GB2077253A - Optically Useful Transparent Materials and Devices Containing Them - Google Patents

Abstract

Optically useful transparent ceramic materials having good transparency and good piezoelectric and electrooptic properties are useful e.g. in buzzers and electrooptical shutters. Each material consists of at least one crystallographically tetragonal ferroelectric solid solution material selected from: (1) (1- alpha )Pb(Zr-Ti)O3- alpha A1-z(M<I>1/2M<II>1/2)z(Zr-Ti)O3 in which 0.15</= alpha </=0.35 and 0.20</=z</=0.99, (2) (1- alpha )Pb(Zr-Ti)O3- alpha A(M<III>1/2M<IV>1/2)O3 in which 0.05</= alpha </=0.2, (3) (1- alpha )Pb(Zr-Ti)O3- alpha A(M<I>2/5M<V>3/5)O3 in which 0.1</= alpha </=0.25, (4) (1- alpha )PbA(Zr-Ti)O3-M<I>M<VI>O3 in which 0.035</= alpha </=0.12, and (5) (1- alpha )PbA(Zr-Ti)O3- alpha R2O3 in which 0.03</= alpha </=0.06 wherein A is at least one of Ba, Sr and Ca, M<I> is at least one of Li, Na and K, M<II> is at least one of La, Nd, Sm, In, Al and Sc, M<III> is at least one of La, Nd, Sm, In, Al, Sc and Bi, M<IV> is at least one of Nd, Ta, Sb and Bi, M<V> is at least one of W and Mo, M<VI> is at least one of Ta, Nb, Sb and Bi, and R is at least one of La, Nd and Sm.

Description

SPECIFICATION Optically Useful Transparent Materials and Optical Devices Containing Them The present invention relates to optically useful transparent ceramic materials, and to optical devices including such materials.

In this specification including the claims, a ceramic material used for optical devices such as a transparent window, an electrooptic shutter and a transparent optical buzzer is called "an optically useful transparent ceramic material".

Optically useful transparent ceramic materials are used mainly as piezoelectric materials in transparent vibrators used as sound sources in transparent sound-producing members for microtalking devices such as transparent buzzers for watches, small radios, small transceivers and talking watches, and also as electrooptic materials for electrooptic shutter devices for electrooptic shutters and stereoscopic glasses for observation of television pictures.

The techniques of micro-talking devices and optical elements using ceramic materials such as electrooptic shutters have become important, and their industrialization has recently been expedited.

Transparent ceramic materials to be used in such devices are required to have complete and excellent transparency, and are limited to ferroelectric transparent ceramics having a high piezoelectric or electrooptic effect.

Hotpress transparent ferroelectric ceramics such as (PbLa)(ZrTi)03, (PbSr)(ZrTi)03, (PbBa)(ZrTi)03 and (PaBaSr)(ZrTi)03 (hereinafter referred to as "PLZT", "PSZT" "PBZT" and "PBSZT" respectively) are available. They are fine and compact ceramics free of foams and have a very high transparency, see for example, the following references: US Patent 3,666,666 US Patent 4,019,915 To improve micro-talking devices and electrooptic shutter devices, we have done research on PLZT, PSZT, PBZT and PSBZT, to find optimum compositions.

It was found that the light transmitted by PLZT is somewhat colored. More specifically, when in an alarm analog quartz watch (in which time is indicated by mechanically turning parts) a transparent buzzer is formed by bonding PLZT to the cover glass, the dial is seen lightly yellow and the watch looks old and sun-burnt. Similarly, when, in an alarm digital quartz watch, a buzzer is formed by bonding PLZT to the cover glass the blue reflection is strong when the face is seen obliquely and the contrast of numbers or letters on the face is reduced, rendering it difficult to read the time. These disadvantages are not observed for PSZT, PBZT and PBSZT, and the dials in such cases appear colorless.

However, the hotpress temperatures for synthesis of PSZT, PBZT and PBSZT are 1300 to 1 4000 C, higher than the temperature of 12000C adopted for synthesis of PLZT. The high hotpress temperature requires not only a large quantity of energy but also exposure of a lead compound in an atmosphere maintained at a temperature higher than 13000C, which causes electric furnace materials and hotpress molds to be drastically deteriorated and damaged, with the result that synthesis costs and maintenance costs of the synthesis installation are increased. Manufacturing costs are considerably increased, which in practice is an industrially serious problem.

Accordingly, if it is possible to sinter such colorless transparent ceramics at temperatures lower than 1 25000, it will be possible to provide excellent devices that cannot be provided by the conventional ferroelectric transparent ceramics represented by PLZT, and this process will be very valuable industrially.

In accordance with the present invention, there is provided an optically useful transparent ceramic consisting essentially of at least one crystallographically tetragonal ferroelectric solid solution material selected from: (1) (1-&alpha;)Pb(Zr-Ti)O3-&alpha;A1-z(M1/2'M1/2")z(Zr-Ti)O3 in which 0.15#&alpha;#0.35 and 0.20#z#0.99, (2) (1-&alpha;)Pb(Zr-Ti)O3-&alpha;A(M2/5'M2/5v)O3 in which 0.05 < < 0.2, (3) (1-&alpha;)Pb(Zr-Ti)O3-&alpha;A(M2/5'M3/5v)O3 in which 0.1 < a < 0.25, (4) (1-a)PbA(Zr-Ti)03-M'MV03 in which 0.035 < a < 0.12, and (5) (1 -a)PbA(ZrJi)03-aR203 in which 0.03#&alpha;;#0.06 wherein A is at least one of Ba, Sr and Ca, M' is at least one of Li, Na and K, M" is at least one of La, Nd, Sm, In, Al and Sc, M"' is at least one of La, Nd, Sm, In, Al, Sc and Bi, Mlv is at least one of Nd, Ta, Sb and Bi, Mv is at least one of W and Mo, MV' is at least one of Ta, Nb, Sb and Bi, and R is at least one of La, Nd and Sm.

Each of these solid solution ceramics (1) to (5) is a tetragonal ferroelectric material.

A typical instant of the optical device of the present invention comprises a vibrating plane plate and a ceramic plate of a material of the invention interposed between a pair of light-transmitting electrodes, wherein said vibrating plane plate is arranged to be vibrated according to vibrations of said transparent ceramic plate.

We will now give a further explanation of the invention and examples, with reference to the accompanying drawings, in which: Figure 1 is a phase diagram of an example of the transparent ceramic material of the present invention, Figure 2 is a diagram illustrating transmittances of various transparent ceramic materials, Figures 3 and 4 are longitudinal sections of transparent buzzers including optically useful transparent ceramic materials, Figure 5 is a longitudinal section of a small electronic device including an optically useful transparent ceramic material, Figures 6 and 7 are diagrams showing the top plane and section of an electrooptic shutter device, Figure 8 is a perspective diagram showing another example of an electrooptic shutter device.

We have experimented with low-temperature sintering of optically useful transparent ceramic materials. Low-temperature sintering is achieved by addition of elements necessary for transparency, for example, Ba and Sr, in compounds that enable low-temperature sintering. Optically useful transparent ceramic materials which have good transparency in high piezo-electric and electrooptic effects are sought.

When a compound of Ba, Sr or other element is added as a doping substance to a solid solution to improve the sintering property, it cannot be said that elements forming such compound are not critical. In other words, certain requirements should be satisfied. For example, when the compound formed is a solid solution in a PZT[Pb(Zr-Ti)031 system, the transparency of this material should not be reduced. Incidentally, Pb(Zr-Ti)03 is a solid solution of PbZrO3 and PbTiO3. Similar expressions are adopted for other compounds. We examined variation of transmittance when all the elements are independently added to ceramic materials of the perovskite structure, and we have found a rule that the effects of doping elements are roughly divided according to the groups of the Periodic Table.

More specifically, the transmittance is hardly affected by addition of elements of group I such as Li, Na, K, Rb, Cs, Cu, Ag and Au and elements of group II such as Be, Mg, Ca, Sr, Ba, Zn, Cd and Hg, but the transmittance is improved by addition of elements of the group Ill such as B, Sc, Y, Al, Ga, In and TI, elements of the group V such as V, Nb, Ta, N, P, As,- Sb and Bi, elements of the group VI such as Cr, Mo, W, Se and Te, and rare earth element. On the other hand, the transmittance is impaired by addition of elements of the group VII such as Mn, Tc, Re, Cl, Br, I and At and elements of the group VIII such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.

The elements capable of improving the transmittance of PSZT, PBZT, (PbCa)(ZrTi)03, i.e. PCZT or (PbBaSrCa)(ZrTi)03, i.e. PBSCZT on doping are mainly La, Sm, Nd, Sc, Al, In, Bi, Sb, Nb, Ta and W. Each of these elements has the effect of improving the sintering property. Accordingly, these elements may be used conveniently.

When rare earth elements such as La, Sm and Nd are singly added in the form of (Ba,Sr,Ca)1~xLaxTir x/403, (Ba,Sr,Ca)1~xNdxTi~x/403 or (Ba,Sr),~xSmxTi~xz403 as in case of PLZT, if the amount of Sm or Nd exceeds 5%, the resulting product becomes opaque, presumably because it is not a complete solid-solution. When the amount of La exceeds 5%, the product becomes prominently yellowish though no turbidity is observed, and in this case, a defect similar to that observed in the case of PLZT becomes conspicuous. Accordingly, in the case of single addition of La, Sm or Nd, the upper limit of the amount added is 5%.

One of the reasons why Sm or Nd is hardly solid-dissolved in an amount exceeding 5% is that Sm or Nd is a trivalent element. More specifically, in the pervoskite structure of the ABO3 type, a part of the divalent ion A is replaced by a part of the tetravalent ion B and lattice defects are readily formed because of asymmetry of the atomic valency, and therefore, the transmittance is degraded if the amount of such doping element exceeds 5%.

As a way of eliminating this disadvantage, there may be considered a method in which La, Sm or Nd is not added singly but is combined with a monovalent element and added in the form of an effectively divalent ion, such as (Li112La112), (Ka1/2Sm"2) or (Na112Nd112), for substitution of Ba or Sr on the site A. If this method is adopted, the transmittance is hardly impaired even if the amount added is increased. A solid solution to be added to PZT is represented by the following general formula: [(BaSrCa)1-x(M1/2'M1/2")x](Zr-Ti)O3 (1) wherein M' stands for Li, Na or K, and M" stands for La, Nd, Sm, In, Al or Sc.

It is preferred that the amount of substitution of this type for PZT be in a range of 1 5 to 35 mol %.

Then, an equivalent to a tetravalent element providing a better sintering property than Ti is used for substitution of the site B. No tetravalent element is included among applicable doping elements.

Accordingly, a trivalent element and a pentavalent element are combined so that an equivalent to a tetravalent element is obtained. More specifically, a solid solution of the following general formula is added: (BaSrCa)(M1/2IIIM1/2IV)O3 (2) wherein M111 stands for La, Nd, Sm Sc, Al, In or Bi, and Mlv stands for Nb or Ta.

It is preferred that the amount of substitution of this type for PZT be in a range of 5 to 20 mol %.

Alternatively, a combination of a monovalent element and a hexavalent element, represented by the following general formula, may be added: (Ba,Sr,Ca)(M2/5IM3/5V)O3 (3) wherein Ml stands for Li, Na or K, and MV stands for W or Mo.

It is preferred that the amount of substitution of this type for PZT in a range of 10 to 25 mol %.

Furthermore, a solid solution represented by the following general formula may be added to PbA(Zr-Ti)03: MlMvlO3 (4) wherein M' stands for Li, Na or K, and MV' stands for Ta, Nb, Sb or Bi.

It is preferred that the amount of substitution of this type for PZT be in a range of 3.5 to 12 mol %.

Furthermore, a doping substance represented by the following formula is added as a solid solution to the above-mentioned PbA(Zr-Ti)03: R203 (5) wherein R stands for La, Nd or Sm.

It is preferred that the amount of doping substance of this type in PZT be in a range of 3 to 6 mol %.

These five kinds of the additives may be separately used, or two or more of them or all of them may be used simultaneously. More specifically, a predetermined amount of a powder of SrTiO3, CaTiO3, BaTiO3 or (Ba,Sr,Ca)TiO3 is added to powders of PbO, ZrO2 and TiO2 as raw materials for synthesis of transparent ceramic materials of PBZT, PSZT, PCZT and PBSCZT, and the mixture is calcined to obtain a powder of the PbZrO3-PbTiO3-(Ba,Sr,Ca)TiO3 system and this powder is subjected to hot pressing to obtain a transparent ceramic material. The mixing ratio by which weighing of the starting powders is conducted is determined according to the kind of the additive so that the conditions of the chemical composition formula described below will be satisfied.

In the present invention, the above-mentioned five kinds of solid solutions having a good -sintering property are added to PbZrO3-PbTiO3. Accordingly, the chemical compositions of the obtained transparent ceramic materials may be expressed as follows.

Class I Pb1~,7[(Ba ,~g~TSrCat) 1-x(M1/2'M1/2)x]# (Zr1~yTiy)03 (6) wherein M' stands for Li, Na or K, and M" stands for La, Nd, Sm, In, Al or Sc.

Class II (Pb1-x1-x2-x3Bax1Srx2Cax3)[Zr1-y1-y2Tiy1(M1/2IIIM1/2IV)y2]O3 (7) wherein MIII stands for La, Nd, Sm, Sc, Al, In or Bi, MIV stands for Nb, Ta, or Sb, and y2 is equal to (xl +x2).

Class III (Pb1-x1-x2Bax1Srx2)[Zr1-y1-y2Tiy1(M2/5IM3/5V)y2]O3 (8) wherein M' stands for Li, Na or K, MV stands for W or Mo, and y2 is equal to (x1 +x2).

Class IV (Pb1-x1-x2-x3Bax1Srx2Cax3)(Zr1-yTiy)O3-MIMVI)3 (9) wherein M' stands for Li, Na or K, and MV' stands for Ta, Nb, Sb or Bi.

Class V (Pbl-x1-x2-x3-x4Baxl Srx2Cax3Rx4) (Zr1~yTiy)o3 (10) wherein R stands for La, Nd or Sm.

The five kinds of solid solutions are independently classified and expressed above, but it is not necessary to regard these solid solutions as being distinguishable from one another. These are basic types for use in classifying the solid solutions of the present invention, and combinations of these basic types are included in the scope of the optical ceramic material of the present invention. For example, 0.88Pb0,694ln0,136Ba0,17(Zr0,Ti0,5)0,966030.12NaNb03 of Class IV shown in Fig. 1 may be regarded as a solid solution of [Pb0,61Ba0,15(ln112Na112)0,24j(Zr0,6Ti0,5)0,8Nb0,12O3 which corresponds to a combination of the formula (6) of Class I and the formula (9) of Class IV.

These solid solutions which are ferroelectric materials of the perovskite structure belonging to the tetragonal system are valuable as optically useful transparent ceramic materials.

An example of a process for the preparation of these solid solutions will now be described.

Predetermined weighed amounts of starting oxide powders are added to the solid solution as the matrix to form a starting material mixture powder. The powder is wet-blended in a ball mill and evaporated to dryness. Then, the mixture is heated at about 6000C, and the temperature is elevated to 8000C at a temperature-elevating rate of 1 C/min and the mixture is maintained at about 8000C for 5 to 10 hours. Then, the mixture is cooled to room temperature, roughly pulverized in a mortar and blended in a ball mill again by using acetone as a solvent. Then, the powder is maintained at 7000C for 1 hour to remove the organic substance. The resulting calcined powder is molded under a pressure of 100 Kg/cm2, for example, into a column having a diameter of 30 mm and a height of 1 5 mm.The compacted powder is placed in an alumina mold and powdery stabilized zirconia is filled around the compacted powder. Then, an alumina punch rod is charged in the mold and the mold is set in an electric furnace. The temperature is gradually elevated while keeping a vacuum of 10-2 Torr in the electric furnace. When the temperature in the electric furnace is elevated to 7000C, oxygen gas is introduced into the furnace. While oxygen is allowed to flow at a low speed, heating is continued, and when the temperature is elevated to 9000C, the pressure is gradually elevated through the punch rod to a maximum level of 350 Kg/cm2 which is then maintained. The temperature-elevating and pressure elevating rates are adjusted to about 1 C/min and about 1 Kg/min, respectively, and the maximum temperature of 12500C is maintained for 5 to 10 hours.Then, the product is gradually cooled to room temperature. It is important that the hot pressing operation should be carried out iri an oxygen gas as described above. A sintered ceramic obtained by conducting hot pressing under the above conditions is taken out from the alumina mold by using a core drill and annealed at about 6000C for about 1 hour.

Then, the ceramic is sliced in a thickness of about 0.5 mm and both surfaces are subjected to rough polishing, mirror polishing and sharp polishing to obtain a disc-like wafer having a thickness of 0.2 mm.

A transparent electrode film of the In203-SnO2 system is applied to each of the two main surfaces of the wafer and the wafer is subjected to a poling treatment by applying a direct current voltage of 500 volts between the electrodes for a certain time to obtain a piezoelectric material. In the case of a shutter element, after annealing, the ceramic is cut into a cube, metal electrodes are applied to the upper and lower surfaces of the cube and the poling treatment is carried out by applying a direct current voltage of scores of thousands of volts between the electrodes for several hours to produce an electric field of about 20 KV/cm2. After the poling treatment, the electrodes are removed, and the cube is sliced in a slice thickness of 0.5 mm in the voltage-applied direction. Then, the slice is polished in the same manner as described above to form a square sheet. Then, transparent electrodes are deposited on both the main surfaces by sputtering at room temperature to form a shutter element.

Various properties, such as transparency, Curie temperature, transmittance, dielectric constant, electromechanical coupling factor and electrooptic constant, of transparent ceramics prepared according to the above synthesis process are shown in Tables 1 through 5.

In these Tables, asterisked samples are materials of the different crystal system showing scattering of light.

Table 1 Class I, A Site Substitution Type (1-&alpha;)Pb(Zr1-yTi)O3-&alpha;[(Ba,Sr,Ca)1-x(M1/2'M1/2")x[(Zr1-yTiy)O3 I-1 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V &alpha;Ba(Na1/2La1/2) &alpha;=22 50 55 45 115 36 34 68 64 4320 58 5.8 =24 50 55 45 105 37 34 69 65 4410 59 5.7 &alpha;Ba(Li1/2La1/2) &alpha;=22 50 55 45 118 35 33 67 63 4120 55 5.8 =24 50 55 45 108 35 33 68 64 4210 56 5.7 &alpha;Ba(K1/2La1/2) &alpha;=22 50 55 45 123 33 30 65 61 3830 53 5.5 =24 50 55 45 113 33 31 66 62 3920 54 5.4 &alpha;Ba(Na1/2Nd1/2) &alpha;=22 50 55 45 117 34 32 68 64 4170 58 5.8 =24 50 55 45 107 35 33 69 65 4260 59 5.7 &alpha;;Ba(Li1/2Nd1/2) &alpha;=24 50 55 45 110 33 31 67 63 3970 56 5.7 &alpha;Ba(K1/2Nd1/2) &alpha;=24 50 55 45 115 31 29 65 61 3770 53 5.5 &alpha;Ba(Na1/2Sm1/2) &alpha;=22 50 55 45 100 30 28 65 62 2860 54 5.3 &alpha;Sr(Na1/2La1/2) &alpha;=2 50 55 45 105 34 32 66 62 3520 65 5.7 &alpha;=24 50 55 45 95 35 32 67 63 3610 66 5.7 Table 1 (cont.).

Class I, A Site Substitution Type (1-&alpha;)Pb(Zr1-yTi)O3-&alpha;[(Ba,Sr,Ca)1-x(M1/2'M1/2")x[(Zr1-yTiy)O3 I-1 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V &alpha;Sr(Li1/2La1/2) &alpha;=24 50 55 45 98 33 31 65 61 3410 63 5.6 &alpha;Sr(K1/2La1/2) &alpha;=22 50 55 45 113 32 29 64 60 3030 60 5.5 &alpha;Sr(Na1/2Nd1/2) &alpha;=22 50 55 45 107 33 31 67 63 3360 64 5.7 &alpha;Sr(Li1/2Nd1/2) &alpha;=24 50 55 45 100 31 29 65 61 3260 61 5.6 &alpha;Ca(Na1/2La1/2) &alpha;=20 50 55 45 97 35 33 67 63 3130 60 5.7 &alpha;=24 50 55 45 88 36 33 68 64 3210 61 6.5 &alpha;Ca(Li1/2La1/2) &alpha;=24 50 55 45 90 34 32 66 62 3010 58 5.7 &alpha;;Ca(K1/2La1/2) &alpha;=22 50 55 45 105 33 30 65 61 2630 58 5.6 &alpha;Ca(Na1/2Nd1/2) &alpha;=22 50 55 45 99 34 32 68 64 2960 60 5.8 &alpha;Ca(Li1/2Nd1/2) &alpha;=24 50 55 45 92 32 30 67 62 2850 58 5.7 &alpha;Ca(Na1/2Sm1/2) &alpha;=16 50 55 45 105 30 28 65 60 1970 63 5.5 Table 1 (cont.).

Class I, A Site Substitution Type (1-&alpha;)Pb(Zr1-yTi)O3-&alpha;[(Ba,Sr,Ca)1-x(M1/2'M1/2")x[(Zr1-yTiy)O3 I-1 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V &alpha;Ba1-x(Na1/2La1/2)zO3 &alpha;=20 99 55 45 120 31 29 66 64 4220 54 6.2 =20.4 90 55 45 118 31 29 66 64 4240 54 6.2 =20.8 80 55 45 116 32 30 67 64 4260 55 6.1 =21.3 70 55 45 114 34 32 68 65 4280 56 6.0 =21.7 60 55 45 112 35 33 68 65 4300 57 5.9 =22.2 50 55 45 107 37 34 69 66 4350 60 5.5 =22.7 40 55 45 106 35 32 67 65 4370 61 5.3 =23.2 30 55 45 104 20 18 45 42 4450 61 5.1 =23.7 20 55 45 102 15 13 42 40 4530 61 5.0 &alpha;;=20.5 50 60 40 115 31 28 66 60 4270 58 6.1 =24 50 50 50 114 35 34 69 66 4420 56 5.8 =25.8 50 45 55 113 34 33 65 63 4500 54 5.7 =27.5 50 40 60 112 33 32 60 58 4560 52 5.6 =29.4 50 35 65 111 32 31 58 57 4610 50 5.5 &alpha;=31.1 50 30 70 105 30 29 60 59 4660 50 5.7 =32.9 50 25 75 104 25 24 57 57 4720 48 5.5 =34.6 50 20 80 103 15 15 42 42 4780 46 5.5 &alpha;=18.3 99 60 40 112 30 27 66 64 4180 56 6.2 Table 2 Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-1 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V 1* Sr(La1/2Nb1/2)O3 5.8 62.5 37.5 178 15 8 45 25 2005 43 6.5 2* 6.0 63 37 166 17 9 47 27 2075 44 6.5 3 60 40 179 14 8 43 25 2050 42 6.3 4* 7.0 65 35 114 25 17 55 35 3035 45 5.8 5 60 40 140 23 20 60 58 2932 43 5.0 6 55 45 163 16 14 45 40 2075 40 6.2 7* 7.5 67.5 32.5 78 27 - 57 - 40 10 - 8 60 40 119 25 20 62 58 3000 37 5.6 9 50 50 167 14 13 42 40 2069 39 6.2 10 8.0 65 35 70 42 - 69 - 4028 - 11 53 47 134 24 21 62 60 2764 42 4.8 10.2 12 47 53 161 14 12 42 42 2040 37 6.1 13 9.0 60 40 52 42 - 69 - 4087 - 14 50 50 103 25 22 61 59 3134 34 6.1 15 40 60 150 14 12 43 42 2615 35 6.0 16 10.0 55 45 35 41 - 67 - 4009 - 17 50 50 60 39 36 66 64 3150 34 5.3 18 40 60 108 23 23 60 60 2780 39 4.5 19 32.5 67.5 148 13 13 40 40 2550 35 5.9 20 12.0 40 60 163 36 - 64 - 3930 - 21 30 70 61 24 24 58 57 2750 30 5.3 22 20 80 126 8 8 34 34 1770 22 3.0 23 13.0 35 65 20 32 - 59 - 3520 - 24 25 75 57 20 20 45 45 2150 27 4.9 25 20 80 82 17 17 42 42 1450 25 4.5 26 14.0 20 80 39 24 - 53 - 2350 - 27* Sr(La1/2Ta1/2)O3 5.0 62.5 37.5 170 15 8 45 25 2001 42 6.4 28* 6.0 65 35 121 24 16 55 35 3050 44 5.8 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-1 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V 29 60 40 140 23 20 59 57 2928 43 5.0 30 55 45 175 15 13 44 40 2059 40 6.3 31 7.0 65 35 74 42 - 68 - 4035 - 32 55 45 128 27 24 64 62 2956 41 4.7 33 47 53 163 14 13 43 43 2060 37 6.2 34 8.0 60 40 52 45 - 69 - 4093 - 35 53 47 90 25 20 64 60 2985 35 6.2 36 40 60 150 15 13 44 42 2007 34 5.9 37 10.0 45 55 32 37 - 65 - 3979 - 38 35 65 84 24 22 62 61 2530 32 5.5 39 20 80 170 8 8 32 30 1754 22 3.1 40 12.0 30 70 37 28 - 54 - 3525 - 41 20 80 84 23 22 52 51 2290 30 5.2 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-2 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Sr(Nd1/2Nb1/2)O3 8.0 60 40 100 35 32 63 61 2740 43 4.5 55 45 126 23 20 61 59 2460 42 4.7 9.0 50 50 108 24 21 60 58 2550 34 6.0 10.0 45 55 90 30 29 62 61 2812 35 4.8 Sr(Nd1/2Ta1/2)O3 7.0 60 40 99 35 32 63 61 2750 42 4.5 55 45 125 23 20 61 59 2427 41 4.7 8.0 50 50 107 24 21 60 58 2565 34 6.0 9.0 45 55 89 30 29 62 61 2825 35 4.8 Sr(Sm1/2Nb1/2)O3 7.0 65 35 98 34 31 66 64 3503 42 4.6 7.5 60 40 101 33 31 65 63 3000 39 5.3 8.0 50 50 131 20 18 64 52 2496 35 6.0 Sr(Sm1/2Nb1/2)O3 6.0 65 35 97 34 31 66 64 3510 42 4.5 6.5 60 40 100 33 31 65 63 3020 40 5.2 7.0 50 50 130 20 18 64 52 2515 35 5.9 Sr(In1/2Nb1/2)O3 14.0 60 40 118 29 28 56 54 1840 32 4.6 50 50 150 27 26 54 52 1350 29 4.5 15.0 60 40 100 31 30 58 56 2110 34 4.5 50 50 132 29 28 57 55 1580 30 4.4 50 50 115 30 29 58 56 1790 29 4.3 Sr(In1/2Ta1/2)O3 14.0 60 40 115 29 28 56 54 1850 32 4.6 15.0 60 40 95 31 30 58 56 2120 34 4.5 16.0 55 45 95 32 31 58 56 2070 33 4.4 Sr(Al1/2Nb1/2)O3 15.0 50 50 115 28 27 56 54 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-2 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Sr(Sc1/2Nb1/2)O3 15.0 60 40 95 31 30 60 59 1860 33 4.5 16.0 55 45 90 32 31 60 59 1800 31 4.3 Sr(1/21/2)O3 7.0 65 35 115 31 27 59 57 2105 38 3.2 7.5 65 35 110 30 30 58 56 2520 39 3.3 8.0 65 35 68 32 31 60 58 2810 41 3.3 Sr(1/21/2)O3 7.0 65 35 122 31 29 59 58 2085 38 3.2 7.5 65 35 116 31 29 59 58 2500 39 3.2 8.0 65 35 94 32 30 60 58 2790 41 3.3 Sr.9Ba.1(La1/2Nb1/2)O3 10 50 50 68 41 38 65 62 3180 36 5.4 Sr.9Ba.1(La1/2Ta1/2)O3 9 50 50 136 25 20 64 60 2757 34 5.9 Sr.8Ba.2(Nd1/2Nb1/2)O3 8 60 40 107 37 34 65 63 2780 43 4.5 Sr.8Ba.2(Nd1/2Ta1/2)O3 7 60 40 106 37 34 65 63 2790 42 4.5 Sr.8Ba.2(In1/2Nb1/2)O3 16 55 45 107 34 32 60 58 2100 33 4.4 Sr.8Ba.2(In1/2Ta1/2)O3 16 55 45 102 33 31 60 57 2230 33 4.4 Sr.9Ba.1(La1/2Nb1/2)O3 10 50 50 66 40 37 64 61 3170 36 5.4 Sr.8Ba.2(Nd1/2Nb1/2)O3 8 60 40 105 36 33 64 62 2760 43 4.5 Sr.8Ba.2(In1/2Nb1/2)O3 16 55 45 105 33 31 59 57 2085 33 4.4 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-3 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V * Ba(La1/2Nb1/2)O3 7.0 65 35 161 36 30 59 54 3280 46 6.3 60 40 173 35 30 58 54 2222 45 5.9 * 7.5 70 30 129 43 25 68 65 4070 47 6.3 60 40 160 37 35 64 62 2672 42 5.7 50 50 192 14 10 53 50 2188 42 5.8 8.0 65 35 125 42 39 70 68 4132 44 6.1 60 40 140 40 38 68 66 3056 40 5.5 50 50 172 25 22 58 55 1750 42 5.9 * 9.0 70 30 73 45 - 70 - 5025 - - 20 60 40 103 43 36 72 70 397036 5.0 55 45 119 42 37 73 71 3300 38 5.5 50 50 134 40 36 72 70 2615 39 5.7 40 60 167 14 10 63 60 2076 40 5.6 10 65 35 53 46 - 74 - 4997 - - 17 50 50 100 42 40 73 71 3190 35 4.9 40 60 131 27 26 65 63 2610 40 5.3 30 70 162 17 16 42 42 2020 36 5.1 11 50 50 64 44 - 72 - 4750 - 40 60 95 39 35 62 60 2850 34 4.7 30 70 126 30 29 51 48 2617 33 4.6 20 80 157 17 10 55 50 2509 27 4.1 12 40 60 59 41 - 63 - 4530 - 30 70 90 39 32 61 58 3150 29 4.3 20 80 121 25 20 58 54 2550 25 3.6 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-3 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Ba(La1/2Ta1/2)O3 7 70 30 110 32 20 65 42 4060 47 6.3 60 40 141 27 25 58 55 2680 42 6.3 50 50 172 13 9 51 47 2190 42 5.8 8 70 30 72 35 - 65 - 3650 - 5.1 60 40 103 33 30 70 67 3620 39 5.6 50 50 134 31 29 61 57 2290 40 5.8 40 60 167 13 12 47 46 2770 39 5.7 9 65 35 53 35 - 70 - 4700 - 50 50 100 31 27 62 60 2911 33 4.9 40 60 131 20 16 57 55 2350 38 5.0 30 70 162 12 11 40 40 1770 34 10 40 60 95 29 25 60 57 2880 33 4.5 30 70 126 20 17 50 47 2650 32 4.4 Ba(La1/2Sb1/2)O3 8 65 35 137 23 17 58 54 3606 37 5.0 9 65 35 101 25 22 59 56 4051 36 4.8 55 45 132 24 22 58 56 2925 38 5.1 10 65 35 65 27 - 57 - 4500 - 50 50 112 24 20 56 54 2715 35 4.7 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-4 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Ba(Nd1/2Nb1/2)O3 8.0 60 40 142 40 38 64 61 3000 40 5.5 9.0 55 45 120 41 38 66 63 3258 38 5.5 50 850 135 40 37 67 64 2597 39 5.7 10 50 50 102 40 37 64 62 3150 35 4.9 40 60 132 27 26 60 58 2537 40 5.3 Ba(Nd1/2Ta1/2)O3 8.0 60 40 110 35 32 60 56 3250 40 5.7 9.0 50 50 102 33 29 64 62 2889 33 4.9 Ba(Sm1/2Nb1/2)O3 8.0 60 40 110 35 32 60 56 3250 40 5.7 9.0 55 45 100 36 33 62 58 3521 39 5.6 50 50 115 35 31 62 59 2846 40 5.8 10.0 50 50 82 35 31 60 56 3407 36 5.1 40 60 115 14 10 45 40 2830 41 5.4 Ba(Sm1/2Ta1/2)O3 8.0 60 40 90 33 30 60 56 3817 38 5.4 Ba(Al1/2Nb1/2)O3 15.0 50 50 132 30 27 58 54 2440 46 Ba(In1/2Nb1/2)O3 15.0 60 40 118 33 32 61 59 2210 34 4.8 50 50 150 31 30 59 57 1720 31 4.7 16.0 60 40 100 35 34 64 62 2480 36 4.7 50 50 132 33 32 63 61 195032 4.6 17.0 55 45 100 36 35 64 62 2430 35 4.6 50 50 115 34 33 64 620 2150 31 4.5 Ba(In1/2Ta1/2)O3 15.0 60 40 100 27 25 58 56 2460 32 4.6 16.0 55 45 98 29 27 59 57 2384 31 4.4 50 50 115 27 25 58 55 2209 30 4.3 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-4 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Ba(Sc1/2Nb1/2)O3 15.0 60 40 115 32 31 64 63 2230 34 4.6 16.0 55 45 112 34 33 63 62 2176 32 4.4 50 50 130 32 30 60 59 1973 30 4.3 Ba(Nd1/2Sb1/2)O3 9 65 35 103 25 23 59 57 3985 34 4.7 55 45 133 24 22 58 56 2870 36 5.0 Ba.8Sr.2(La1/2Nb1/2)O3 9 55 45 110 43 37 68 63 3200 38 5.5 Ba.8Sr.2(La1/2Ta1/2)O3 8 50 50 124 32 30 62 59 2150 40 5.8 Ba.9Sr.1(La1/2Nb1/2)O3 10 50 50 103 38 34 63 57 3230 35 5.2 Ba.5Sr.5(La1/2Nb1/2)O3 9 55 45 110 42 37 67 63 3150 39 5.5 Ba.8Sr.2(La1/2Ta1/2)O3 8 55 45 108 32 30 61 58 2800 40 5.6 Ba.8Sr.2(La1/2Sb1/2)O3 9 55 45 122 24 22 59 56 2950 38 5.1 Ba.8Sr.2(Nd1/2Nb1/2)O3 9 55 45 110 41 38 66 63 3300 39 5.5 Ba.8Sr.2(Nd1/2Ta1/2)O3 8 60 40 110 35 32 63 60 3700 39 5.5 Ba.8Sr.2(Nd1/2Nb1/2)O3 9 55 45 110 41 38 66 63 3200 38 5.6 Ba.8Sr.2(Nd1/2Ta1/2)O3 9 60 40 100 36 33 64 61 3400 38 5.6 Ba.8Sr.2(In1/2Nb1/2)O3 16 50 50 122 34 33 64 62 2200 33 4.6 Ba.8Sr.2(In1/2Nb1/2)O3 16 50 50 120 35 34 65 63 1900 32 4.6 Ba.8Sr.2(In1/2Ta1/2)O3 16 50 50 105 27 25 58 55 2150 30 4.3 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-5 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V * Ca(La1/2Nb1/2)O3 6.0 65 35 148 38 20 65 55 1650 42 3.4 7.0 65 35 119 40 35 67 62 2300 43 3.3 7.5 68 32 90 42 - 74 - 3142 - 60 40 128 34 32 69 67 3004 42 3.6 8.0 65 35 98 41 - 74 - 3008 - 60 40 114 39 37 73 70 2700 42 3.3 55 45 138 38 36 72 69 2384 42 3.3 50 50 162 25 22 63 58 1937 41 3.4 8.6 50 50 145 36 26 68 66 2523 43 2.3 9.0 55 45 103 38 - 73 - 3030 - 50 50 133 37 33 70 68 2867 42 3.1 40 60 157 30 23 60 55 2312 4.0 3.0 30 70 181 10 5 45 30 1869 4.1 3.0 10.0 30 70 152 24 - 60 - 3010 - Ca(La1/2Ta1/2)O3 7.0 65 35 94 32 27 65 61 2275 41 3.4 7.5 60 40 103 28 26 65 63 2986 40 3.5 8.0 60 40 89 30 28 68 66 2654 40 3.2 55 45 113 32 30 65 63 2351 40 3.2 9.0 50 50 109 28 23 67 65 2820 40 3.0 40 60 157 20 16 56 50 2300 39 2.9 Ca(La1/2Sb1/2)O3 7.0 65 35 120 34 31 62 57 2002 38 3.2 7.5 65 35 115 33 30 63 58 2421 39 3.3 8.0 65 35 91 35 32 63 58 2708 41 3.3 60 40 115 24 21 62 57 2418 38 3.1 55 45 139 22 28 59 54 2084 38 3.1 9.0 55 45 111 28 25 60 55 27 44 38 2.9 50 50 135 26 23 60 55 2530 35 2.8 40 60 183 20 17 36 27 2017 33 2.7 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-5 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Ca(Nd1/2Nb1/2)O3 7.0 65 35 124 39 35 66 61 2630 43 3.3 7.5 65 35 109 40 33 67 64 3065 42 3.7 8.0 60 40 119 35 30 66 63 2679 42 3.3 9.0 50 50 138 34 30 64 61 2244 42 3.1 Ca(Nd1/2Ta1/2)O3 7.0 65 35 100 30 28 65 61 2252 40 3.4 8.0 60 40 95 32 29 66 62 2628 41 3.2 9.0 50 50 114 28 26 64 60 2017 39 3.3 Ca(Nd1/2Sb1/2)O3 7.5 65 35 117 33 30 63 58 2400 39 3.3 8.0 65 35 103 35 32 63 58 2685 41 3.3 Ca(Sm1/2Nb1/2)O3 7.0 65 35 104 34 31 60 56 2530 42 3.3 8.0 55 45 123 34 31 61 57 2652 41 3.2 9.0 50 50 118 33 30 61 57 2494 42 3.1 Ca(Sm1/2Ta1/2)O3 6.0 65 35 108 32 30 59 56 1835 41 3.3 7.0 55 45 127 32 29 59 56 2485 42 3.2 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-6 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Ca(In1/2Nb1/2)O3 15 60 40 109 32 31 60 58 2160 33 4.8 50 50 141 29 28 58 56 1650 30 4.6 16 60 40 91 34 33 63 60 2430 35 4.6 55 45 110 33 32 62 59 2180 33 4.6 50 50 128 32 31 61 58 1910 30 4.6 17 55 45 105 35 34 63 60 2380 34 4.5 50 50 124 33 32 63 60 2120 30 4.5 Ca(In1/2Ta1/2)O3 15 50 50 136 29 28 58 56 1670 30 4.6 16 50 50 124 32 31 61 58 1920 30 4.6 17 50 50 118 33 32 63 60 2140 30 4.5 Ca(In1/2Sb1/2)O3 15 60 40 119 24 21 52 50 1860 30 4.6 16 60 40 101 26 23 55 53 2130 32 4.4 55 45 120 25 22 54 52 1880 30 4.4 Ca(Al1/2Nb1/2)O3 15 55 45 98 28 26 59 55 2460 45 4.0 50 50 114 29 27 60 56 2190 43 4.2 16 50 50 106 30 28 61 57 2410 44 4.1 Ca(Al1/2Ta1/2)O3 15 55 45 93 28 25 59 56 2480 45 4.0 50 50 109 29 26 60 57 2210 43 4.2 16 50 50 101 30 28 61 58 2430 44 4.1 Ca(1/21/2)O3 15 60 40 104 32 30 60 58 2180 33 4.8 16 50 50 105 33 31 62 60 2200 33 4.7 Ca(1/21/2)O3 15 60 40 99 31 29 58 56 2150 32 4.6 16 50 50 100 32 30 60 58 2170 32 4.6 Table 2 (cont.).

Class II, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M1/2IIIM1/2IV)O3 II-6 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V Ca(Bi1/2Nb1/2)O3 14 50 50 100 23 21 54 52 1810 30 4.8 15 50 50 90 32 - 55 - 2060 Ca(Bi1/2Ta1/2)O3 14 50 50 95 22 20 52 50 1840 30 4.6 15 50 50 85 22 - 54 - 2090 Ca.8Sr.2(La1/2Nb1/2)O3 10 50 50 91 35 29 68 64 3420 32 5.0 Ca.8Sr.2(La1/2Ta1/2)O3 9 50 50 90 36 30 68 64 3430 32 5.0 Ca.8Sr.2(Nd1/2Nb1/2)O3 8 60 40 110 38 33 69 66 2830 45 3.3 Ca.8Sr.2(Nd1/2Ta1/2)O3 9 50 50 105 30 28 66 62 2260 40 3.3 Ca.8Sr.2(In1/2Nb1/2)O3 16 55 45 100 34 33 63 61 2380 34 4.6 Ca.8Sr.2(In1/2Ta1/2)O3 17 50 50 115 34 33 64 61 2340 31 4.5 Ca.8Sr.2(La1/2Nb1/2)O3 7.5 68 32 100 42 39 70 66 3250 45 3.3 Ca.8Sr.2(La1/2Ta1/2)O3 7.0 65 35 104 33 28 66 62 2380 42 3.4 Ca.8Sr.2(La1/2Sb1/2)O3 8.0 65 35 101 36 33 64 59 2810 42 3.3 Ca.8Sr.2(Nd1/2Nd1/2)O3 7.5 65 35 119 41 34 68 65 3170 42 3.7 Ca.8Sr.2(Nd1/2Ta1/2)O3 8.0 60 40 105 33 30 67 63 2730 42 3.2 Ca.8Sr.2(In1/2Nb1/2)O3 16 60 40 101 35 34 64 61 2530 36 4.6 Ca.8Sr.2(In1/2Ta1/2)O3 18 50 50 110 34 33 64 61 2350 32 4.5 Ca.8Sr.2(In1/2Sb1/2)O3 16 60 40 111 27 23 56 64 2250 33 4.4 Ca.8Sr.2(La1/2Nd1/2Nb1/2)O3 7.5 65 35 106 42 40 70 67 3200 43 3.5 Table 3 Class III, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M2/5IM3/5V)O3 III-1 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTi)O3 ture before after before after Constant Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/v m/V * Sr(Na1/2W3/5)O2 13 65 35 118 26 20 62 58 1615 62 5.2 60 40 142 13 10 50 47 1411 59 5.3 14 65 35 95 27 20 63 58 1818 64 5.1 60 40 120 20 17 56 54 1614 59 5.2 15 60 40 95 25 22 61 59 1823 60 5.1 55 45 122 18 16 54 52 1602 57 5.2 16 55 45 98 23 21 59 57 1759 59 5.1 50 50 123 16 14 52 50 1583 55 5.2 17 50 50 101 21 19 57 55 1408 55 5.0 40 60 143 16 15 52 50 1398 49 4.9 18 45 55 95 20 18 56 55 1790 55 4.7 35 65 142 14 13 49 48 1321 48 4.6 20 35 65 100 19 18 55 54 1503 52 4.2 Table 3 Class III, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M2/5IM3/5V)O3 III-2 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol%) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V * Ba(Na2/5W3/5)O3 14 65 35 106 28 20 64 60 2219 54 5.5 15 65 35 82 29 21 65 61 2470 55 5.4 60 40 104 26 22 60 58 2222 49 5.6 16 60 40 80 28 24 62 60 2478 54 5.5 55 45 105 24 21 58 56 2102 48 5.7 50 50 128 20 17 54 52 1736 47 5.6 17 55 45 79 26 23 60 58 2374 52 5.5 50 50 103 22 20 56 54 1955 47 5.6 18 50 50 82 24 22 57 56 2169 49 5.3 45 55 105 18 16 52 51 1901 45 5.4 19 45 55 83 20 18 54 53 2126 48 5.4 40 60 103 16 15 50 49 1880 45 5.2 35 65 131 13 13 47 48 1633 44 4.8 Ca(Na2/5W3/5)O3 15 60 40 95 26 23 60 57 1601 52 5.5 55 45 122 21 19 56 54 1385 47 5.8 Table 3 (cont.).

Class III, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(M2/5IM3/5V)O3 III-3 Electro- Electrooptic Curie Transmittance (%) mechanical Constant Composition (mol %) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha; ;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp (%) m/V m/V Ca(Na2/5W3/5)O3 16 55 45 98 24 22 57 55 1576 49 5.7 50 50 123 18 16 52 50 1360 45 5.7 17 50 50 101 21 19 55 53 1548 49 5.6 45 55117 15 14 49 47 1336 45 5.5 18 45 55 95 18 17 52 50 1517 48 5.4 40 60 126 12 11 47 45 1307 44 5.3 (Ba.8Sr.2)(Na2/5W3/5)O3 16 55 45 103 24 22 58 56 2050 50 (Ba.5Ca.5)(Na2/5W3/5)O3 16 55 45 102 28 26 62 60 1850 49 (Ba.8Ca.2)(Li2/5W3/5)O3 16 55 45 110 21 19 53 51 1920 51 (Ca.8Sr.2)(Na2/5W3/5)O3 16 55 45 98 24 22 57 55 1580 53 Sr(Na2/5Mo3/5)O3 15 60 40 90 23 21 58 56 1715 56 Ca(Na2/5Mo3/5)O3 15 60 40 92 23 21 58 56 1510 48 Ba(Na2/5M3/5)O3 15 60 40 101 24 22 59 57 2120 45 * Sr(Li2/5W3/5)O3 13 65 35 121 22 16 57 52 1461 64 5.1 60 40 145 11 8 47 45 1263 60 5.2 Table 3 (cont.).

Class III, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(MI2/5MV3/5)O3 Electro- Electrooptic III-4 Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V * 14 65 35 98 24 17 60 55 1664 65 5.0 60 40 123 13 10 50 48 1464 60 5.2 15 60 40 98 16 13 55 53 1660 62 5.0 55 45 125 10 8 45 43 1452 59 5.2 16 55 45 101 11 9 50 48 1644 60 5.1 50 50 126 9 7 43 42 1438 57 5.1 17 50 50 104 12 10 48 47 1644 59 4.9 40 60 146 9 8 40 40 1258 52 4.7 18 45 55 98 11 9 45 44 1655 57 4.6 35 65 145 8 7 38 38 1186 50 4.5 20 35 65 103 15 14 47 46 1378 54 4.3 * Ba(Li2/5W3/5)O3 15 65 35 98 23 17 58 53 2300 57 5.2 60 40 116 22 18 56 53 2054 52 5.3 16 60 40 90 26 23 59 56 2308 55 5.1 55 45 112 18 16 51 48 1980 50 5.2 Table 3 (cont.).

Class III, B Site Substitution Type (1-x)Pb(Zr1-yTiy)O3-xA(MI2/5MV3/5)O3 Electro- Electrooptic III-5 Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 17 55 45 88 22 20 55 53 2200 54 5.0 50 50 116 14 12 47 45 1767 49 5.2 18 50 50 92 18 16 50 48 1998 52 5.1 45 55 115 12 11 43 41 1733 47 4.9 19 45 55 93 15 14 43 1956 50 4.8 40 60 113 8 8 38 37 1711 47 4.7 Ca(Li2/5W3/5)O3 15 60 40 105 24 21 58 55 1431 54 5.2 55 45 132 19 17 54 52 1215 49 5.3 16 55 45 108 22 20 55 53 1406 52 5.2 50 50 133 16 14 50 48 1190 47 5.2 17 50 50 111 19 17 53 51 1378 52 5.0 45 55 127 13 12 47 45 1166 47 4.9 18 45 55 105 16 15 50 48 1347 50 4.8 40 60 136 10 9 45 43 1137 45 4.5 Sr(K2/5W3/5)O3 14 65 35 103 20 16 58 55 1600 60 III-6 Ba(K2/5W3/5)O3 16 60 40 95 25 22 57 54 2000 50 Ca(K2/5W3/5)O3 16 55 45 113 20 18 54 51 1350 50 Table 4 Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;;MIMVIO3 IV-1 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (Pb1-2xMxRx)(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) M/R 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 2&alpha; &alpha;NaNbO3 Bax1/Cdx2 X1=X2 = 1-&alpha; &alpha;=3.5 7.25 65 35 155 37 30 60 54 3176 48 6.3 60 40 175 37 30 59 55 2125 47 5.9 &alpha;=4.0 8.33 65 35 120 43 30 67 58 4003 45 6.1 60 40 135 42 40 66 63 2961 42 5.5 50 50 170 30 27 60 57 1652 44 5.9 &alpha;=4.5 9.42 70 30 65 46 - 71 - 4878 - - 20 60 40 97 44 38 70 67 3826 38 5.0 55 45 113 43 38 69 66 3186 40 5.5 50 50 129 41 37 67 64 2518 40 5.7 40 60 180 15 11 53 50 1978 42 5.6 &alpha;=5 10.53 65 35 48 46 - 71 - 4882 - - 17 50 50 95 43 36 39 65 3175 37 4.9 17 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-2 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (Pb1-2xMxRx)(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) M/R 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 45 55 110 35 32 64 61 2786 39 5.0 40 60 125 28 27 61 59 2515 42 5.3 30 70 175 18 17 42 42 1935 38 5.1 50 50 50 45 - 66 - 4600 - - 15 40 60 55 43 - 63 - 4400 - - 14 2&alpha; &alpha;NaNbO3 Sr/La X1=X2 = 1-&alpha; &alpha;3.5 7.25 65 35 109 27 19 57 37 2880 46 5.8 60 40 135 25 22 62 60 2778 44 5.0 &alpha;=4.0 8.33 65 35 65 43 - 69 - 3863 - 55 45 103 34 31 66 64 3235 45 5.3 50 50 142 24 21 62 60 2612 43 4.8 &alpha;;=4.5 9.42 60 40 47 43 - 69 - 3754 - 50 50 98 32 30 63 61 2265 35 6.1 40 60 145 16 14 45 44 1766 36 6.0 &alpha;=5 10.53 55 45 30 42 - 68 - 3821 - - Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-3 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (Pb1-2xMxRx)(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) M/R 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 50 50 55 41 38 68 66 3000 35 5.3 45 55 79 33 31 65 64 2815 38 5.0 40 60 103 25 25 62 62 2630 40 4.5 2&alpha; &alpha;NaNbO3 Ca/La X1=X2 1-&alpha; &alpha;=3 65 35 143 39 21 66 55 1530 43 3.4 &alpha;=3.5 7.25 65 35 114 42 37 68 63 2150 44 3.3 &alpha;=4 8.33 65 35 85 43 - 70 - 2847 - 60 40 109 39 36 68 65 2550 43 3.3 55 45 133 36 30 65 60 2232 43 3.3 50 50 157 20 13 63 58 1800 42 3.4 &alpha;;=4.5 9.42 55 45 98 38 - 66 - 2871 - 50 50 128 38 35 69 66 2713 43 3.1 40 60 152 32 25 62 57 2168 41 3.0 &alpha;=5 10.53 30 70 147 26 - 62 - 2856 - - Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-4 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V LiNbO3 Ba La &alpha;=4.0 8.33 8.33 65 35 123 41 36 67 64 3803 45 5.9 4.5 9.42 9.42 60 40 100 42 37 68 65 3626 38 4.9 5.0 10.53 10.53 55 45 83 42 37 67 64 3475 38 4.9 LiNbO3 Sr La &alpha;=4.0 8.33 8.33 55 45 106 32 29 64 62 3035 44 5.4 4.5 9.42 9.42 50 50 101 30 28 61 59 2065 33 5.9 LiNbO3 Ca La &alpha;;=3.5 7.25 7.25 65 35 117 40 35 66 61 1950 43 3.8 4.0 8.33 8.33 60 40 112 37 34 68 65 2350 42 3.6 4.5 9.42 9.42 50 50 131 36 33 67 64 2513 42 3.6 LiNbO3 Ba Nd &alpha;=4.0 8.33 8.33 60 40 140 40 38 64 61 2620 40 5.6 4.5 9.42 9.42 55 45 118 41 37 66 63 2910 38 5.6 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-5 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V LiNbO3 Sr Nd &alpha;=4.0 8.33 8.33 60 40 98 35 32 63 61 2405 43 4.6 5.0 10.53 10.53 45 55 88 30 29 62 16 2455 35 4.9 LiNbO3 Ca Nd &alpha;=3.5 7.25 7.25 65 35 122 39 35 66 61 2280 43 3.4 4.0 8.33 8.33 60 40 117 35 33 66 63 2330 42 3.4 LiNbO3 Ba Sm &alpha;=4.5 9.42 9.42 55 45 93 39 37 65 62 3210 40 5.4 LiNbO3 Ca Sm &alpha;=3.5 7.25 7.25 65 35 97 38 34 64 61 2495 44 3.6 LiNbO3 Ba La &alpha; ;=4.0 8.33 8.33 60 40 113 35 32 60 58 3170 40 5.2 4.5 9.42 9.42 55 45 91 31 28 56 54 3390 39 5.2 LiTaO3 Sr La &alpha;=3.5 7.25 7.25 60 40 113 25 22 62 60 3090 46 5.7 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-6 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V LiTaO3 Ca La &alpha;=3.5 7.25 7.25 65 35 92 34 31 63 60 2360 45 3.4 LiTaO3 Ba Nd &alpha;=4.0 8.33 8.33 60 40 115 33 30 58 56 3030 41 5.6 4.5 9.42 9.42 55 45 93 35 34 60 58 3310 39 5.5 LiTaO3 Sr Nd &alpha;=4.0 8.33 8.33 55 45 99 24 21 62 60 2530 43 6.0 LiTaO3 Ca Nd &alpha;=3.5 7.25 7.25 65 35 97 33 30 62 59 2290 44 3.4 LiTaO3 Ba Sm &alpha;=4.0 8.33 8.33 60 40 90 31 28 56 54 3260 46 5.4 LiTaO3 Ca Sm &alpha;;=3.5 7.25 7.25 60 40 102 31 29 60 58 3003 44 3.2 2&alpha; NaNbO3 Ba Nd X= 1-&alpha; &alpha;=4.0 X=8.33 60 40 137 42 40 66 63 2820 41 5.5 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-7 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V &alpha;=4.5 9.42 9.42 55 45 115 43 40 68 65 3100 39 5.5 50 50 130 41 39 69 66 2437 40 5.7 5.0 10.53 50 50 97 41 39 66 64 2982 37 4.9 40 60 127 29 28 62 60 2401 41 5.3 NaNbO3 Sr nd &alpha;=4.0 8.33 8.33 60 40 95 37 34 65 63 2600 44 4.5 55 45 121 25 22 63 61 2325 43 4.7 4.5 9.42 9.42 50 50 103 26 23 62 60 2404 36 6.0 5.0 10.53 10.53 45 55 85 32 31 64 63 2655 36 4.8 NaNbO3 Ca Nd &alpha;;=3.5 7.25 7.25 65 35 119 41 37 68 63 2480 44 3.3 4.0 8.33 8.33 60 40 114 37 35 68 65 2530 43 3.3 4.5 9.42 9.42 55 45 118 37 34 67 65 2476 44 3.2 NaNbO3 Ba Sm &alpha;=4.0 8.33 8.33 60 40 112 40 38 66 63 3040 45 5.3 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-6 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V &alpha;=4.5 9.42 9.42 55 45 90 41 39 67 64 3310 41 5.2 NaNbO3 Sr Sm &alpha;=4.0 8.33 8.33 55 45 96 32 30 65 62 2535 44 4.7 NaNbO3 Ca Sm &alpha;=3.5 7.25 7.25 65 35 94 40 36 66 63 2695 45 3.3 4.0 8.33 8.33 60 40 89 38 36 66 63 2750 44 3.3 4.5 9.42 9.42 55 45 93 36 33 64 62 2690 45 3.2 NaTaO3 Ba La &alpha;=4.0 8.33 8.33 60 40 110 37 34 62 60 3370 41 5.0 4.5 9.42 9.42 55 45 88 33 30 58 56 3590 40 5.0 NaToA3 Ba Nd &alpha;;=4.0 8.33 8.33 60 40 112 35 32 60 58 3230 42 5.4 4.5 9.42 9.42 55 45 90 37 34 62 60 3510 40 5.3 NaTaO3 Ba Sm &alpha;=4.0 8.33 8.33 60 40 87 33 30 58 56 3460 46 5.2 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-2xMxRx)(Zr1-yTiy)O3-&alpha;MIMVIO3 IV-9 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) x 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V NaTaO3 Sr La &alpha;=3.5 7.25 60 40 110 27 24 64 62 3290 47 5.5 NaTaO3 Sr Nd &alpha;=4.0 8.33 8.33 55 45 96 26 23 64 62 2730 44 5.8 NaTaO3 Ca La &alpha;=3.5 7.25 7.25 65 35 89 36 33 65 62 2560 46 3.2 NaTaO3 Ca Nd &alpha;=3.5 7.25 7.25 65 35 94 35 32 64 61 2490 45 3.2 NaTaO3 Ca Sm &alpha;=3.5 7.25 7.25 60 40 99 33 31 62 60 3200 46 3.0 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-x1-x2Mx1Lx2)(Zr1-yTiy)1-2/4O3-&alpha;MIMVIO3 IV-10 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;;(ABO3) X1 X2 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V NaNbO3 M=Ba L=In 12 12 13.6 50 50 130 49 42 73 70 2800 49 12 15 13.6 50 50 122 50 43 74 71 2900 50 12 17 13.6 50 50 110 51 44 74 72 3020 51 12 19 13.6 50 50 100 49 43 72 70 3100 52 M=Ba L=Al 12 15 13.6 50 50 100 43 40 69 65 3200 53 12 17 13.6 50 50 88 45 42 70 67 3300 54 Sr In 12 12 13.6 55 45 122 37 34 68 62 2900 50 12 15 13.6 50 50 125 37 34 67 61 2800 49 12 17 13.6 50 50 103 40 37 69 63 2900 50 Sr Al 12 17 13.6 50 50 110 40 37 68 64 3200 60 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-x1-x2Mx1Lx2)(Zr1-yTiy)1-2/4O3-&alpha;MIMVIO3 IV-11 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;;(ABO3) X1 X2 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V Ca In 12 12 13.6 50 50 120 42 39 67 64 1900 43 12 15 13.6 50 50 115 44 40 69 66 2040 44 12 17 13.6 50 50 105 48 43 71 68 2060 44 Ca Al 12 17 13.6 50 50 102 43 40 69 66 2430 46 Ca Bi 12 17 13.6 50 50 90 36 33 60 57 2200 45 LiNbO3 Ba In 12 17 13.6 50 50 113 42 40 66 64 2810 49 12 19 13.6 50 50 103 40 38 64 62 2900 49 12 Sr In 12 17 13.6 50 50 103 40 38 64 62 2510 47 12 19 13.6 50 50 95 38 36 62 60 2600 47 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-x1-x2Mx1Lx2)(Zr1-yTiy)1-2/4O3-&alpha;MIMVIO3 IV-12 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) X1 X2 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V LiNbO3 Ca In 12 15 13.6 55 45 105 41 39 65 63 1800 42 12 17 13.6 50 50 115 42 40 66 64 1730 42 Ba Al 15 13.6 50 50 100 40 38 66 64 3150 52 17 13.6 50 50 90 42 40 68 66 3250 53 Ca Al 15 13.6 50 50 105 42 39 66 64 1900 43 17 13.6 50 50 95 43 40 67 65 2030 44 Sr Al 15 13.6 50 50 95 40 38 65 63 2700 48 17 13.6 50 50 85 38 36 63 61 2810 49 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-x1-x2Mx1Lx2)(Zr1-yTiy)O3-&alpha;MIMVIO3 X2=&alpha; IV-13 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) X1 X2 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V NaTaO3 Ba In 12 12 13.6 50 50 115 40 37 65 62 2600 51 15 13.6 50 50 107 42 39 67 64 2720 53 17 13.6 50 50 95 44 41 69 66 2800 56 Ba Al 8 10 8.7 55 45 109 39 36 65 62 2800 63 11 8.7 50 50 110 42 40 67 64 2920 64 Ba Bi 8 11 8.7 50 50 100 37 34 64 61 2810 64 Ca In 12 12 13.6 50 50 107 39 36 63 61 1850 50 15 13.6 100 41 38 65 62 1970 52 17 13.6 89 43 41 67 64 2110 55 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-Tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-x1-x2Mx1Lx2)(Zr1-yTiy)O3-&alpha;MIMVIO3 X2=&alpha; IV-13 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400nm #=600nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;(ABO3) X1 X2 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V NaTaO3 Ca Al 8 8 8.7 55 45 100 38 35 63 60 1960 62 11 50 50 101 41 39 65 62 2080 63 Ca Bi 8 11 8.7 50 50 90 35 33 62 59 1930 63 Sr In 12 12 13.6 50 50 107 38 35 63 60 2500 53 15 13.6 50 50 99 40 37 65 64 2680 58 Sr Al 8 8 8.7 55 45 98 36 33 61 58 2640 11 8.7 50 50 98 39 36 63 60 2760 LiTaO3 Ba In 8 8 8.7 55 45 115 36 34 63 61 2400 51 11 50 50 120 38 36 65 62 2450 55 Table 4 (cont.).

Class IV, Solid Solution with Monovalent-tetravalent Type (NaNbO3 Type) (1-&alpha;)(Pb1-x1-x2Mx1Lx2)(Zr1-yTiy)O3-&alpha;MIMVIO3 X2=&alpha; IV-15 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition(mol%) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance (1-x)Pb(Zr1-yTiy)O3 ture before after before after Constant, Factor, 10-10 10-16 &alpha;;(ABO3) X1 X2 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V LiTaO3 Ba Al 8 8 8.7 55 45 95 38 36 64 62 2820 63 11 50 50 96 41 39 66 64 2950 64 Ca In 8 8 8.7 55 45 106 38 36 62 60 1950 50 11 50 50 98 40 38 61 2010 51 Ca Al 8 8 8.7 55 45 85 37 34 62 60 1980 61 11 50 50 86 40 38 64 61 2100 62 Sr In 8 11 8.7 50 50 86 34 32 59 57 2410 55 Sr Al 8 11 8.7 50 50 83 36 33 61 58 2660 58 Table 5 Class V, Rare Earth Element Addition Type (Pb1-x1-x2Mx1Rx2)(Zr1-yTiy)1-X2/4O3 V-1 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance ture before after before after Constant, Factor, 10-10 10-16 Sr La 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 15 5 55 45 68 20 19 56 54 6170 - 16 4 55 45 92 23 21 58 56 3850 42.5 5.6 17 3 55 45 107 14 13 55 54 3450 48 5.8 15 5 50 50 81 28 27 64 63 4600 41 5.5 16 4.5 50 50 88 26 25 64 63 4150 42 5.6 16 4 50 50 92 23 22 62 61 3850 43 5.7 18 4.5 50 50 120 26 25 64 62 4350 51 5.8 18 4 50 50 110 25 24 63 61 4050 48 5.7 20 4 50 50 100 26 25 64 63 4230 45 5.7 22 4 50 50 79 25 24 64 63 4540 41 5.6 24 4 50 50 58 23 22 62 61 4750 36 5.5 26 4 50 50 37 20 - 60 - 4950 31 5.3 Table 5 (cont).

Class V, Rare Earth Element Addition Type (Pb1-x1-x2Mx1Rx2)(Zr1-yTiy)1-X2/4O3 V-2 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance ture before after before after Constant, Factor, 10-10 10-16 Ba La 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 12 6 55 45 78 26 25 59 58 5860 37 5.5 12 5 55 45 106 31 30 65 63 4050 42 5.6 12 4.5 55 45 120 28 27 61 59 3650 44 5.7 14 4.5 55 45 99 32 30 66 64 4630 43 5.6 16 4 55 45 95 31 29 65 63 4800 44 5.6 12 6 50 50 91 30 28 63 61 4370 38 5.4 12 5 50 50 119 29 27 62 60 3920 44 5.5 14 4.5 50 50 112 30 28 64 62 4160 46 5.5 16 4 50 50 105 31 29 65 63 4280 48 5.4 Ca La 12 6 55 45 87 28 26 61 59 5610 37 5.6 12 5 55 45 115 29 27 62 60 3820 42 5.8 14 4.5 55 45 108 30 28 64 62 3430 44 5.7 16 4 55 45 104 31 29 65 63 4600 44 5.7 Table 5 (cont).

Class V, Rare Earth Element Addition Type (Pb1 x1-x2Mx1Rx2)(Zr1-yTiy)1-X2/4O3 V-3 Electro- Electrooptic Curie Transmittance(%) mechanical Constant Composition (mol%) Tempera- #=400 nm #=600 nm Dielectric Coupling #C R Doping Substance ture before after before after Constant, Factor, 10-10 10-16 1-y y Tc( C) poling poling poling poling #s Kp(%) m/V m/V 12 6 50 50 100 32 30 66 64 4150 38 5.6 14 4.5 50 50 121 26 24 60 58 3960 44 5.7 16 4 50 50 114 29 27 62 60 4090 46 5.7 Sr Nd 18 4.5 50 50 125 24 23 62 60 4325 50 5.6 Ba Nd 14 4.5 55 45 104 30 28 64 62 4605 41 5.8 Ca Nd 12 6 50 50 105 30 28 64 62 3950 36 5.8 Ba Sm 12 5 50 50 90 28 26 61 59 4120 46 5.4 (Sr1/2Ba1/2) . 14 La=4.5 55 45 110 30 28 64 62 4230 43 5.8 An example of the phase diagram of ( 1 -a:)Pb(Zr-Ti)03-crSr(Lal,2Nb1,2)03 is shown in Figure 1.In Figure 1, FE Trig, Fe Tet, AFE and Pc indicate regions of the ferroelectric trigonal system, the ferroelectric tetragonal system, the antiferroelectric pseudo-cubic system (including an a-phase and a ,l-phase) and the normal dielectric cubic system, respectively.

Accordingly, optically useful transparent ceramic materials of the present invention are limited to solid solutions of the ferroelectric tetragonal system of the region FE Tet in which the amount of the added solid solution, Sr(La"2Nb1,2)03, is 5 to 25 mol %. It is preferred that the content of Ti, that is, PbTiO3, be within 80 mol %. If the Zr/Ti ratio is too low, the piezoelectric property is degraded.

From the viewpoint of transparency, a solid solution of the FE Tet, which is separated from the phase boundary between AFEp and FE Tet within 5 mol %, especially within 3 mol %, is preferred.

Numbers shown in Figure 1 correspond to sample numbers given in 11-1 of Table 2.

In connection with solid solutions of the other types, similar ideas may practically be held on the amount added of the solid solution, the Zr/Ti ratio and the allowable range of separation from the phase boundary between AFEp and FE Tet.

It will now be described how good materials of the present invention are as materials to be used for a transparent piezoelectric device or electrooptic device, that is, as an optically useful transparent ceramic material while comparing the material of the present invention with PLZT. A composition of PLZT optimum as an optically useful transparent material is close to the trigonal system. For example, PLZT-10/55/45 can be mentioned. The spectral transmittance of a wafer of PLZT polished to an optically flat plate having a thickness of 0.2 mm as in case of ceramic materials of Table 1 is shown by a broken line 1 in Figure 2. The transmittance on the short wavelength side is low as is seen from this line, and hence, the wafer is seen lightly yellowish.When transparent electrodes are applied to both the main surfaces of this wafer, since the electrodes exert a function of preventing reflection, the transmittance is ordinarily increased. If the thickness of the electrode film is 350 nm, the wafer shows a transmittance as indicated by a broken line 3 in Figure 2, and when the thickness of the electrode film is 700 nm, the spectral transmittance is substantially constant in the visible region as indicated by a solid line 2 in Figure 2 and the wafer is substantially colorless but since the transmittance is as low as about 80%, the wafer is seen relatively dark as a whole.

In contrast, a wafer formed by polishing the material of the present invention, for example, 0.2Pb(ZrO 6Tio 4)03-0.8Ca(La1,2Nb1/2)03 shown in 11-5 of Table 2 or 0.88Pb0693ln0,136Ba0,17(Zr06Ti05)096603 shown in lV-5 of Table 4, to an optically flat plate having a thickness of 0.2 mm has a spectral transmittance as indicated by a broken line 3 in Figure 2 and as is seen from this line 3, the transparency of this wafer is higher throughout the entire region than that of PLZT-10/55/45 and the wafer is characterized in that the absorption is small on the short wavelength side.Accordingly, the spectral transmittance of a sample formed by applying transparent electrodes to the wafer of the material of the present invention is 90 to 93% throughout the visible region and is equivalent to that of a glass sheet as indicated by a solid line 4 in Figure 2. Therefore, this electrodeapplied wafer is transparent and colorless and seen bright. This is in practice important. Namely, by using such an optically useful transparent ceramic material of the present invention, it is made possible to render a transparent sound producer for a micro-talking device or an electrooptic shutter colorless and transparent, and such material can now be applied to a high-grade device.

A transparent buzzer or electrooptic shutter including an optically useful ceramic material of the present invention will now be described.

Figure 3 is a diagram illustrating the section of a transparent buzzer including an optically useful ceramic material of the present invention.

A transparent buzzer 10 is constructed by sandwiching a plate 13 of an optically useful ceramic material having a predetermined composition between transparent electrodes 12 and 1 4 formed of tin oxide (SnO2) or indium oxide (In203) and bonding the assembly to a transparent plate 1 This is a transparent buzzer of the so-called bimorph type. When a predetermined signal is applied to the electrodes through lead-in lines 1 5 and 16, the transparent bimorph type buzzer 10 produces refracting vibrations and sounds are radiated to all sides.

Figure 4 is a diagram illustrating the section of another transparent buzzer including an optically useful ceramic material of the present invention. More specifically, transparent electrode plates 22, 24 and 25 having voltage-applying lead-in lines 26, 27 and 28 connected thereto are laminated through plates 23 of an optically useful ceramic material having a composition included in the scope of the present invention to form a transparent piezoelectric buzzer 20 of the bimorph type.

When a voltage is applied to the electrode plates 22, 24 and 25, flexural deformation is caused in each of the optically utilizing ceramic plates. The buzzer shown in Figure 3 is included in the unimorph or monomorph type in a broad sense, butthe buzzer shown in Figure 4 has a structure of the bimorph type in a narrow sense and is characterized in that a sound output much larger than the voltage input can be produced. Incidentally, since the bimorph type buzzer is relatively poor in mechanical strength, a transparent plate 11 may be inserted as a reinforcing plate between the two ceramic plates, or two bimorph structures may be bonded to one surface of a transparent plate 11 for reinforcement.

In the embodiment shown in Figure 4, a thickness of 0.2+0.1 mm is preferred for the optically utilizing ceramic plate from the practical viewpoint. In this embodiment, 0.8Pb(ZrO 5sTio 4s) 3~ 0.2Ca(La1,2Nb1,2)03, is used as the optically utilizing ceramic material.

Figure 5 is a diagram illustrating the section of a watch including the optically utilizing ceramic material of the present invention. A transparent piezoelectric buzzer 32 is formed into a disc and the disc is attached to the inner side of a transparent lid 31, such as a cover lens, of a watch to form a transparent buzzer. When a watch alarm signal composed of modulated pulse waves having a frequency of 2 or 4 KHz and an amplitude of 10 Vpp is given, a pleasant sound having a rich volume is produced.

A display zone 34 composed of a liquid crystal or illuminating diode is formed in the central portion of the interior of the watch body to indicate the time. The buzzer plate 32 composed of the transparent piezoelectric ceramic material of the present invention is attached to this region to cover this region. Since the size of the buzzer is sufficientiy larger than this display region, the transparent electrodes and conductor elements of the buzzer can easily be eiectrically connected to lead-in lines 36. The glass plate or lid 31 is fixed as a cover glass to a watch case by a packing ring 33. A time indicator 34, a driving module 35-and a sound producing IC chip for announcement of the time are built in the case.When a time switch is actuated, a clear announcement talking, for example, "it is nine-thirty", is produced according to a preset program. In this embodiment, the voice generator is a transparent speaker of the monomorph structure comprising a laminate of the glass plate 31 and piezoelectric buzzer 32, and the signal of the IC module 35 is amplified to a voice wave signal of 8 Vpp and applied to the piezoelectric buzzer 32. Piezoelectric vibrations corresponding to voice signals of the buzzer are changed to refracting vibrations by the laminate effect of the glass sheet and buzzer, with the result that voice waves are radiated to the outside from the glass surface.Since the talking frequency is selected in the range of 1 to 3 KHz where many refracting resonances of vibration modes of the monomorph buzzer laminated to the glass plate are superposed in continuity, a clear human voice can be produced though a very low voltage signal is used.

An electrooptic shutter device will now be described as another application example of the present invention.

Figures 6 and 7 are top plan and sectional views diagrammatically illustrating an electrooptic shutter device.

An optically useful ceramic material, 0.88P b0,694-Ba0,1 7Al0,136(Zr0,55Ti046)0,96603-0. 1 2NaNbO3 is subjected to the poling treatment, and the resulting column is sliced at pitches of 0.8 mm vertically to the longitudinal direction by a diamond cutter to obtain a disc having a thickness of 0.6 mm, and the disc is polished to obtain an optically flat transparent disc 41 having a thickness of 0.35 mm. The disc is maintained at 5000C for 30 minutes to remove processing strains, and as shown in Figure 7, inter digital Al electrodes 421, 422 and 421', 422', are arranged at confronting positions on both the main surfaces of the disc 41,so that the electrodes 421 and 422 are located on the front side and the electrodes 421' and 422' are located on the back side.The digit pitch is 500 ym, the electrode width is 50 ,um and the electrode spacing is 450 ym. Lead-in lines 431 and 432 are laid out so that short circuits are formed between 421 and 421' and between 422 and 422', respectively, and a voltage can be applied between 421, 421' and 422, 422'. The so constructed electrooptic element is inserted between two polarizing plates 44 and 45 arranged to cross each other at a right angle, so that the inter digital electrodes are directed to the vibrating plane of polarized light at an angle of 45". The electrooptic element and polarizing plates are fixed to a frame 46 to construct an electrooptic shutter device.When no voltage is applied, the electrooptic shutter device is in the closed state where light is shut off, but when a voltage of 250 V is applied between the inter digital electrodes through the lead-in lines 431 and 432, the electrooptic shutter device is instantaneously opened.

The above-mentioned electrooptic shutter device can be used for a stereoscope of the stereoscopic television.

The color stereoscopic television is accomplished according to the following procedures. At first, an object is photographed by two left and right cameras L and R in the same manner as a viewer sees the object with the two eyes. Signals of the two cameras are synthesized according to the field sequential system by a mixer, and pictures of the left camera and right camera are recorded on odd number fields and even number fields, respectively, by using VTR.

Left pictures and right pictures are reproduced on a monitor TV according to the field sequential system. Therefore, the reproduced pictures look like double image pictures. Accordingly, a viewer observes the reproduced pictures while wearing electrooptic shutter glasses which are arranged so that the left and right glasses are alternately put on and off synchronously with the reproduced pictures.

The left eye selectively sees the left pictures and the right eye selectively sees the right pictures.

Accordingly, the viewer can see steric pictures as if he directly sees the object while standing at the position of the cameras.

Figure 8 is a fragmentary perspective view illustrating parts of another application embodiment of the electrooptic shutter device according to the present invention.

Silver electrodes are coated on the upper and lower main surfaces of a column of an optically utilizing ceramic material having a diameter of 40 mm and a height of 25 mm, and a voltage of 50 KV is applied between the electrodes for 30 minutes to effect the poling treatment. Then, the silver electrodes are removed, and a rectangular column having a height of 25 mm and a section of 30 mmx24 mm is cut out from the so treated column, and the column is sliced at a pitch of 0.7 mm along the height thereof to obtain a plate of 30 mmx25 mmx0.5 mm (thickness). Then, the plate is polished to obtain an optically flat plate having a thickness of 0.25 mm. Transparent electrode films (ITO) 121 and 122 of ln203-SnO2 (91 :9) are formed on both the main surfaces of the polished rectangular plate by sputtering and lead-in lines 431 and 432 are connected thereto.Since the transparent electrode films have a reflection-preventing effect, the transmittance is as high as 87% at a wavelength # of 540 nm under optimum conditions. Since the birefringence of this electrooptic device plate 41 is 2.2 x 10-3, the retardation is 550 nm.

The device plate 41 is diagonally inserted between two polarizing plates 51 and 52 arranged to cross each other at a right angle, and in this state, the device plate and polarizing plates are fixed to a frame 54 to construct an electrooptic shutter device.

When no voltage is applied, the shutter device is closed, but when a voltage of 75 V is applied between the lead-in wires 431 and 432, the shutter device is opened. If a short circuit is formed between the electrodes, the device is closed again. Thus, the device can act as an electrooptic shutter.

Reference number 53 represents a plate of the half wave voltage V#/2 This plate, however, need not be disposed.

In the foregoing embodiments, only electrooptic shutter devices for stereoscopic TV glasses are illustrated. However, those skilled in the art will readily be understand that the transparent ceramic material of the present invention can similarly be applied to any of electrooptic shutter devices used for controlling the light beam intensity, for example, electrooptic shutter devices for visual apparatuses such as a light intensity modulator used in a TV camera for edition of picture films or video tapes, video game machine, observing apparatuses and cameras.

Claims (11)

Claims

1. An optically useful transparent ceramic consisting essentially of at least one crystallographically tetragonal ferroelectric solid solution material selected from: (1) (1-&alpha;)Pb(Zr-Ti)O3-&alpha;A1-z(MI1/2MII1/2)z(Zr-Ti)O3 in which 0.1 5 < c < 0.35 and 0.20 < z < 0.99, (2) (1-a) Pb(Zr-Ti)03-aA (M t121M ' ,2) 3 in which 0.05#&alpha;#0.2, (3) (1-&alpha;)Pb(Zr-Ti)O3-&alpha;A(MI2/5MV3/5)O3 in which 0.1 < a < 0.25, (4) (1-)PbA(Zr-Ti)03-MIM'V03 in which 0.035 < a < 0.1 2, and (5) (1-&alpha;)PbA(Zr-Ti)O3-&alpha;;R2O3 in which 0.03 < < 0.06 wherein A is at least one of Ba, Sr and Ca, Mis at least one of Li, Na and K, M" is at least one of La, Nd, Sm, In, Al and Sc, M"' is at least one of La, Nd, Sm, In, Al, Sc and Bi, MIV is at least one of Nd, Ta, Sb and Bi, MV is at least one of W and Mo, MVX is at least one of Ta, Nb, Sb and Bi, and R is at least one of La, Nd and Sm.

2. An optical device comprising at least a vibrating plane plate and a ceramic plate formed of a material according to Claim 1 sandwiched between a pair of light-transmitting electrodes, said vibrating plane plate being arranged to be vibrated by the ceramic plate.

3. An optical device comprising a prepoled ceramic plate whose polarization lies in the plane of the ceramic plate and a pair of polarizers between which said prepoled ceramic plate is placed in the diagonal position, wherein said ceramic plate is formed of a material according to Claim 1.

4. An electrical apparatus including an optical device according to Claim 2 or Claim 3.

5. A watch including an optical device according to Claim 2 or Claim 3.

6. An audio set including an optical device accordirig to Claim 2 or Claim 3.

7. A talking set including an optical device according to Claim 2 or Claim 3.

8. An electrooptic shutter device which is an optical device according to Claim 2 or Claim 3.

9. Stereoscopic TV glasses which are an optical device according to Claim 2 or Claim 3.

1 0. Each material according to Claim 1 herein disclosed.

11. An electrooptic device including a material according to Claim 1 or any one of the materials of Claim 10 and substantially as any such device herein described with reference to and as shown in the accompanying drawings.