Jpn, J. Appl. Phys. Vol. 31 (1992) pp. 3108-3112 Part 1, No. 9B, September 1992 Crystal Growth, Dielectric and Polarization Reversal Properties of BisTigOy2 Single Crystal Yoichiro Masupa, Hiroshi Masumoro!, Akira BABA, ‘Takashi Goro! and Toshio HiRat! Department of Elecrial Engineering, Faculty of Engineering, Hachinohe Institue of Technology, 88:1 Ohbiraki, Myoh, Hachinohe, Aomori 031 “nsttute for Material Research, Tohoku University, 22:1 Kalahira, Aoba-ku, Sendai, Mivagi 980 (Received May 18, 192: accepted for publication July 18, 1992) [A Bi.O,-TiO, phase diagram was determined using diferent thermal ysis (DTA) apparatus. BigT}O,. (BIT) rmicalike single crystals grown by a flax method were clear and slightly grayish in color. Ferroelectric and dielectric prop- ‘erties of BIT crystals were observed from measurements of eletric displacement vs electric held hysteresis loops and the liclecric constant. Also, the polarization switching characteristics of BIT crystals were investigated. The switching time and switching KEYWORDS: $1. Introduction Recently, electronic equipment has been miniaturized with improved performance at high speed, as LSI tech- niques have been developed. Functional electronic materials used for piezoelectric and electrooptic devices stich as passive elements have been required for use in se- verely limited conditions. Moreover, with increasing memory capacity of D-RAM devices, the integrated technique using dielectric and ferroelectric thin films" has attracted much attention. Since bismuth layer-structured compounds (BIT) were synthesized by Aurivillius*” in 1949, these crystal struc- tures have been investigated in detail by X-ray analysis. To date, it has been confirmed that more than sixty kinds of these compounds have layer-structure perovskite phases and most of these compounds are ferroelectric. However, since these compounds have special crystal structures, it has been very difficult to grow single crystals except in some cases, but a micalike BisTisO): single crystal was grown quite easily by a flux method.® Dielec- tric and ferroelectric properties and crystal structures of the BiTisOx: (BIT) single crystal have previously been reported by many researchers,” Many researchers have reported on the preparation of BIT films deposited on sapphire," Si and MgO" substrates by the electron cyclotron resonance (ECR),"" ‘and rf sputtering and chemical vapor deposition CVD)" methods, respectively. The present paper describes the crystal growth of a BIT single crystal and the phase diagram of the Bi,Os~ TiO; system, which has dielectric, ferroelectric and polarization reversal properties. §2. Crystal Structure with Polarized Orientation and Switching Mechanism of —_Layer-Structured BiTiO,, Single Crystal Bi:TisO; compounds have remarkable structural nt density were read from the transient waveforms. ferroelectric, BiTIs0,2, flux method, layer structure, polarization reversal, domain wall features such as a large crystal anisotropy. The crystal structure of BIT was determined by Aurivillius.*® General formulae of these compounds are as follows: (Bi:0.)? (Ag iBnOsms) OF BizAq- Bn Oss. Here, A can be mono-(Na', K'"), di(Pb**, Ba"), or trivalent (Bi*---) ions or a mixture of them, B represents Tit*, Nb**, Ta®* and so on, and m can have values of 2, 3, dy. Bismuth titanate, BisTiO,2, is an example of such compounds with m=3, of which the symmetry is pseudotetragonal. The crystal structure may be described asa stacking of layers of (Bi:O,) and (Bi;Tis0,0) along the pseudotetragonal c-axis, Cummins and Cross have ob- tained the following results from X-ray analysis, optical observation and ferroelectric measurements, using thin sections of flux-grown Bi,TisO,, single crystals. ‘The crystal class is monoclinic and belongs in the point group m. Moreover, the spontaneous polarization has a magnitude larger than 30 zC/cm? and lies in a direction tilted approximately 7° from the major crystal surface in a plane parallel to the pseudoorthorhombie by-cy plane. When an electric field was applied on the major crystal surface with electrodes, the polarization along the c) direction yielded values of approximately 4 xC/em?. Fur- thermore, when the electric field was applied with elec- trodes on opposite major crystal surfaces, switching oc- curred by a unique change in the monoclinic tilt. These results suggest a change in the sign of the polarization in the ¢ direction but no change in the sign in the larger components in the by direction. §3. Experimental Procedure 3.1. Single-crystal growth by a flux method Powders used for single-crystal growth were prepared as follows: Bi:O, (Wako Pure Chemical Industries, Ltd. 99,9%) and TiO; (Fuji Titanium Co., 99.9%) powders were mixed in the ratio ByO,:TiOy= 10:1, 20:1, 21:1 and 22:1 by in weight. The mixed powders were charged into 3108Jpn. J. Appl. Phys. Vol. 31 (1992) Pt. 1, No. 9B a platinum crucible and it was set into an alumina cru: ble. As the melting point of mixed powder was deter mined to be 800°C by thermal differential analysis (DTA), the mixed powder in the platinum crucible was heated to 1200°C at a rate of 100°C/h and this temperature was maintained for $ h. Then the temperature was decreased to 800°C at a rate of $°C/h, and finally it was allowed to cool fo room temperature naturally. ‘These micalike crystals are separated by intervening layers of Bi:O; mineral acid solutions. The crystals are clear and slightly grayish in color, 3.2. Phase diagram and erystallinity ‘ABi,0;-TiO: phase diagram was determined using the differential thermal analysis. (DTA) — apparatus (RIGAKU-TAS-100). The solidus temperature was ‘measured by the heating curve, whereas the liquidus tem- perature was determined from cooling cycles. The struc- tures of the BIT single erystal and the Bi:O;-TiO; system were analyzed by X-ray diffraction (XRD) (Rigaku RAD- system). The temperature dependence of lattice parameters of BisTisOi: was determined by the diffrac- tometer tracing using a high-temperature furnace. Moreover, the pole-figure and Laue spots were measured using Mo radiations. The observation of domain walls and extinction direction of the erystal were performed us- ing a polarized microscope. 3.3. Dielectric, polarization reversal and optical proper- ties ‘The dielectric constant of BisTisO,: was measured with deposition of gold on major crystal surfaces at a fre- queney of 1 KHz and the measuring field was 10 V/cm, using an ADEX-221A LCR meter. Optical properties were determined using a double- beam spectrometer (Shimadzu UV-210). The remanent polarization and coercive field were obtained from the 50Hz D-E hysteresis loop, using @ modified Sawyer- Tower circuit. The pulsed polarization switching charac teristic was measured using a handmade transistorized high-voltage pulser. The specimens were micalike plates of about 4mm? in area and 230 um in thickness, Gold electrodes were deposited onto both major crystal sur faces. The electric capacitance of the specimens was main- tained below 50 pF. In order ¢o investigate the transient current carefully, the voltage response of a small cross resistor in series with the specimens was examined in photographs of waveforms displayed on the oscilloscope. The applied voltages generated by a high-voltage pulser were variable from 400 V to 2 KV, and the rise and fall times were $ and 6 xs, respectively, for pulse width of 10 ms. ‘The switching times were measured as the time where the switching current was attenuated to 10% of the max- imum, §4. Results and Discussion Figure 1 shows the Bi;0,-TiO; phase diagram obtained by Speranskaya er al." and added to our measurement results, ‘As many solid solutions can be synthesized in the Y. Masups eral. 3108 asof- 4 1300} 200} L100} 1000} Batis soot Tonperature oof too soa Tide w Mot Fig 1. The phase diagram (ater Speranskayat et a.) of the BLOTIO. system Bi,O,-TiO: system, the detailed phase diagram has not yet been defined. The melting points of each composi- tion, Bi:TO;, (BiOs:TIO;=1:4), BETO, (122), Bi,TisQ}» (2:3) and Bi,TiOu (4:1) determined by TG-DTA. equipment, were 1240, 1210, 1200 and 850°C, respec tively, ‘These results are similar to Speranskaya’s data. The crystal structures of BisTi:O; and Bi,TisO\2 com- pounds are formulated as a pyrochlore type, and the layer-structured perovskite and the lattice parameters of these compounds are a=5.39A, 5.45 A, and 32.84 A. Moreover, those of Bi,TijQ,2 are obtained as 5.45 A, 1.43 A and c=33.01 A, respectively. ‘The ceramic BizTi,O; specimen was confirmed to show ferroelectricity from the D-E hysteresis measurement. The X-ray diffraction of BisTijO; shows a single phase, but the structure is not yet defined clearly. From Xray diffraction results, the BisTiOss solid solut confirmed to be mixed Bi,O, and TiO: complex com- pounds. This compound shows excess Bi:O; in this region; therefore, bismuth oxide (Bi,0s) is assumed to act, as a liquidus solution. In this experiment, a mixing ratio of charged BisO; and TiO: materials is 21 vs 1 in weight percent for single-crystal growth. The excess bismuth ox- ide (Bi:Os) affected the flux solvent. BizTiOn, BisTiO; and Bi,TiO,2 complex compounds exist without weight change from room temperature to 1200°C, but slight weight change appears in the vicinity of 1250°C, whereas BiTIOy composition shows a sharp weight change around 850°C. It seems that the bismuth oxide (Bi:O.) evaporated. Figure 2 shows typical micalike BisTisO,2 single crystals grown by the flux method. These crystals are separated by intervening layers of BisO; mineral acid solutions. The crystals are clear and slightly grayish in col- or. Figure 3 shows X-ray diffraction patterns of reflected.3110 Jpn. J. Appl. Phys, Vol. 31 (1992) Pt. 1, No. 9B (a) Fig. 2, Micalike BiTi,O, single crystals grown by the flux method: (@) BAOTIO,=21:, (6) BLOsTI0,=21.5:1 a L | | | | w 70 Ww w $0 cy 16 Fig. 3. X-ray dlifraction pattern of surface of BiTIO, single crystals CuKa radiation to incident the perpendicular on the ma- Jor crystal surface. Reflection from the (001) plane was ob- served and the crystal surface was defined as the ¢ plane. In order to examine the optical behavior by viewing inci- dent light perpendicular to the major surface between the crossed nicols state on the polarized microscope, the (wo distinction directions were observed for the major crystal surface. This distinction angle is 90° and lies between the distinction direction axes @ and b. The powder X-ray pattern of the BiiTisO.: single crystal grown with excess Bi;Os flux solvent was similar to that of sintered ceramic data. The lattice parameters of BisTisO,2 were determined by CuKe radiation. The ¢ parameter was computed from the (001) reflection with 1=14. The @ and b parameters were obtained from (028), (2113) and (006) reflections. Bi,TisO,, has orthorhombic symmetry with a=5.45 A, b=5.43 A and c=33.01 A at room temperature. ‘These values are in agreement with those of Aurivillius and of Subbarao."” Figure 4 shows (a) the pole-figure and (b) Laue spots of BIT single crystals mixed with solid solution synthesized in various growing conditions. This, Y. Masupa etal @ or aord baxis / “4 NX vor w sorb Fig. 4. Pole-igure (a) and Laue spots (b of Bi:T,O}, single crystals crystal has a c-axis belonging to the perpendicular to the major crystal surface, and the a- and b-axes exist as only one pair on the major surface. Crystals of different or tation were not observed in these specimens because lat- tice constants were similar to the a- and b-axes, and direc- tions of the axes were not defined with certainty, Figure 5 shows temperature dependence of lattice parameters. On heating Bi,Ti,O,2, the lattice parameters expand at essentially a linear rate until the phase change around 660°C. paraneter( too aaa Tonperature("C) Fig. 5. ‘The temperature dependence of lattice parameters of BiTiO\s single crystal.Jpn. J. Appl. Phys, Vol. 31 (1992) Pt, 1, No. 98 ‘The parameters expand at a faster rate than b, so that the orthorhombic distortion (b/ a) decreases with inereas- ing temperature. ‘Around 660°C, a and ¢ parameters undergo a sudden, expansion; however, b is constant. Above the phase tran- sition, the orthorhombic distortion disappears, and the symmetry seems to be tetragonal. It is noted that tetragonal a of Bi:TisO)2is 3.86 A, which is approximate- ly the same as the lattice constant of perovskite-type com- pounds, Figure 6 shows the temperature dependence of the dielectric constant of BiyTijOj: measured on a gold- evaporated major crystal surface. The dielectric constant and dielectric loss factor of the e-direction are about 110 and 0.02 at room temperature, respectively. These values increased with temperature, reaching a peak of about 5800 at 650°C, and beyond 650°C, the dielectric constant decreased according to the Curie-Weiss law. The Curie point of the crystal corresponded to the phase transition temperature observed from the differential thermal analysis (DTA) curve and the dielectric measurement of Bi,Tis0,, ceramics. Figure 7 with a magnification of 200 shows the major crystal surface texture viewed with a crossed polars polarized microscope. A large number of herringbone- type domain walls were viewed from the surface, where the magnitudes of domain walls are about 1~2 ym. Transmittance of the major surface of BisTiO.. was about 40% for A=450 nm, and the absorption edge ex- isted in the vicinity of 380 nm in the visible range, The Fig. 6. The temperature dependence of dielectric constant of BLTLO, single crystals Fig. 7, Domain wall structure of Bi,TAO,. crystals viewed with polarized microscope. YY. Masups etal. 3111 remanent polarization P, and coercive field E. are 3.5 4uC/em? and 7.8 kV/cm, as shown in Fig. 8(a), respec tively. Cummins and Cross" reported P, values of 40.1 4C/em of the e component of P, on a crystal with electrodes on the major surface. However the spon- taneous polarization has a magnitude of 50 xC/em* and forms an angle of approximately 4.5 degrees with the ma- jor surface. In this study, the spontaneous polarization of a and b directions has not yet been observed in detail When a step-function voltage is applied to the specimen, the switching current shown in Fig. 8(b) is ob- served, where the switching time 1, is defined as the time until the switching current attenuates t0 10% of inns, the maximum of the changing current. The switching current waveform would suggest. a polarization reversal mechanism. Merz!” proposed a relationship between the switching time ¢, and the applied field E as KE 4 wo ‘The switching current waveform for a step function is shown in Fig. 8(c). With increasing applied field, the switching current increases and switching time decreases. Figure 9 shows the dependence of reciprocal switching time f;' and polarization current density on pulsed voltage. The r, tends to increase with increasing ap- plied voltage. The curve shows a nonlinearity at the lower field but becomes nearly linear under the field higher than 3000 V/mm. The value of coercive field in this crystal is about 800 V/mm. An integration of the tail of the switching current leads to a large number of charges. (3) Fig. 8. (a) Typical D-E hysteresis loop (80 Hz, oom temperature), (6) Schematic switching waveform of ferroelectrics and (c) typical Switching waveform Bi3,O,, crystals3112, Jpn. J. Appl. Phys. Vol. 31 (1992) Pt 1, No. 9B au) © 1e00 wooo 000 «00d (ve) Jopliod electric field Fig. 9. The applied field dependence of reciprocal switching time (61) and the switching curzent density of Bi,T,0}; erystals ‘This seems to indicate that the conventional definition, of &.is inadequate. The tail of the switching transient is approximately described by a power law of the form icct7", where K; linearly depends on E. In the case of BaTiO; single crystals, Ki is given by A exp (—a/E), as shown by Chynoweth." As mentioned above, the switching behavior in BIT single crystals is ordinary and the values of K and 1 in eq. (1) are calculated to be 2.3 and 1.5, respectively. §5. Conclusions The crystal growth of BIT single crystals obtained by a flux method and the phase diagram of the Bi;O;-TiO, system, which have dielectric, ferroelectric and polariza- tion reversal properties were investigated. The results ob- tained are as follows: (1) BisTisO,: single crystals were synthesized by the flux method using mixed powder (Bi;03:TiO}=21:1 in weight). The crystals were micalike, clear and slightly grayish in color. (2) The major surface of the micalike crystal was de- termined to be the (001) plane, from observation of the X-ray diffraction pattern, (3) From viewing the polarized microscope measure- ments, two distinct directions were observed in the major Y. Masupa et al. crystal surface, and these distinct directions correspond to a- and b-axes. Moreover, a large number of her- ringbone-type domain walls were viewed on the surface. (4)_ The remanent polarization P, and coercive field E. of BIT single crystals were 3.5 wC/cm? and 7.8 kV/cm re- spectively, where the direction was perpendicular to the major surface. The dielectric constant and the dielectric loss factor along the c-axis are about 110 and 0.02 at room temperature, respectively. (5) The polarization reversal switching time becomes shorter with increasing applied field, and the applied field dependence of switching time is well described by the well-known formula &,=KE™~", where the values of K and n are 2.2 and 1.5, respectively. The present study was supported by the Facility for Development Research of Advanced Materials in the In- stitute for Materials Research, Tohoku University. The authors would like to thank Dr. T. Suzuki for valuable discussion. References 1) M. Okuyama, Y. Matsui, H. Nakano, . Nakagaws ‘Yamakawa: Jpn. J. Appl. Phys. 18 (1979) 1633 2) -H. Adachi, T. Kawaguchi, K. Setsune, K. Ohji and K, Wasa: J Appl. Phys. Lett. 42 (1983) 867. 3) T. Shiozaki, M. Adachi, A. Mochizuki and A, Kawabata Ferroelectrics 63 (1985) 227 4). Aurivilis: Ark. Kem, 1 (1939) 463, 5) B, Aurivlis: Ark. Kem, § (1952) 39 ©) C.F, Pulvari and A. S. dela Paz: J. Appl. Phys. 37 (1966) 1754 1) LE. Cross and R. C, Pohanka: J. Appl. Phys. 39 (1968) 3992, 8) S!E. 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