi(2)-O(3)
Bi(2)-O(3)
Bi(2)-O(3)
Bi(2)-O(3)
Bi(2)-O(2)
Bi(2)-O(2)
Bi(2)-O(2)
Bi(2)-O(2)

x=0.0
1.78(2)
1.79(8)
2.12(9)
2.24(1)
2.08(4)
1.93(4)

x=0.0
2.38(12)
2.29(7)
3.14(7)
3.07(12)
2.56(5)
2.82(4)
2.51(9)
2.66(10)

x=0.0
2.55(13)
2.38(13)
2.18(13)
2.11(13)
2.66(4)
3.11(4)
3.11(4)
2.65(4)

x=0.2
1.91(3)
1.69(1)
2.22(10)
2.28(1)
2.41(5)
1.63(5)

x=0.2
2.38(9)
2.15(7)
3.30(7)
3.09(9)
2.39(4)
2.85(4)
2.63(9)
2.64(4)

x=0.2
2.54(3)
2.45(1)
2.17(1)
2.07(1)
2.53(4)
3.07(12)
3.20(6)
2.77(8)

140

x=0.4
1.90(2)
2.07(5)
1.84(5)
2.23(9)
2.00(4)
2.05(4)

x=0.4
2.45(1)
2.30(4)
3.13(4)
3.01(1)
2.27(4)
3.16(4)
2.86(4)
2.41(4)

x=0.4
2.53(9)
2.15(2)
2.47(2)
2.11(3)
2.60(4)
2.66(3)
3.23(4)
3.11(3)

x=0.6
2.00(3)
1.89(7)
1.94(7)
2.29(2)
2.34(6)
1.80(7)

x=0.6
2.36(7)
2.38(7)
3.07(7)
3.10(7)
2.17(5)
2.81(2)
2.48(4)
2.97(5)

x=0.6
2.56(1)
2.47(1)
2.13(3)
2.10(2)
2.53(3)
2.76(8)
3.05(8)
3.17(3)

x=0.8
1.99(3)
1.90(10)
1.92(9)
2.23(1)
1.76(7)
2.36(7)

x=0.8
2.52(8)
2.57(9)
2.87(9)
2.87(9)
2.81(5)
2.93(2)
2.49(2)
2.93(2)

x=0.8
2.46(1)
2.14(1)
2.50(1)
2.10(1)
2.57(5)
2.68(8)
3.12(8)
3.12(8)

141

Figure 6.6: Crystal structure of Bi2LaTiNbO9, viewed along [110] direction (space group
Pmcb)

142

Table 6.5
Bond Lengths () in Bi2LaTiNbO9
Ti-O(3)

2.40(2)

Nb-O(2)

Ti-O(4)

2.12(3)

Nb-O(5)

Ti-O(6)

2.44(4)

Nb-O(4)

Ti-O(7)

1.63(6)

Nb-O(6)

Ti-O(4)

2.12(3)

Nb-O(4)

Ti-O(6)

2.45(11)

Nb-O(6)

(La(1)-O(4))x4
(La(1)-O(6))x4
(La(1)-O(5))x2
(La(1)-O(3))x2

2.43(3)
2.39(4)
2.718(1)
2.718(2)

2.29(6
)
2.08(1
)
1.65(3
)
1.80(5
)
1.65(5
)
1.80(6
)

(La(2)-O(4)x4
(La(2)-O(6)x4
(La(2)-O(5)x2
(La(2)-O(3)x2

Bi(1)-O(1)
Bi(1)-O(1)
(Bi(1)-O(1))x2
(Bi(1)-O(2))x2
(Bi(1)-O(7))x2

3.08(3)
2.91(4)
2.710(1)
2.718(1)

2.55(4)
2.28(4)
2.22(4)
2.80(2)
2.86(2)

6.4 Conclusions
The combined powder X-ray diffraction and electron diffraction studies confirm that the
two end members (x=0 and x=1) crystallize in the orthorhombic system. The refinements
also confirm that in the n=2 series lanthanum is distributed only in the perovskite A
sites and not in the [Bi2O2]2+ Bi sites.
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