MICROWAVE DIELECTRIC CERAMIC COMPOSITION

Abstract: An object of the present invention is to obtain a dielectric ceramic composition wherein the dielectric constant epsilon is large, the temperature coefficient tau f of the resonance frequency is close to 0, and which has a large Q value, by adding to and blending with a ceramic composition whose tau f of the resonance frequency is large on the plus side a ceramic composition whose temperature coefficient tau f is large on the minus side. In an Li>2<O-R>2<O>3<-TiO>2<-based composition where R is one or two or more of Nd, Sm, Pr and La, an improved dielectric constant epsilon can be achieved by introducing a specific quantity of Bi>2<O>3<, and tau f can be shifted to the plus side and in addition a considerable improvement in Qf achieved by introducing a specific quantity of MO (where M is one or two of Ca and Sr). Furthermore, by introducing a specific quantity of Na>2<O together with the MO (where M is one or two of Ca and Sr), in particular in the case of material of epsilon r>/= 150, it is possible to control tau f to the vicinity of 0 while maintaining Qf at an high value.

Description: DESCRIPTION MICROWAVE DIELECTRIC CERAMIC COMPOSITION TECHNICAL FIELD The present invention relates to a microwave dielectric ceramic composition employed in resonator materials or capacitor materials etc used in the microwave region of a few GHz. BACKGROUND ART Dielectrics are used in the resonators, filters, or capacitors that are used in transceivers for for example satellite communication broadcasting or mobile identification devices using microwaves of a few GHz. As such dielectric ceramic materials, for example BaO-TiO2- Nd2θ3-Bi 2 θ 3 compositions have been proposed (Laid-open Japanese Patent Application No. Sho. 61-8806). The dielectric constant ε of this composition is of the order or 70 to 110; when dielectric resonators or capacitors are constructed, materials of larger dielectric constant ε are preferred since the larger the dielectric constant ε of the material that is used, the smaller are the dimensions of the resonator. Conventional materials of large dielectric constant ε include for example SrTiθ 3 and CaTiθ 3 etc; while their dielectric constant ε is very large at 300 and 180, the temperature coefficient xf of the resonance frequency is extremely large at + 1700 ppm/°C and + 800 ppm/°C, which means that it is not possible to use them. Accordingly, as a method of lowering the temperature coefficient xf of a dielectric ceramic composition, the method is available of preparing a material whose dielectric constant ε is as large as possible and whose temperature coefficient xf has a negative value; with this method, a ceramic composition can be obtained by a suitable composition whose dielectric constant ε is large and whose temperature coefficient xf of resonance frequency is small. For example, Laid-open Japanese Patent Publication No. H. 5- 211009 proposes the obtaining of a ceramic composition of large dielectric constant ε and whose temperature coefficient of resonance frequency xf is close to zero, by preparing a material represented by the compositional formula (Al + 1 /2 . B3 + 1/2 ) TiO 3 where Al + is Lil + , and B3 + is Nd3 + , Sm3 + , Co 3 + or Pr3 + , constituting a material of large dielectric constant ε and wherein the temperature coefficient xf has a negative value. However, the demands for miniaturization of portable electronic terminal equipment have today become so exacting that a material having even higher dielectric constant ε is earnestly sought for the dielectric material of resonators, filters and capacitors employed in such devices. DISCLOSURE OF THE INVENTION In view of the characteristics required for a dielectric ceramic composition for microwaves, an object of the present invention is to obtain a dielectric ceramic composition wherein the dielectric constant ε is large, the temperature coefficient xf of the resonance frequency is close to 0, and which has a large Q value, by adding to and blending with a ceramic composition whose xf of the resonance frequency is large on the plus side to a ceramic composition whose temperature coefficient xf is large on the minus side. With the object of providing a dielectric ceramic composition whose dielectric constant ε is large, whose temperature coefficient of resonance frequency xf is close to 0, and whose Q value is large, the present inventors have previously proposed a dielectric ceramic composition represented by the compositional formula Li2θ-Na2θ-Bi2θ3-R2θ3-Tiθ2, where R2O3 is one or two or more of La2θ3, Nd2θ 3 , Sm.20 3 , C02O 3 or Pr2θ 3 (Japanese Patent Application Number 2000-337141). Also, the present inventors have proposed (Japanese Patent Application Number 2000-340104) a dielectric ceramic composition represented by the compositional formula Li2θ-Bi2θ 3 -R2θ 3 -SrTiθ 3 , where R2O 3 is one or two or more of La2θ3, Nd2θ3, Sm2θ3, C02O3 or Pr2θ3. As a result of further assiduous investigation, the present inventors discovered that an excellent dielectric characteristic could be obtained in stable fashion by co-presence of specific quantities of Bi2θ 3 , Na2θ and MO (where M is one or two of Ca and Sr) in the one or two or more of La, Nd, Pr and Sm constituting R, in the Li2θ-R2θ3-Tiθ2-based composition. Specifically, the present inventors discovered that, in an Li2θ- R2θ 3 -Tiθ2-based composition, an improved dielectric constant ε could be achieved by introducing a specific quantity of Bi2θ3, and xf could be shifted to the plus side and in addition the effect of a considerable improvement in Qf achieved by introducing a specific quantity of MO (where M is one or two of Ca and Sr). They discovered that, by introducing MO, xf becomes too large, making it difficult to make xf approach 0 while maintaining Qf at a fixed value, so, by introducing a specific quantity of Na O together with the MO (where M is one or two of Ca and Sr), in particular in the case of material of εr > 150, it was possible to control xf to the vicinity of 0 while maintaining Qf at an high value, and thereby perfected the present invention. Specifically, the present invention consists in a microwave dielectric ceramic composition represented by the compositional formula aLi2θ-bNa2θ-cR 2 θ3-dBi2θ3-eMO-iTiθ2 (where a + b + c -l- d -l- e -f- f = 100, a, b, c, d, e and f being mol%) where R includes one or two or more of Nd, Sm, Pr, and La, M includes one or two of Ca and Sr and a, b, c, d, e, f satisfy 5 < a < 15, 0 < b < 10, 3 < c < 15, 1 < d < 15, 1 < e < 30, and 40 < f < 75. BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in the Li2θ-Na 2 θ-R2θ 3 -Bi 2 θ 3 -MO- Tiθ 2 -based composition (where R is one or two or more of Nd, Sm, Pr, and La and M is one or two of Ca and Sr), if Li2θ is less than 5 mol %, the dielectric constant is low and xf becomes too large on the plus side; while if it exceeds 15 mol%, Li2θ being of low melting-point, this is undesirable because there is the problem that the ceramic composition reacts and fuses with the base plate or base powder during sintering. A range of 5 < a < 15 mol% is therefore specified for Li2θ (a). Also, if Na2θ exceeds 10 mol%, this is undesirable because it gives rise to the problem that xf becomes too large on th.e plus side, and Qf falls. Accordingly, a range of 0 < b < 10 mol% is specified for Na2θ (b). If R2O3 (R3+ is one or two or more of Nd3+, Sm.3 + , Pr3 + , and La 3 +) is less than 3 mol%, the dielectric constant is low and Q is also poor; if it exceeds 15 mol%, there is little benefit and costs are increased, which is undesirable. A range of 3 < c < 15 mol is therefore specified for R 2 O3 (c). Bi2θ 3 has the effect of increasing the dielectric constant ε and a content thereof of at least 1 mol% is necessary; however, because of its lower melting-point, if it exceeds 15 mol%, there is a risk that the ceramic composition will react and fuse with the base plate or base powder on sintering; this is therefore undesirable. Accordingly, a range of 1 < d < 15 mol% is specified for Bi2U 3 (d). Also, the content of MO (where M is one or two of Ca and Sr) has the benefit of improving Qf and improving the temperature coefficient xf; however, if it is less than 1 mol , there is little benefit in terms of improving Qf and improving the temperature coefficient xf and if it exceeds 30 mol%, the temperature coefficient xf becomes too large on the plus side, which is undesirable. Accordingly, a range of 1 < e < 30 mol% is specified for MO (e). In addition, if Tiθ2 is less than 40 mol%, the required crystalline phase is not obtained and the required dielectric characteristic is not obtained; if it is more than 75 mol%, the problem arises that a phase consisting of TiO on its own appears, severely lowering Qf, which is undesirable. A range of 40 < f < 75 mol% is therefore specified for Tiθ2 (f). EXAMPLE High-purity TiO 2 , Bi 2 O 3 , Li 2 CO 3 , Nd 2 O 3j Sm 2 O 3 , Pr 6 On, La 2 O 3 , Na 2 CO 3 , CaCO 3 , and SrCO3 were weighed out and blended such that the required mol percentages were obtained in the raw material, as in Table 1 to Table 2, so as to obtain a mixture of compositional formula a i 2 θ-bNa2θ- cR2θ3-dBi 2 θ3-eMO-iTiθ2 (where a + b + c + d + e + f = 100, a, b, c, d, e and f being mol%, R includes one or two or more of Nd, Sm, Pr, and La, M includes one or two of Ca and Sr); mixing was performed for 5 to 20 hours using a ball mill. After mixing, calcining was performed for one hour to five hours at 700°C to 1000 ° C. After this, the mixture was again pulverized for 2 to 50 hours, and the pulverized powder was mixed with organic binder and pelletized, then sieved and molded into the shape of a disc of diameter 10 mm, thickness 6 mm with a pressure of 2 to 3 T/cm2. This molding was then sintered for one to five hours at 1200°C to 1400°C, and both faces thereof polished so that the thickness of the sintered body was half its diameter, thereby producing a measurement sample. The dielectric constant ε, Q value and temperature coefficient xf of resonance frequency of the measurement samples obtained were measured at a measurement frequency of 3 GHz, using the method of Hakki and Coleman. The measurement results for the dielectric characteristic of the measurement samples are shown in Table 3. Table 1 Table 2 Table 3 INDUSTRIAL APPLICABILITY In an Li2θ-R2θ 3 -Tiθ2-based composition, an improved dielectric constant ε can be achieved by introducing a specific quantity of B12O3, and xf can be shifted to the plus side and in addition the effect of a considerable improvement in Qf achieved by introducing a specific quantity of MO (where M is one or two of Ca and Sr). Furthermore, by introducing a specific quantity of Na2θ together with the MO (where M is one or two of Ca and Sr), in particular in the case of material of εr > 150, it is possible to control xf to the vicinity of 0 while maintaining Qf at an high value. A dielectric ceramic composition according to the present invention is ideal for the dielectric material of resonators, filters and capacitors used in transceivers for satellite communication broadcasting or mobile identification devices etc that make use of microwaves of a few GHz, since, as is clear from the Practical Examples, its dielectric constant ε is large, its temperature coefficient xf of resonance frequency approaches 0, and a large Q value is obtained therewith.

Claims: CLAIMS 1. A microwave dielectric ceramic composition represented by the compositional formula aLi2θ-bNa2θ-cR 2 θ3-dBi2θ3-eMO-fTiθ2 (where a + b + c + d + e + f = 100, a, b, c, d, e and f being mol ), wherein R includes one or two or more of Nd, Sm, Pr, and La, M includes one or two of Ca and Sr, and a, b, c, d, e and f satisfy: 5 < a < 15, 0 < b < 10, 3 < c < 15, 1 < d < 15, 1 < e < 30, 40 < f < 75.

Inventors: FUKAGAWA TOMOKI, NISHIKAWA KAZUHIRO, FUKAGAWA, TOMOKI, NISHIKAWA, KAZUHIRO
Applicants: FUKAGAWA TOMOKI, NISHIKAWA KAZUHIRO, SUMITOMO SPEC METALS, FUKAGAWA, TOMOKI, NISHIKAWA, KAZUHIRO, SUMITOMO SPECIAL METALS CO., LTD
Application year: 2001
Main classification: C04B35
IPC codes: C04B35, H01B3, H01G4