J. Phys. Chem.

Solids

Pergamon Press 1962. Vol. 23, pp. 665-676.

Printed in Great Britain.

A FAMILY OF FERROELECTRIC BISMUTH COMPOUNDS*

E. C. SUBBARAO

Westinghouse Research Laboratories, Beulah Road, Churchill Borough, Pittsburgh 35, Pa. (Received 9 June 1961 ; revised 31 August 1961)

Abstract--A large number of compounds of the general form (Bi202) z+ (Mera_lRmO3m+l)~- are synthesized. Me and R represent ions of appropriate size and valency and m equals 2, 4 and 5. A dielectric study revealed ferroelectrieityin the following compounds: MeBi2RzO9 (Me = Ba,Pb, Sr and R = Nb, Ta), MeBi4Ti4Oa5 (Me = Ba, Pb, Sr), Me0.~Bi4.~Ti4015 (Me = K, Na) and Me~Bi4TisOls (Me = Pb, Sr). Curie temperatures exist over a wide range from about 100C to perhaps as high as 900-950C (for BizTiNbOg). The presence of Bi ions seems related to the high (Te > 500C) Curie temperatures of many members. In a given series, the Curie points decreased with the divalent ion in the order: lead-strontium-barium. At the Curie temperature, a symmetry change from tetragonal to orthorhombic takes place, with the largest orthorhombic distortion observed being 1-007 BizTiNbO9 at room temperature. Dielectric studies on single crystals indicate the ferroelectric axis to be the pseudo-tetragonal e-axis.

1. INTRODUCTION FERROELECTRIC oxides m a y be classified into four structure types: (1) perovskite (e.g. BaTiO3, K N b O 3 etc.), (2) pyrochlore (e.g. Cd2Nb2OT), (3) tungsten bronze (e.g. PbNb206 and PbTa206) and (4) layer-type bismuth compounds (e.g. PbBi2Nb209). A feature common to these four structures is the presence of ions of small size and large charge (e.g. T i 4+, N b a+, T a 5+ etc.) in oxygen octahedra, which are linked through corners forming continuous chains of oxygen-metal-oxygen. MATTHIAS(11,and S MOLENSKIIand KOZHEVNIKOVA(2) have pointed out that such a structural arrangem e n t is favorable for the occurrence of ferroelectricity in oxides. PbBi2Nb209 was the first ferroelectric compound with a layer-type structure to be found and it was discovered by SMOLENSKII, ISUPOV and AGRANOVSKAYA. (3) T h i s compound is a m e m b e r of a family of mixed bismuth oxides of the general formula

where M e and M e ' = mono-, di-, or trivalent ions, or a mixture of them, R = T i 4+, N b 5+, T a 5+ etc., singly or in combination, m = 2, 3, 4 etc.

A b o u t a decade prior to the ferroelectric interest in these oxides, AUmVILLIUS14) synthesized several compounds in the family and examined their crystal structure using single crystals. One half of the unit cells of PbBi2Nb209 (m = 2), BiaTi3012 (m = 3), and BaBi4Ti4Oa5 (m = 4) is depicted in Fig. 1. T h e s y m m e t r y is pseudo-tetragonal (actually orthorhombic). T h e structure comprises a stacking of m perovskite-like units of nominal composition MeRO3 between Bi202 layers along the pseudo-tetragonal c-axis. I t is noteworthy that the continuous extension of the O - R - O chains along the c-axis is interrupted not only by the presence of (BizO2) layers but also by the translation of the perovskite units in the plane perpendicular to the c-axis as is shown more clearly in / (MezO2) 2+ (Mem-lRmO3m+ l) 2Fig. 2. On the other hand, unbroken chains o f O - R - O are present in the plane perpendicular to * Supported in part by contract with the Army- the c-axis. There are two molecules per unit cell. Prompted b y the existence of a structural Ordnance Corps. 665

666

E.C.

SUBBARAO

~L

i:7:
= Zi

!
OBi oTi 0 0 oBaBi oTi O 0 (b)
[c)

I:

oBi P b e N b O 0

(a}

Fro. 1. One half of the pseudo-tetragonal unit cell of (a) PbBizNb~Og, (b) Bi4Ti3012, and (c) BaBi4Ti4015 (from z _'2 0.25 to z -- 0"75). C denotes Bi20~* layers, and B units of hypothetical perovskite structure PbNbOa in (a), BiTiOa in (b), and (BaBi)TiO8 in (c). A denotes the perovskite layer PbNbzO~- in (a), BlzT13Oto' in " ~(b), and BaBi~Ti40~ in (c) (after AURIVILLIUS(4)). arrangement favorable for the appearance of spontaneous polarization and the discovery of ferroelectricity in one member of the family, viz. PbBi2Nb~O0, m) an extensive dielectric study of mixed bismuth oxides with layer-type structure
A
-

2o ,~

-io

-0

@ Ba Bi oTi o @

Pb
Bi Nb 0 Bi eTi

0 A

was initiated. Rather detailed results on Bi4Ti3Oj 2 and its solid solutions with m = 3 have already been published, m) T h e purpose of the present paper is to report on the ferroelectric properties of bismuth compounds with m = 2, 4, and 5. Phase transitions were examined by dielectric, X-ray, optical and dilatometric methods. T h e earlier resuits on compounds with m = 3 are extended and are made use of for a discussion of the properties of the entire family. Ferroelectric properties of compounds with well-defined dielectric anomalies are presented first. Then, a more detailed account of the dielectric properties and phase transitions in Bi3TiNbO9 is given. A preliminary account of this workm) listed PbBi2TazO9 (m = 2), PbBi4Ti4015 (m = 4) and BaBi4Ti4015 (m = 4) as ferroelectrics. During the course of the present work, ferroelectricity in Bi4TiaOl~ (7) (m = 3), BaBi4Ti4015 (s) (m = 4) and Ba2Bi4TisOls m) (m = 5) has been reported independently.
2. EXPERIMENTAL PROCEDURE

O0

(a)

(b)

(c)

Fro. 2. Schematic pictures of the structures of (a) PbBi~Nb~Og, (b) Bi4TiaO12, and (c) BaBi4Ti4Ols. The vertical lines indicate the lines 00z and , , z in the unit cells. A denotes perovskite regions in the structures.

Bismuth compounds with m = 2, 4, and 5 in the general formula were prepared by solid state reaction in air of the constituent oxides or carbonates using covered platinum crucibles in globar furnaces. T h e final sintering of a two-step firing proeedure was carried out at temperatures between

A FAMILY

OF FERROELECTRIC

BISMUTH

COMPOUNDS

667

1000 and 1250C for one hour. T h e weight loss (beyond that required for COz evolution) due to the heat treatment was always less than one per cent and in most cases less than 0"5 per cent. T h e chemicals used were of reagent grade or better. Thus, for example, Bi2Os of spectroscopic purity was supplied b y Johnson, Matthey and Company, 99"5 per cent grade Nb205 and Ta205 were obtained from Kennametal, Inc., and "very high p u r i t y " TiO2 was supplied by National L e a d Company. T h e phase identification of the sintered products was by X - r a y diffraction powder techniques using Cu K~ radiation. T h e temperature dependence of dielectric constant was measured on silvered ceramic disks at a frequency of 100 kc/s with a measuring field of about 10 V/cm using a General Radio capacitance bridge. Measurements were made with increasing and decreasing temperature. T h e rate of heating and cooling was about l C / m i n in the vicinity of the transition temperature. M o s t of the ceramic disks used for dielectric study had over 90 per cent theoretical density. A few had densities as low as 75 per cent of theoretical. T h e measured densities are given in T a b l e 1. No cor-

rection for the porosity was made in the dielectric data.

3. R E S U L T S

(A) Dielectric properties

T h e temperature dependence of dielectric constant of compounds with m = 2 viz. Me2+Bi2Nb209 and Me2+Bi2Ta209 (Me 2+ = Pb, Sr, and Ba) is shown in Fig. 3. Similar data for m = 4 compounds of the type Me2+Bi4Ti4015 (Me 2+ = Pb, Sr, and Ba) are depicted in Fig. 4 and those of the type Me~+5 Bia.sTi4015 ( M O + = N a and K) in Fig. 5. Dielectric behavior of Me~+Bi4Ti5018 (Me 2+ = Pb and Sr) with m = 5 is shown in Fig. 6. All these materials have dielectric constants of the order of 100 at room temperature and reach a peak at a characteristic (Curie) temperature in a manner typical of ferroelectrics. T h e m a x i m u m value of dielectric constant varied from a few hundreds to several thousands, the highest value being generally observed for the lead compounds in a given series. Above the Curie temperature, the dielectric constant (E) decreases at a rate that can approximately be described by the Curie-Weiss law

7'able 1. Dielectric properties of layer-type compounds (BizO2) 2+ (Mem-lRraOara+l) em

Compound

Density (g/cm a)

Dielectric constant
l

Curie temp (C)

cu:Zw2s
I

d88

c/N)

Ref. DiX-ray electric 4,9 4 4,9 9 4 4 4 4,9

I

25C
r

Peak ---1100 550 540 450 2100 340 1630 5500 1630 1600 1700 5900 1400
i

(15Cc)

O(C) ]

BiBi~TiNbO9 BiBi2TiTaO9 CaBi~Nb~O9 CaBizTa209 SrBizNb~O9 SrBizTa209 BaBi2Nb~O9 BaBi2Ta~O9 PbBizNb209 PbBi2Ta209 BaBi4Ti4015 PbBi4TiaO15 SrBiaTi4Ol~ CaBiaTi4015 BisTi3GaO15 Nao.sBi4.sTi4015 Ko.sBi4.5Ti4015 Pb~Bi4TisOas Sr2Bi4TisOls

6-4 8"5 5"0 7"5 6-9 7.5 6.3 8.4 7'6 9.0 5.7 6"6 5.2 4.7 7.3 6.3 6.7 6.6 5.3

100 140 80 140 190 180 280 400 170 180 150 220 190 120 150 200 140 4O0 280

440 335 200 110 560 430 395 570 530 655 550 310 285

0.55 2.0 1'3 0.37 2.5 1"4 0.68 0.79 0.74 4.1 0.47

390 190 510 325 335 552 485 610 515 280 255

10 23 15 5 12 23 15 10 10 25 25

-------3
8

668

E.C.

SUBBARAO

X 102 6 Nle2+ BI2Ta2091 srl

5-Ba

E)

X 103
I
m

Me2+ Bi4Ti4015

Pb Pb 3 2 ---

i'
k~ Sr

I
I

i -~ X102 -.~ 22
,5
o/ I

I)

I ~,Pt i" ~

00

100

200

300

400

500

600

Temperature, C
FIG. 4. Dielectric constant versus temperature of Me2+Bi4Ti4015: (A) PbBi4Ti4015, (B) SrBi4Ti4015, and (C) BaBi4Ti4015.

;x 1416182Me2+BI2Nb209 _12 108

-[ 100 I 200 I 300

(B)~ j/
I 400 I 500

2 0

600

Temperature, C
FIG. 3. Dielectric constant versus temperature of Me~+Bi2Nb2Og. (A) PbBi~Nb~Og, (B) SrBi2Nb2Og, and (C) BaBi~NbaOg; and Me2+Bi2Ta~O9; (D) PbBiaTa~Og, (E) SrBisTa~Og, and (F) BaBi~Ta2Og. ~_ C / ( T - 0 ) . T h e extrapolated Curie-Weiss temperature 0, was in all cases at least 20 lower than the Curie temperature. T h e Curie constant, C, was of the same order of magnitude (105 C) as that for other oxide ferroelectrics such as BaTiOa, Cd2Nb207, and PbNb206. T h e dielectric parameters for the different compounds are listed in T a b l e 1. O f the compounds investigated, those that were previously synthesized and examined by X-ray methods by AURIVILLIUS or ISMAILZADE are (4) (9) indicated in T a b l e 1. T h e other compounds were

synthesized for the first time in the present study. Ferroelectricity was previously reported only in two compounds of this Table, viz. PbBi2Nb209 m) and BaBi4Ti4015. (8) T h e dielectric properties of these two compounds in the present study are in good agreement with those of SMOLENSKII et al. (3) and FANG et al.,(8) but the transition temperatures are significantly different.* I n the case of other compounds of this study, no published dielectric data is available for comparison.t * The Curie temperature of PbBizNb~O9 was found to depend upon the heat treatment, particularly the cooling rate. Cooling from 1100C at the rate of 150C/hr gave a Curie temperature of 595C and a cooling rate of 30C/hr resulted in phase change at 550C. Annealing of the fast-cooled samples at 700C lowered the phase transition to about 560C. A value as low as that reported by SMOLIqNSKnet al.(z) (526C), however, has not been observed. It has been established that this is a true behavior of the ceramics and was not due to the electrodes or the measuring equipment. The possible ordering of Bi and Pb ions in the two types of Me sites in the structure may be the explanation for the observed behavior. ~"After this manuscript was completed, a publication by SMOLENSKII, IsuPov and AGRANOVSKAYA came to (17) the author's attention. These workers made a dielectric study of some of the same compounds up to 500C. The results of the two studies are in good agreement.

A F A M I L Y OF F E R R O E L E C T R I C B I S M U T H C O M P O U N D S
X 103
! I I I I ] l

669

Meo.5Bi4. 5Ti4015

00

i00

200

300

400

500

600

700

Temperature, C

FIG. 5. Dielectric constant versus temperature of (K) Ko.sBi4.sTi4O15 and (Na) Nao.sBi4.sTi4015. Attempts were made to observe the D - E hysteresis loops using a standard Sawyer and Tower circuit. The applied a.c. field was between 20 and 50 kV/cm and temperature was in the range 100-250C. Increased conductivity prevented employing higher temperatures. Welldefined hysteresis loops were observed only for a few compounds (e.g. SrBi2Ta2Og, PbBi2Ta2Og, Pb2Bi4Ti5018, and Sr2Bi4Ti5Oas). Estimated values of spontaneous polarization in tzC/cm 2 for the ceramic specimens are as follows: 5"8 for SrBi2Ta209 at 25C, 6 for Pb2Bi4Ti5Ols at 235C, and 3-5 for Sr2Bi4Ti5018 at 255C. In the case of other compounds, either the coercive field is too large at the temperatures employed (as in PbTiO3) or the polarization cannot be reversed (as in antiferroelectrics). Piezoelectric activity can be induced in polycrystalline ferroelectrics. Therefore, ceramic specimens were "poled" under a d.c. field of 2050kV/cm, while the samples were immersed in silicone oil kept at 200-250C. The piezoelectric coefficient, dzs, measured on the poled disks under static loading, ranged from 0 to 25 10-12 C/N; the observed values are given in Table 1. At least the compounds for which specific values of d33 are given in the table may be considered as ferroelectrics.

X 103
] I I

- Me2+Bi4Ti5018

Pb

Sr

100

200

300

400

500

Temperature, C

;. 6. Dielectric constant versus temperature of (Sr) Sr2BiaTisOls and (Pb) Pb2Bi4Ti5Ols.

670

E. C. S U B B A R A O

(B) Phase transitions

Linear thermal expansion of several compounds was measured on ceramic specimens using a quartz tube dilatometer with an optical lever magnification of about 1800. Changes in expansion coefficients were noted at temperatures corresponding to the respective Curie points, indicating a phase change. High-temperature X-ray studies on Bi4Ti3Oa~,(5) PbBi2Nb209, c9) and Bi3TiNbO9 (see below) have shown that the orthorhombic, ferroeleetric modification transforms to the high temperature tetragonal form at the Curie point. It appears that the symmetry change in other compounds of this family is analogous. The orthorhombie modification may be considered to be derived from the tetragonal form by an elongation of one of the face diagonals perpendicular to the c-axis. The relation of the orthorhombic form to the tetragonal modification is shown in Fig. 7.

Some of the twin boundaries had a bow-shape, originating and terminating in sharp points in the middle of the crystal. The twin boundaries make 45 with the extinction direction i.e. they are parallel to the tetragonal a-axes of the para-electric phase. Thus the twin configuration is very similar to that observed in ferroelectric KH2PO4 (10) and orthorhombic BaTiO3. Crystals about 6 10-acre in thickness and 0'025 cm 2 in area were used for dielectric study. Well-defined, but somewhat asymmetric, hysteresis loops were observed at room temperature when a field of about 10 kV/cm was applied with the major faces electroded. Spontaneous polarization was estimated to be about 3/~ C/cm 2 at room temperature, in agreement with the reported value for single crystalsC7) and ceramics. (5) No loops could be obtained with an a.c. field of about 5 kV/cm applied perpendicular to the c-axis; the sample dimensions do not permit a very desirable electrode geometry in this case. The c-axis therefore is the polar axis in Bi4Ti3Ol~. (D) Bi3TiNbO0 and BiaTiTaO9 These compounds crystallize with the layer-type structure with relatively large orthorhombic distortion (b/a _ 1.007). Differential thermal analyses showed two phase transitions at 750 and 930C for BizTiNbO9 and at 660 and 870C for Bi3TiTaOg, on heating. On cooling, the lower transition occurs at about 150 below that during heating. These data prompted a detailed study of phase transitions in Bi3TiNbO0.

c aT

F i t . 7. Schematic representation of the unit-cell axes of the layer-type compounds, showing the relation of the axes of the high temperature tetragonal modification (at) to those of ferroelectric, orthorhombic form (a0 and b0). a0 "" b0 -- M'(2)aT.

(1) Thermal expansion. Dilatometric study of ceramic specimens confirmed the two phase changes, the transition at the higher temperature exhibiting the larger volume change (Fig. 8). A high temperature X-ray study was carried out using a Norelco diffractometer and a furnace, previously employed for a study of ( C) Polar axis BiaTi3012.(5) The c-parameter was calculated from In order to determine the ferroelectric axis (00l) reflections with l = 8, 10, 14, and 20. The uniquely, plate-like crystals of Bi4Ti3012 (m = 3) orthorhombic a0 and b0 were obtained from the were grown by a method suggested by VAN following pairs of reflections: (020), (200) and UITERT and EGERTON.(7) X-ray study showed that (135), (315). These lines appear between 28 and c-axis was perpendicular to the plate. Optical 76 20 and were measured with a relative accuracy examination of the plates along the c-axis revealed of + 0"02 20. The lattice parameters increased twin lamallae, running at right angles to each with increasing temperature (Fig. 9) until, between other, as was noted by VaN UITnRT and EGEaTOr~. 900 and 950C, b0 and co contract slightly and a0

A FAMILY OF FERROELECTRIC BISMUTH COMPOUNDS

X 10-3 10
,

671

(B)

(2) Optical study For an optical examination of the phase transitions, plate-like crystals were obtained by melting Bi3TiNbO9 in a platinum crucible at 1300C ansi cooling slowly. Plates 0.020.03 cm in thickness were examined under the microscope and found to exhibit regions that were twinned with two sets of lamallae essentially perpendicular to each other. Other regions were free of twins. The twin boundaries were at 45 to the extinction position. On heating the crystals on a Leitz microscope, birefringence disappeared at 950+ 10C, indicating this to be the orthorhombic-tetragonal phase change. At the same temperature, the twins disappeared. On cooling, the original twinning was again observed. No anomalous optical behavior could be detected in the vicinity of 600C (the lower transition). The twin structure of Bi3TiNbO9 is similar to that of Bi4Ti3012. (3) Dielectric study. The dielectric constant of Bi3TiNbO9 is about 100 at room temperature (Table 1) and no dielectric anomalies could be detected below 700C in the ceramic specimens. Dielectric measurements could not be continued up to upper phase change due to increased conductivity. In order to determine which of the two phase transitions corresponds to the Curie temperature, if Bi3TiNbOo were ferroelectric, solid solutions based on Bi3TiNbO9 were prepared. (Bia+Ti4+) was replaced by (Me2+Nb 5+) so that the general formula of the solid solutions may be written as Bi 3- zMe 2 + Ttl+ xNbl+zO9 where M e Z + = x Pb, Sr, or Ba and O < x < 1. Continuous variations of lattice parameters (Fig. 10 and Table 2) and absence of extra lines in the X-ray powder patterns confirmed solid solution formation between BisTiNbO9 and MeBi2Nb209 (Me = Pb, St, and Ba). Temperature dependence of dielectric constant of several solid solution compositions with Tc < 700C was measured. Typical results for Bia-xSrzTil-xNbl+xO9 are shown in Fig. 11. Dielectric data for other systems are presented in Table 2. The dielectric behavior of the solid solution composkions was typical of that of ferroelectrics. Extrapolation of the Curie temperatures of the three solid solution systems indicates a transition temperature between 900 and 950C for Bi3TiNbO9 (Fig. 12). Therefore it can be concluded that the ferroelectric Curie temperature of

,100

I u

500

600

700

800

900

1000

Temperature, C

Fro. 8. Linear thermal expansion of (A) BiaTiNbO0 and (B) Bi3TiTaOg.

expands by a small amount. On heating, a0 expands at a faster rate than b0, so that bo/ao decreases with temperature until it becomes equal to unity above 900C. The high temperature phase therefore appears to be tetragonal. In addition to the phase change at 900-950C, lattice parameters, particularly a0 and bo/ao, showed anomalous changes in the vicinity of 600C, in agreement with differential thermal and dilatometric data. However, the compound had orthorhombic symmetry above the transition at 600C, as shown by the similarity of X-ray patterns taken at 800C and at room temperature. A small orthorhombic distortion can be detected in the lines (315), (135) even at 900C. These data are at variance with those of ISMAILZADE, (9) who reported the orthorhombic-tetragonal phase change between 600 and 650C on the basis of X-ray powder study.

672 1" 010

q

E.C.
I
0

SUBBARAO
I I E L I I

t
u

1" 005 -

bo/a

1- 000 -

-....
,

5.50,-

,4
~ 5.42
(3-

J
i Tetra-

~- 5-4o,~ 25-4' _ 25"2 -Orthorhombic

I gonal
i cT

_o.......o.---Z5.0
0

I
100

1
200

I
300

I
400

I
500
Temperature,

I
600
C

I
700

I
800

I
900

I
1000

Fxc. 9. Lattice parameters of Bi3TiNbOg.

gable 2. Prol~erties of solid solutions with layer-type structure (Bi202) 2+ (Mem-lRraO3m+l) 2/

m [ Composition Pseudo-tetragonal cell parameters (A) a~ BaBi~NbeO9 Bao.75Bi2.2~Tio.~sNbl.7509 Bao.5Bi~.sTio.sNbl.509 Bao.e5Bi~.75Tio.75Nb1.2509 BisTiNbO9 SrBi2Nb~O9 Sro.sBiz.2Tio.2Nbl.sO9 Sro.6Bi~.4Tio.4Nbl.609 Bi3TiNbO9 PbBi~Nb~O9 Pbo.75Bi~.25Tio.~sNbl.7509 Pb6.sBi~.sTio.sNbl.509 Pb6.~sBi~.75Tio.75Nbl.~509 Bi3TiNbO9 PbBi4Ti4Ol~ Pbo-75Bi4.z6Tis-75Gao-85015 Pbo.sBi4.sTis.5Gao.5Ox5 BisTisGaO15 3.928 3"911 3-876 3-847 3-836 3"894 3"885 3.865 3.836 3.886 3.871 3.858 3"844 3"836 3.845 3.84~ 3.84~ 3"835 c 25'60 25"60 25"50 25"35 25"1o 25'00 25'05 25'05 25"1o 25"55 25"5o 25"4o 25"30 25"1o 41"35 41"% 41"% 41.05 Dielectric constant 25C 280 310 240 170 100 190 225 155 100 170 180 100 220 180 175 150 Peak 540 840 1080 1100 980 700 2100 1000 200 315 5O0 440 500 600 560 675 Curie temp (C)

5500 3050 1930

570 600 620

A FAMILY OF FERROELECTRIC

BISMUTH COMPOUNDS

673

BiaTiNbO9 is between 900 and 950C. The nature of the phase change at about 600C remains unclear at present. By analogy, the phase
I ] I

I000

800 25'6

NN#~..C~L,~

Pb

25'4

I= (D L..f

o< a~

25"2
25"0

200

5-52

[ O.25

J O.50

I O.75

r 1. O0

Value of x in Bi3-xMe2+Til-xNbl+xO9x

5 5.~
FIG. 12. Transition temperatures of Bi3_zMez2+Til_z

Nbl+xOg, (Me 2+ = Pb, Sr, or Ba). transition at 870C may correspond to the Curie temperature of BiaTiTaOg.

~.~I, " ~ " 0

0"25

0"50

0-75

1"00

Value of x in Bi3_xPbxTil_xNbl+xO9
FIG. I0. Lattice parameters in the system Bi3_xPbx

(E) Galliumcompounds
An attempt was made to substitute (BiS+Ga3+) for (Pbe+Ti4+) in PbBi4Ti4015. Lattice parameter and Curie temperature changes indicate complete replacement of Pb, the resulting end member being BisTisGaO15 (Table 12). No reliable dielectric measurements could be made on BisTi3GaO15 itself, however; extrapolation of Curie temperatures in the solid solution system indicate a transition temperature of about 670C for BisTizGaOls.
4. DISCUSSION

Tit_xNbl+zOg.
X 102 12 10

.'-' 6

(_>

~4

Attention may be drawn to three outstanding features of this family of ferroelectrics: (A) large number of compounds, (B) spontaneous strain, and (C) high Curie temperatures.

(A) Large number of compounds

2

100

200

300

400

500

600

Temperature, C FIC. 11. Dielectric constant versus temperature of

Bis_=SrxTil_ =Nbl+zOg.
2X

The three variables (Me, R, and m) in the general formula of bismuth compounds with layertype structure generate a large number of compounds, many of which proved to be ferroelectric. In fact, this family represents the largest group of ferroelectrics. Thus the number of ferroelectric compounds in a ternary phase diagram like Me2+O-Bi2Os-TiO2 is remarkable (Fig. 13).

674

E. C. SUBBARAO

If the perovskite-type units in the structure are the only ones responsible for the appearance of ferroelectricity in Bi4TisOz2, the polar axis may be expected to be perpendicular to the c-axis. 02 This is so because the perovskite units are separated by (Bi202) layers in the c-direction. The expansion of the b-axis and the contraction of the other two axes as a crystal is cooled through the Curie temperature has led to the suggestion that b-axis may be the polar axis in Bi4Ti3012. (5) However, dielectric studies have shown the c-direction as the polar axis in Bi4TisO12. This apparent discrepancy can be resolved if the distortion caused by spontaneous strain is a shear instead of an extension. This could then account for the small magnitude of the measured distortion b/a in the bismuth compounds. The b/a of the bismuth oxides cannot be directly compared with the spontaneous strain of perovskite-type or Me 0 2+ B i203 tungsten-bronze-type ferroelectrics. A true FIG. 13. Ferroelectric compounds in the system measure of the spontaneous strain in bismuth MeO-Bi~.Oa-TiO~. MeO cart be PbO, SrO, or BaO. compounds is a change in c. Perovskite-type MeS+TiOs and layer-type compounds The appearance of spontaneous polarization m = 3, 4-, and 5 are shown. along the c-axis suggests that the (Bi2Os) layers also take part in the cooperative phenomenon reIn addition to the compounds discussed here, sponsible for the occurrence of ferroelectricity in unsuccessful attempts to synthesize other bismuth mixed bismuth oxides. Another factor that seems compounds were made. The crystal-chemical to lend support to the role of (BisO2) layers for the criteria favoring the formation of mixed bismuth cooperative process is the following: PbBi4TiaOxs oxides with layer-type structure is an interesting and PbsBi4TisOl8 may be derived from Bi4TisOls topic in itself and this forms the subject of a by inserting one and two units, respectively, of separate publication. Also, not all the compounds perovskite-type PbTiOz between the (Bi2Oz) that were synthesized are ferroelectric. As exam- layers of Bi4TizO12. The Curie temperature of ples of compounds in which ferroelectricity is Bi4TisOi2 drops from 675 to 570C with the introabsent or very weak, we may cite the calcium duction of one PbTiO3 and to 310C with the incompounds (CaBizNbzOg, CaBi2Ta2Og, and sertion of two PbTiO3 units. The role of SrTiO8 CaBi4Ti4015) which crystallize with the layer- appears to be similar to that of PbTiO3 in this type structure. Dilatometric and X-ray studies (9) respect. The decrease of Curie temperature with locate a phase change (apparently orthorhombic- increasing separation of (Bi~Oe) layers, other things tetragonal) in the range 550-650C for the three being equal, may be a significant fact. compounds. The dielectric constant at room temperature was about 100 (Table 1) and no detectable ( C) Curie temperatures It has not been possible so far to account for the dielectric anomalies could be found below 700C.

Here, when MeO is PbO, three layer-type compounds (BiTiaOz2, PbBi4Ti4015, and Pb~Bi4TisO18) and one perovskite-type PbTiO3 are ferroelectric. There is a striking resemblance between the ferroelectric compounds of layertype structure and the group of ferrimagnetic compounds (t2) in the system Me2+O-BaO-Fe203 in which the structure of the intermediate compounds is related to that of the end members by certain stacking sequences. (zs)

No piezoelectric activity or hysteresis loops could be observed in these compounds. It must therefore be concluded that if the phase change in the calcium compounds is related to ferroelectricity, the ferroelectric behavior is indeed very weak.

(B) Spontaneous strain

Ti ~ B

A Me2Bi4TisO]. 8 B-Me 4Ti40]5 Bi i4Ti3012

-

A F A M I L Y OF F E R R O E L E C T R I C B I S M U T H C O M P O U N D S variation of the Curie points in a consistent manner even in the case of the (structurally) simplest compounds like BaTiO3 and its isomorphs. Therefore, in the present state of our knowledge, all that can be done about the complex compounds discussed in the present paper is to draw attention to some systematic trends. This is facilitated by the availability of a large number of structurally related compounds. (1) The niobates always have a higher Curie temperature than the corresponding tantalates (Table 1). Whether the consistently different behavior of Nb and Ta in regard to the ferroelectric Curie temperature, in spite of the similarity of their chemistry and ionic size, is due to the difference in their masses, electronegativities (1.6 for Nb and 1.5 for Ta),(14) electronic configuration, or some other factor is not known at present. (2) A plot of transition temperature versus ionic radius (15) (Fig. 14), polarizability or atomic weight of divalent metal ion (Ca, Sr, and Ba) in MeBi2Nb2Og, MeBi2Ta209 and MeBi4Ti4Olg showed an approximately linear relationship; the slope is less for MeBi4Ti4015 series due to the smaller concentration of the Me 2+ ions compared to the other series. It may be noted that lead compounds do not occupy their appropriate position in Fig. 14. (3) For a given series of compounds such as MeBi2Nb209, MeBi2Ta2Og, MeBi4Ti4Olg, and Me2Bi4Ti5Ols, the Curie temperature decreased with the divalent metal ion in the following order: lead, strontimn, and barium (Table 1 and Figs. 3, 4 and 6). Nao.5Bi4.5Ti4015 has a higher Curie temperature than Ko.5Bia.sTi4Ols (Table 1 and Fig. 5). The presence of Bi 3+ in the Me sites of (Mem_lRmO3m+l) 2- units always gave high Curie temperatures. Replacement of (Me2+Nb 5+) in a given compound by (Bi3+Ti 4+) consistently raised the Curie temperature, as in m = 2 (Table 2) and m = 3 series. (5) The observed trend of the influence of metal ions on the Curie points may be related to the tendency of these ions towards covalency. For example, for a given value of m, the ferroelectric Curie temperatures and electronegativities (14) (which are believed to be a rough measure of covalency) increase in the order; Ba(0"9), Sr(1.0), Pb(1.6), (16) and Bi(1.9); and again K(0-8) a n d Na(0.9) [note also the electronegativity values for Ta(1.5) and Nb(1.6)].

675

More oxide ferroelectrics and antiferroelectrics contain lead or bismuth than any other cation e.g. Ba, Sr, Cd, K, Na, etc. Further, these two ions lead to relatively high Curie temperatures. An explanation for these observations may be sought in the fact that both Pb 2+ and Bi3+ ions have a pair 800 ~- 600 X 4O0 E g
:'~ 200 (:
IR ! i

Me2+ Bi2Ta209 2+ Ca Sr
il

~
"~a

0 0.9

El

1"0 1"1 12 1-3 Ionic Radius (A) of Divalent Metal

1-4

Fro. 14. Transition temperatures versus radius of divalent metal ion (Ca, Sr, and Ba) in some layer-type compounds. The data for CaBi2NbaO9 and CaBi2Ta~O9 are t a k e n from ISMAILZADE.(9) of 6s-electrons beyond the closed shell. ORGEL(11) has suggested that the possible hybridization of the 6s- and 6p-orbitals causes a tendency to antisymmetric distortions in a cubically coordinated ion. Such bonds increase ionic polarizability and dielectric constant. These considerations should favor the occurrence of ferroelectricity and of high Curie temperatures in lead and bismuth compounds. Of the trends of Curie temperatures versus metal ions noted for layer-type compounds, the ones that appear to be valid for oxide ferroelectrics of other structure types are that niobates have higher Curie temperatures than the corresponding tantalates (KNbO3 430C, KTaO3 - 2 6 0 ; PbNb206 570C, PbTa206 260C) and that Pb 2+ ion leads to higher Curie points than other divalent cations Acknowledgements--The author is indebted to G. SHIRANE for illuminating discussions on many aspects of this work. The author is grateful to F. L. CARTER,A. J. CORNISH,L. W. DOREMUS,D. E. HARRISONand W. D. JOHNSTON for helpful discussions. J. HRIZO played a major role in sample preparations and measurements.

676

E.C.

SUBBARAO

REFERENCES 10. MITSUI T. and FURUXCHIJ., Phys. Rev. 90, 193 1. MATTHIASB. T., Science 113, 591 (1951). (1953). 2. SMOLENSKIIG. A. and KOZHEVNIKOVA V., Dohl. N. 11. ORGELL. E.,J. Chem. Soc. 12, 3815 (1959). Akad. Nauk. S S S R 76, 519 (1951). 3. SMOLENSKIIG. A., XsuPov V. A. and AGRANOVSKAYA 12. JONKER G. H., WIJN H. P. J. and BRAUN P. B., Philips Tech. Rev. 18, 145 (1956). A. I., Fiz. Tverdogo Tela 1, 169 (1959); [Trans13. BRAUNP. B., Philips Res. Rept. 12, 491 (1957). lation: Soviet Phys. Solid State, 1, 149 (1959)]. 14. PAULING L., The Nature of the Chemical Bond, 4. AUmVlLLIUSB., Ark. Kemi 1, 463, 499 (1949); Ibid. (3rd ed.), p. 93. Cornell University Press 2, 519 (1950). (1960). 5. StmBARAOE. C., Phys. Rev. 122, 804 (1961). 15. AHaENS L. H., Geochim. et Cosmoch. Acta 2, 155 6. SUBBARAO C., J. Chem. Phys. 34, 695 (1961). E. (1952). 7. VAN UITERT L. G. and EG~RTONL., J. Appl. Phys. 16. HAISSINSKY J. Phys. Moscow 7, 7 (1946) quoted in J., 32, 959 (1961). PRITCrlARD H. O. and SKINNERH. A., Chem. Rev. 8. FANGP. H., ROBBINSC. and FORRATF., C.R. Acad. 55, 745 (1955). Sci. Paris 252, 683 (1961). G. 9. ISMAILZADEI. G., lzv. Akad. Nauk. S S S R 24, 1198 17. SMOLm'CSKU A., IsuPov V. A. and AGRANOVSKAYA A. I. Fiz. Tverdogo Tela 3, 895 (1961). (1960).