Abstract:
A microwave dielectric ceramic composition exhibiting excellent relative permitting (∈) and high Qf-value, enabling the temperature coefficient of resonance frequency to be easily adjusted, and being best suited for a filter having cavities made of, e.g., iron or copper exhibiting a large temperature coefficient of resonance frequency. The ceramic is of a BaO—TiO 2 —Nd 2 O 3 —Sm 2 O 3  ceramic, type wherein Nd 2 O 3  is partly substituted by Bi 2 O 3 , Nd 2 O 3  is Partly substituted by Ln 2 O 3  (where Ln is La, Ce or Pr) and, the above substituted Ln 2 O 3  is partly substituted by EU 2 O 3  to improve the properties so that ∈ is 82.5 to 92.5, Qf is 6000 to 7300 GHz and τf is 10-20 ppm/° C. This makes it possible to impart favorable electric characteristics to resonance cavities of various materials and sizes.

Description:
This is a 371 of PCT/JP98/02467 filed Jun. 4, 1998. 
    
    
     DESCRIPTION 
     1. Technical Field 
     The present invention relates to a dielectric ceramic composition whose chief constituents are Ba, Ti, Sm. Nd, La, Ce, Pr, Bi and O 2 , additionally containing Eu 2 O 3  and having the properties ∈=82.5 to 92.5, Qf=6000 to 7300 GHz, τf=10 to −20 ppm/° C. which is capable of being employed as a dielectric resonance material or frequency adjusting rod thereof. 
     2. Background Art 
     In recent years, with the development of new media in the field of electronic technology, there has been rapid progress in miniaturization and digitization. In particular, in the field of communications using microwaves such as satellite communication, car phones, and mobile telephones, advanced miniaturization of components and high levels of reliability are being demanded. 
     In conventional microwave circuits cavity resonators or waveguides are employed as filter or transmission circuits so this has presented an obstacle to such miniaturization and enhanced reliability. Specifically, in cavity resonators or waveguides, basically the stability of air or vacuum as a propagation medium for electromagnetic waves is made use of; in order to miniaturize a microwave circuit portion as aforesaid, a propagation medium may be employed which has a larger dielectric constant than the dielectric constant of air or vacuum and which has the same level of high stability in respect of temperature as air or vacuum. If this is done, the propagation wavelength of the microwaves in the medium is 1/{square root over ((∈r))} (where ∈r is the relative permittivity), so the resonant wavelength is also 1/{square root over ((∈r))} and miniaturization can be achieved. 
     Previous microwave dielectric ceramic compositions that have been proposed include BaO—TiO 2 —Nd 2 O 3 —Bi 2 O 3  based ceramics (Laid-open Japanese Patent Publication Sho. 56-102003) and BaO—TiO 2 —Sm 2 O 3 —CeO 2 —Bi 2 O 3  based ceramics (Laid-open Japanese Patent Publication Sho. 62-187162). However, these materials suffered from the problems of their Qf value as a microwave communication dielectric being low at 4000 to 6500 and that adjustment of the temperature characteristic of frequency for various cavities was not easy. 
     Also, BaO—TiO 2 —Ln 2 O 3  based ceramics (where Ln 2 O 3  represents addition of Cr 2 O 3  to Nd 2 O 3  or Pr 6 O 11 ) (Japanese Laid-open Patent Publication H. 7-169326) have a relative permittivity value (∈) of 91 to 93, but they were subject to the problems that their Q value is low at 5700 to 6000, and their temperature coefficient τf of resonance frequency is 6 to 9 ppm/° C., so that they cannot be employed in filters where the cavity material has a large temperature coefficient of resonance frequency, such as iron or copper. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to provide a microwave dielectric ceramic composition whereby the problems of the prior art microwave dielectric ceramic composition are solved, which is of excellent relative permittivity (∈) characteristic, has a high Qf value, whereby adjustment of the temperature coefficient of the resonance frequency can easily be achieved, and which is ideal for filters where the cavity material has a large temperature coefficient of resonance frequency, such as iron or copper. 
     As a result of various studies of ceramic compositions with the object of providing a microwave dielectric ceramic composition of high Qf value and of improved temperature characteristic, the present inventors discovered that the properties: ∈=88.5 to 92.5, Qf=6000 to 7300 GHz, τf=3 to −10 ppm/° C. could be obtained by, in a BaO—TiO 2 —Nd 2 O 3 —Sm 2 O 3  based ceramic, substituting some of the Nd 2 O 3  by Bi 2 O 3  and further substituting some of the Nd 2 O 3  by Ln 2 O 3  (where Ln=La, Ce, Pr). 
     Furthermore, they discovered that, by substituting some of the aforementioned substituted Ln 2 O 3  with Eu 2 O 3 , a material could be provided with temperature coefficient τf of resonance frequency improved to 10 to −20 ppm/° C. and furthermore, the foregoing material may be sintered in the atmosphere; however, they discovered that, by sintering in an atmosphere containing at least 80% of oxygen, excellent properties in respect of the Qf value and/or τf value mentioned above are provided, and in addition the permittivity ∈ of frequency is improved to 82.5 to 92.5, thereby perfecting the present invention. 
     BEST MODE FOR CARRYING OUT THE INVENTION 
     The present invention consists in a microwave dielectric ceramic composition whose compositional formula is represented by: 
     
       
         Ba 6−3x ·{Sm 1−y ·(Nd 1−w−v Eu w Ln v ) y−z Bi z } 8+2x ·Ti 18 O 54  (where Ln=La,Ce,Pr) 
       
     
     where the values of x, y, z, y−z, w and v in the compositional formula satisfy the following values: 
     0.5&lt;x&lt;0.8, 0.3&lt;y&lt;0.5, 0&lt;z&lt;0.4, y−z&gt;0, 0&lt;w≦1,0&lt;v≦1. 
     The reasons for the restrictions in the composition of the present invention will now be described. In a dielectric ceramic composition of compositional formula Ba 6−3x ·{Sm 1−y ·(Nd 1−w−v Eu w Ln v ) y−z Bi z } 8+2x ·Ti 18 O 54 , if x is less than 0.5, the Q value of the dielectric falls; if it is more than 0.8, the permittivity falls; these are therefore undesirable. Also, if y is less than 0.3, this tends to cause a drop in permittivity, while if it is more than 0.5, the Q value falls: these are therefore undesirable. Furthermore, if z exceeds 0.4, the Q value drops severely; this is therefore undesirable. 
     Also, in the above compositional formula, if w and v are both zero, the permittivity becomes low, and furthermore the temperature characteristic becomes negative and the temperature characteristic cannot be controlled even by addition of Eu, so it is desirable that w and v are not both zero: at least either one of w or v should preferably have a positive value. 
     The properties of the dielectric ceramic composition of the present invention can be continuously varied between ∈=82.5 to 92.5, temperature characteristic of frequency 10 to −20 ppm/° C. Excellent electrical properties can thereby be conferred on resonance cavities of various materials and sizes. 
    
    
     EXAMPLES 
     Example 1 
     BaCO 3 , Sm 2 O 3 , Nd 2 O 3 , Eu 2 O 3 , La 2 O 3 , Bi 2 O 3 , and TiO 2  powder of grain size of 1 μm or less, according to the compositional formula Ba 6−3x ·{Sm 1−y ·(Nd 1−w−v Eu w Ln v ) y−z Bi z } 8+2x ·Ti 18 O 54  were blended and mixed with x=0.7, y=0.4, z=0.1, and v=(0.45, 0.4, 0.35, 0.3, 0.25, 0), w=(0.05, 0.1, 0.15, 0.2, 0.25, 0.5) before molding under pressure of 1.5 T/cm 2  followed by sintering for three hours at 1370° C. in air and in a 100% O 2  atmosphere to manufacture dielectric ceramics which were used to produce 4.7 GHz band resonators whose properties are shown in Table 1. 
     Example 2 
     BaCO 3 , Sm 2 O 3 , Nd 2 O 3 , Eu 2 O 3 , CeO 2 , Bi 2 O 3 , and TiO 2  powder of grain size of 1 μm or less, according to the same compositional formula as in Example 1 were blended and mixed with x=0.7, y=0.4, z=0.1, and v=(0.45, 0.4, 0.35, 0.3, 0), w=(0.05, 0.1, 0.15, 0.2, 0.5), before manufacturing dielectric ceramics under the same manufacturing conditions as in Example 1 which were used to produce 4.7 GHz band resonators whose properties are shown in Table 2. 
     Example 3 
     BaCO 3 , Sm 2 O 3 , Nd 2 O 3 , Eu 2 O 3 , Pr 6 O 11 , Bi 2 O 3 , and TiO 2  powder of grain size of 1 μm or less, according to the same compositional formula as in Example 1 were blended and mixed with x=0.7, y=0.4, z=0.1, and v=(0.45, 0.4, 0.35, 0.3, 0), w=(0.05, 0.1, 0.15,0.2, 0.5), before manufacturing dielectric ceramics under the same manufacturing conditions as in Example 1 which were used to produce 4.7 GHz band resonators whose properties are shown in Table 3. 
     Comparison 
     BaCO 3 , Sm 2 O 3 , Nd 2 O 3 , Eu 2 O 3 , La 2 O 3 , Bi 2 O 3 , and TiO 2  powder of grain size of 1 μm or less, according to the compositional formula Ba 6−3x ·{Sm 1−y ·(Nd 1−w−v Eu w Ln v ) y−z Bi z } 8+2x ·Ti 18 O 54  were blended and mixed with x=0.7, y=0.4, z=0.1, and v=0, w=0 before manufacturing dielectric ceramics under the same manufacturing conditions as in example which were used to produce resonators the same as in the examples whose properties are shown in Table  1 . Also, with the aforesaid compositional formula, dielectric ceramics of the composition x=0.7, y=0.4, z=0, v=1, Ln=La were manufactured under the same conditions as in the examples and their properties are shown in Table 1. 
     
       
         
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
             
             
               
                   
                   
                 v = 0.45 
                 v = 0.4 
                 v = 0.35 
                 v = 0.3 
                 v = 0.25 
                 v = 0 
               
               
                   
                   
                 w = 0.05 
                 w = 0.1 
                 w = 0.15 
                 w = 0.2 
                 w = 0.25 
                 w = 0.5 
               
               
                   
               
               
                 In air 
                 Qf (GHz) 
                 7157 
                 7175 
                 7116 
                 6935 
                 6124 
                 6003 
               
               
                   
                 ε 
                 91.48 
                 91.15 
                 90.45 
                 89.73 
                 87.43 
                 82.91 
               
               
                   
                 τf (ppm/° C.) 
                 2.62 
                 −8.24 
                 −5.38 
                 −9.16 
                 −12.36 
                 −15.0 
               
               
                 In 
                 Qf (GHz) 
                 7181 
                 7248 
                 7155 
                 6951 
                 6238 
                 6015 
               
               
                 100% O 2   
                 ε 
                 92.46 
                 92.21 
                 91.76 
                 90.65 
                 88.58 
                 83.11 
               
               
                 atmosphere 
                 τf (ppm/° C.) 
                 2.59 
                 −3.22 
                 −5.58 
                 −9.00 
                 −17.35 
                 −19.9 
               
               
                   
               
               
                   
                   
                   
                 w = 0 
               
               
                   
                   
                 w = 0 
                 v = 1 
               
               
                   
                 Composition 
                 v = 0 
                 Ln = La 
               
               
                   
               
               
                 Comparison 
                 Qf (GHz) 
                 6100 
                 9000 
               
               
                   
                 ε 
                 89.5 
                 83 
               
               
                   
                 τf (ppm/° C.) 
                 −20 
                 16 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 v = 0.45 
                 v = 0.4 
                 v = 0.35 
                 v = 0.3 
                 v = 0 
               
               
                   
                 w = 0.05 
                 w = 0.1 
                 w = 0.15 
                 w = 0.2 
                 w = 0.5 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 In air 
                 Qf (GHz) 
                 7131 
                 7118 
                 7005 
                 6510 
                 6132 
               
               
                   
                 ε 
                 91.00 
                 90.81 
                 90.13 
                 89.87 
                 85.30 
               
               
                   
                 τf (ppm/° C.) 
                 0.11 
                 −6.21 
                 −10.0 
                 −14.2 
                 −17.7 
               
               
                 In 
                 Qf (GHz) 
                 7136 
                 7010 
                 7018 
                 6967 
                 6389 
               
               
                 100% O 2   
                 ε 
                 91.02 
                 90.97 
                 90.56 
                 90.12 
                 87.18 
               
               
                 atmosphere 
                 τf (ppm/° C.) 
                 0.03 
                 −8.35 
                 −12.3 
                 −14.8 
                 −16.9 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 v = 0.45 
                 v = 0.4 
                 v = 0.35 
                 v = 0.3 
                 v = 0 
               
               
                   
                 w = 0.05 
                 w = 0.1 
                 w = 0.15 
                 w = 0.2 
                 w = 0.5 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 In air 
                 Qf (GHz) 
                 7051 
                 7003 
                 6987 
                 6513 
                 6212 
               
               
                   
                 ε 
                 90.30 
                 89.98 
                 89.31 
                 88.86 
                 84.11 
               
               
                   
                 τf (ppm/° C.) 
                 −1.53 
                 −7.18 
                 −12.6 
                 −14.3 
                 −17.5 
               
               
                 In 
                 Qf (GHz) 
                 7093 
                 7096 
                 7016 
                 6888 
                 6319 
               
               
                 100% O 2   
                 ε 
                 90.88 
                 90.54 
                 90.02 
                 89.58 
                 85.97 
               
               
                 atmosphere 
                 τf (ppm/° C.) 
                 −2.30 
                 −8.13 
                 −12.9 
                 −15.1 
                 −18.24 
               
               
                   
               
             
          
         
       
     
     INDUSTRIAL APPLICABILITY 
     In a BaO—TiO 2 —Nd 2 O 3 —Sm 2 O 3  based ceramics, by substituting some of the Nd 2 O 3  by Bi 2 O 3  and furthermore by substituting some of the Nd 2 O 3  by Ln 2 O 3  (where Ln=La, Ce, Pr), the properties ∈=88.5 to 92.5, Qf=6000 to 7300 GHz, τf=3 to −10 ppm/° C. were obtained. Also, by substituting with Eu 2 O 3  instead of Ln 2 O 3 , a dielectric having the properties: ∈=85, Qf=6000 GHz, τf=−1.5 ppm/° C. can be obtained. Furthermore, by combining the aforementioned two effects, i.e. by substituting with Eu 2 O 3  part of the substituted Ln 2 O 3 , improvement can be achieved to ∈=82.5 to 92.5, Qf=6000 to 7300 GHz, τf=10 to −20 ppm/° C.; in this way, excellent electrical properties can be provided for resonance cavities made of various materials and of large size.