Abstract:
A piezoelectric ceramic composition that is based on a layered bismuth compound composed of Sr, Bi, Nb, oxygen, contains an additional monovalent metallic element. The piezoelectric ceramic composition has an elevated Curie point, is highly reliable at higher temperatures, that is, minimizes the reduction in the piezoelectric effect, and is useful as a material for piezoelectric ceramic devices that contain little or no lead or lead compounds. The layered bismuth compound contains not more than about 0.125 mol and more than 0 mol of the monovalent metallic element for 1 mol of Nb.

Description:
BACKGROUND OF THE INVENTION  
         [0001]    1. Field of the Invention  
           [0002]    The present invention relates to a piezoelectric ceramic composition and a piezoelectric ceramic device composed of the piezoelectric ceramic composition. In particular, the present invention relates to a piezoelectric ceramic composition that is useful as a material for piezoelectric ceramic devices, such as a piezoelectric ceramic filter, a piezoelectric ceramic resonator and a piezoelectric ceramic oscillator, and to a piezoelectric ceramic device composed of the piezoelectric ceramic composition.  
           [0003]    2. Description of the Related Art  
           [0004]    Hitherto, a lead zirconate titanate, (Pb(Ti x Zr 1-x )O 3 ) or a lead titanate- (PbTiO 3 ) based piezoelectric ceramic composition has been widely used in piezoelectric ceramic devices, such as a piezoelectric ceramic filter, a piezoelectric ceramic resonator and a piezoelectric ceramic oscillator. However, the lead zirconate titanate- or the lead titanate-based piezoelectric ceramic composition contains a large amount of lead, which vaporizes as lead oxide during production of the piezoelectric ceramic device, and thereby results in poor product uniformity. Thus, a piezoelectric ceramic composition that contains little or no lead is desired to overcome this problem. In addition, a lower amount of lead is also desirable in view of environmental pollution.  
           [0005]    On the other hand, a piezoelectric ceramic composition based on a layered bismuth compound, such as SrBi 2 Nb 2 O 9 , is free of lead oxide and does not cause such problems.  
           [0006]    In addition, SrBi 2 Nb 2 O 9 -based materials, as disclosed in Japanese Unexamined Patent Application Publication No. 2001-328865, exhibit a significantly small change in frequency when temperature changes, and therefore have received attention as piezoelectric materials for resonators recently.  
           [0007]    While the piezoelectric ceramic device is typically used at a temperature range, for example, from 60° C. to 200° C., those that can be used at a higher temperature of, for example, about 400° C., are desired for use in a resonator. Since the piezoelectric ceramic resonator cannot be used above its Curie point, where it has no piezoelectric effect, the piezoelectric ceramic resonator must has a Curie point higher than operating temperatures.  
           [0008]    According to M. J. Forbess et al. (Applied Physics Letters, Vol. 76, 2943, (2000)), SrBi 2 Nb 2 O 9  has a Curie point of 418° C. and has a lowered piezoelectric effect when used for a piezoelectric ceramic resonator at a temperature close to 400° C. A preferred Curie point in this case is at least 430° C.  
         SUMMARY OF THE INVENTION  
         [0009]    Accordingly, it is an object of the present invention to provide a piezoelectric ceramic composition that is based on a layered bismuth compound composed of Sr, Bi, Nb, oxygen, and an additional monovalent metallic element. The piezoelectric ceramic composition has an elevated Curie point, is highly reliable at higher temperatures, that is, minimizes the reduction in the piezoelectric effect, and is useful as a material for piezoelectric ceramic devices that contain little or no lead or lead compounds.  
           [0010]    The piezoelectric ceramic composition according to the present invention contains not more than about 0.125 mol (and more than 0 mol) of monovalent metallic element per 1 mol of Nb. This amount of monovalent metallic element leads to an increased Curie point of the piezoelectric ceramic composition. However, more than about 0.125 mol of monovalent metallic element will adversely decrease the Curie point of the piezoelectric ceramic composition.  
           [0011]    Preferably, the monovalent metallic element used in the present invention is at least one selected from the group consisting of Li, Na and K, which give further advantages of the present invention.  
           [0012]    Furthermore, the piezoelectric ceramic composition according to the present invention preferably contains not more than about 0.175 mol (and more than 0 mol) of trivalent metallic element other than Bi per 1 mol of Nb. When the ceramic device composed of the piezoelectric ceramic composition is used as a resonator, this amount of trivalent metallic element other than Bi gives a practicable Q max  factor (the maximum electrical quality factor Q (1/tan δ) within a band, that is, at frequencies between the resonance frequency and the anti-resonance frequency).  
           [0013]    Preferably, the trivalent metallic element other than Bi is at least one selected from the group consisting of Sc, Y, La, Ce, Nd, Sm, Gd, Dy, Er and Yb, which give further advantages of the present invention. More preferably, the trivalent metallic element other than Bi is Nd, which give still further advantages of the present invention.  
           [0014]    In the main component of the piezoelectric ceramic composition according to the present invention, not more than about 10 molar percent (and more than 0 molar percent) of Nb may be replaced with Ta. As a result, the amount of Ta will be up to 10% based on the total mols of Nb and Ta present. Replacing more than about 10 molar percent of Nb with Ta will result in a too low Q max  factor for the piezoelectric ceramic composition to function as a resonator.  
           [0015]    Further, the main component of the piezoelectric ceramic composition according to the present invention may contain not more than about 0.01 mol (and more than 0 mol) of Mn per 1 mol of the main component. Manganese in amounts larger than that will result in a too low Q max  factor for the piezoelectric ceramic composition to function as a resonator.  
           [0016]    The piezoelectric ceramic device according to the present invention includes a piezoelectric ceramic that is composed of piezoelectric ceramic composition according to the present invention, and electrodes on the piezoelectric ceramic.  
           [0017]    The foregoing and other objects, features, and advantages of the present invention will be more apparent from the detailed description of the following embodiment according to the present invention.  
       
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0018]    [0018]FIG. 1 is a perspective view of a piezoelectric ceramic oscillator according to an embodiment of the present invention; and  
         [0019]    [0019]FIG. 2 is a sectional view of the piezoelectric ceramic oscillator shown in FIG. 1. 
     
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0020]    SrCO 3 , Bi 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , Na 2 CO 3 , K 2 CO 3 , Li 2 CO 3 , Nd 2 O 3 , La 2 O 3 , Ce 2 O 3 , Sc 2 O 3 , Y 2 O 3 , Sm 2 O 3 , Gd 2 O 3 , Dy 2 O 3 , Er 2 O 3 , Yb 2 O 3  and MnCO 3  were firstly prepared as starting materials. These compounds were weighed to meet the composition formula (Sr a Bi b Nb c O 9 +w mol M1+x mol M3+y mol Ta+z mol MnCO 3  (wherein, M1 is Na, K or Li, M3 is Nd, La, Ce, Sc, Y, Sm, Gd, Dy, Er or Yb, and a, b, c, w, x, y and z are as shown in Tables 1 and 2)) and were wet-blended in a ball mill for about 16 hours. The resulting mixture was dried, and was then calcined at 800 to 1000° C. The product was mixed with an organic binder, a dispersant, an anti-foaming agent, a surfactant and pure water in proper quantities, and was pulverized in the ball mill. The resulting slurry was applied with a doctor blade into sheets 40 to 80 μm in thickness. Electrodes were printed on some of these sheets with a Pt paste, and then the printed sheets were dried. The printed sheets and other sheets were stacked. The resulting laminate was compacted and was baked at 1100 to 1300° C. Then, the laminate was polarized in an insulating oil at 100 to 200° C. under 5 to 10 kV/mm dc voltage for 10 to 30 min, yielding an energy-confinement piezoelectric ceramic oscillator 10 (sample) shown in FIGS. 1 and 2.  
         [0021]    A piezoelectric ceramic oscillator  10  shown in FIGS. 1 and 2 includes a piezoelectric ceramic  12  in, for example, a rectangular parallelepiped shape. The piezoelectric ceramic  12  is polarized in the direction from the bottom face to the top face as indicated by an arrow. The piezoelectric ceramic  12  has vibrating electrodes  14   a  and  14   b  on its top and bottom faces, respectively. The vibrating electrodes  14   a  and  14   b  are of, for example, a circular shape and are disposed at the center of each face. Thus, the vibrating electrode  14   b  is disposed right below the vibrating electrode  14   a.  The piezoelectric ceramic  12  also has an internal vibrating electrode  14   c  in, for example, a circular shape. The vibrating electrode  14   c  is disposed in the middle of the vibrating electrodes  14   a  and  14   b.  Thus, the vibrating electrodes  14   a,    14   b  and  14   c  are vertically aligned. Leading electrodes  16   a,    16   b  and  16   c  in, for example, a T shape are disposed between their respective vibrating electrodes  14   a,    14   b  and  14   c,  and a side face of the piezoelectric ceramic  12 . Specifically, the leading electrodes  16   a  and  16   b  are disposed between their respective vibrating electrodes  14   a  and  14   b,  and one side face of the piezoelectric ceramic  12 , and the leading electrode  16   c  is disposed between the vibrating electrode  14   c  and the other side face of the piezoelectric ceramic  12 . A voltage is applied between the leading electrodes  16   a  and  16   b  and the leading electrode  16   c  to cause electric potential difference between the exterior vibrating electrodes  14   a  and  14   b  and the interior vibrating electrode  14   c,  and thus to excite a thickness-longitudinal vibration second harmonic mode.  
         [0022]    The piezoelectric ceramic oscillator  10  (sample) was tested for the Q max  factor at room temperature in the thickness-longitudinal vibration second harmonic mode. In addition, the temperature dependence of permittivity and the Curie point were measured. The results are shown in Tables 1 and 2.  
                                                                                                                                   TABLE 1                           Samples with asterisks are outside of the scope of the present invention.            Sample                                               Curie           No.   a   b   c   M1   w   M3   x   y   z   w/c   x/c   point (° C.)   Q max                       1*   1.0   2.0   2.0   —   0   —   0   0   0   0   0   418   9.8        2   1.0   2.0   2.0   Na   0.05   —   0   0   0   0.025   0   480   10.1        3   1.0   2.0   2.0   Na   0.1   —   0   0   0   0.05   0   480   10.5        4   1.0   2.0   2.0   Na   0.2   —   0   0   0   0.1   0   455   10.4        5   1.0   2.0   2.0   Na   0.25   —   0   0   0   0.125   0   435   10.3        6*   1.0   2.0   2.0   Na   0.3   —   0   0   0   0.15   0   360   9.6        7   1.0   2.0   2.0   K   0.1   —   0   0   0   0.05   0   480   10.2        8   1.0   2.0   2.0   K   0.2   —   0   0   0   0.1   0   450   10.5        9*   1.0   2.0   2.0   K   0.3   —   0   0   0   0.15   0   370   8.9       10   1.0   2.0   2.0   Li   0.1   —   0   0   0   0.05   0   480   9.8       11   1.0   2.0   2.0   Li   0.2   —   0   0   0   0.1   0   435   10.3        12*   1.0   2.0   2.0   Li   0.3   —   0   0   0   0.15   0   370   8.6       13   1.0   2.0   2.0   Na   0.05   Nd   0.05   0   0   0.025   0.025   490   12.5       14   1.0   2.0   2.0   Na   0.1   Nd   0.2   0   0   0.05   0.1   470   11.5       15   1.0   2.0   2.0   Na   0.1   Nd   0.35   0   0   0.05   0.175   450   10.3       16   1.0   2.0   2.0   Na   0.1   Nd   0.4   0   0   0.05   0.2   435   8.9       17   0.9   2.0   2.0   Na   0.1   Nd   0.1   0   0   0.05   0.05   470   15.2       18   0.8   2.0   2.0   Na   0.1   Nd   0.2   0   0   0.05   0.1   465   12.3       19   0.8   2.0   2.0   Na   0.15   Nd   0.3   0   0   0.075   0.15   460   11.4       20   0.8   2.2   2.0   Na   0.15   Nd   0.3   0   0   0.075   0.15   470   13.3       21   0.9   2.0   2.0   Na   0.1   La   0.1   0   0   0.05   0.05   460   14.6                  
 
         [0023]    [0023]                                                                                                                             TABLE 2                       Sample                                               Curie           No.   a   b   c   M1   w   M3   x   y   z   w/c   x/c   point (° C.)   Q max                                  22   0.8   2.0   2.0   Na   0.1   La   0.2   0   0   0.05   0.1   440   13.2       23   0.9   2.0   2.0   Na   0.1   Sc   0.1   0   0   0.05   0.05   470   14.3       24   0.8   2.0   2.0   Na   0.1   Sc   0.2   0   0   0.05   0.1   460   13.2       25   0.9   2.0   2.0   Na   0.1   Y   0.1   0   0   0.05   0.05   475   15.5       26   0.8   2.0   2.0   Na   0.1   Y   0.2   0   0   0.05   0.1   460   14.1       27   0.9   2.0   2.0   Na   0.1   Sm   0.1   0   0   0.05   0.05   470   13.5       28   0.8   2.0   2.0   Na   0.1   Sm   0.2   0   0   0.05   0.1   455   12.8       29   0.9   2.0   2.0   Na   0.1   Dy   0.1   0   0   0.05   0.05   470   14.3       30   0.8   2.0   2.0   Na   0.1   Dy   0.2   0   0   0.05   0.1   460   13.7       31   0.9   2.0   2.0   Na   0.1   Yb   0.1   0   0   0.05   0.05   475   13.9       32   0.8   2.0   2.0   Na   0.1   Yb   0.2   0   0   0.05   0.1   465   13.1       33   0.9   2.0   2.0   Na   0.1   Ce   0.1   0   0   0.05   0.05   480   13.5       34   0.8   2.0   2.0   Na   0.1   Ce   0.2   0   0   0.05   0.1   460   13.0       35   0.9   2.0   2.0   Na   0.1   Gd   0.1   0   0   0.05   0.05   485   13.9       36   0.8   2.0   2.0   Na   0.1   Gd   0.2   0   0   0.05   0.1   470   12.9       37   0.9   2.0   2.0   Na   0.1   Er   0.1   0   0   0.05   0.05   475   13.4       38   0.8   2.0   2.0   Na   0.1   Er   0.2   0   0   0.05   0.1   470   13.0       39   1.0   2.0   1.9   Na   0.05   Nd   0.05   0.1   0   0.0263   0.0263   460   13.1       40   1.0   2.0   1.8   Na   0.05   Nd   0.05   0.2   0   0.0277   0.0277   440   12.6       41   1.0   2.0   2.0   Na   0.05   Nd   0.05   0   0.005   0.025   0.025   490   13.8       42   1.0   2.0   2.0   Na   0.05   Nd   0.05   0   0.01   0.025   0.025   480   14.1                    
         [0024]    The Q max  factor was determined for each sample under the conditions (calcination temperature, firing temperature, temperature of insulating oil during polarization, and dc voltage) that exhibited the largest Q max  factor. The Q max  factor depended on the shape of the sample, the mode of vibration and the type of the electrode. The applications of the piezoelectric ceramic device, in particular, a piezoelectric ceramic resonator, at a higher temperature according to the present invention are of very special use, and a high Q max  factor as required in general-purpose piezoelectric ceramic devices, in particular, piezoelectric ceramic resonators that are used in household electric appliances, is not required. This is because even a low Q max  factor is practicable depending on the circuit design. Under the present conditions, a Q max  factor of at least 10 at room temperature is a practical level.  
         [0025]    The Curie points in Tables 1 and 2 were determined for each sample under the conditions (calcination temperature and firing temperature) that gave the highest density. When the piezoelectric ceramic device is used at a high temperature close to 400° C., a Curie point of at least 430° C. is required for practical use.  
         [0026]    It is apparent from Tables 1 and 2 that the piezoelectric ceramic compositions within the scope of the present invention have Curie points higher than 430° C. and thus are useful materials for piezoelectric ceramic devices, in particular, piezoelectric ceramic resonators at a high temperature close to 400° C.  
         [0027]    The samples that are within the scope of the present invention and contain not more than about 0.175 mol (and more than 0 mol) of trivalent metallic elements other than Bi per 1 mol of Nb have Q max  factors of not less than the practical level of 10, and thus are useful materials particularly for piezoelectric ceramic resonators.  
         [0028]    The piezoelectric ceramic composition according to the present invention is not limited to the embodiment described above, and is effective within the scope of the present invention.  
         [0029]    The present invention can be applied not only to the piezoelectric ceramic oscillator  10  described above, but also to other piezoelectric ceramic devices, such as piezoelectric ceramic oscillators, piezoelectric ceramic filters and piezoelectric ceramic resonators.