TW200900373A - Dielectric ceramic composition - Google Patents

Abstract

A dielectric ceramic composition includes a bulk phase, a glass phase additive and a modified additive. The bulk phase is composed of BaO-TiO2. The glass phase additive is a material selected from the group consisting of B2O3, ZnO, SiO2, BaO, Al2O3 and Bi2O3. The modified additive is a material selected from the group consisting of GeO2, Dy2O3, Mn2O3, BaCO3, CaCO3 and CuO. The ceramic composition can be cofired with metal copper, and has characteristics of low dielectric loss, low electric capacity, and low temperature coefficient to significantly reduce the manufacturing cost for the ceramic composition.

Description

200900373 IX. Description of the Invention: [Technical Field] The present invention relates to a ceramic material which is suitable for use in a temperature-compensated dielectric-type low-temperature reducing atmosphere sintering process for high-frequency applications. . . Applicable to [Prior Art] Laminated ceramic capacitors are made of ceramic, | mussels and internal electrode precious metals (such as palladium (Pd) and palladium (Pd) / silver (Ag) alloys) Once long cubes and ceramics components, this component has the characteristics of small size and high density capacitance. It is widely used in the design of densely-formed circuit boards. In recent years, with the rapid development of electronic technology, the application requirements of multi-layer ceramic pot containers have also developed in the direction of high capacitance, high power and high frequency applications. At the same time, the price of precious metals such as (4) used as internal electrodes has rapidly and dramatically increased, resulting in a rapid increase in component costs, and has also driven manufacturers to find process methods and materials that combine low production costs with high functionality. On the premise of reducing the manufacturing cost, the process of sturdy metal electrode (electro-electrode) is opened, which is a cheaper nickel (Ni) or copper (Cu) metal under the sintering treatment of a reducing atmosphere. Instead of expensive palladium or palladium/silver alloys as internal electrodes. In addition, in the application environment of high-frequency communication, it is necessary to achieve lower equivalent series resistance (ESR, Equivalent Series).

Resistance and Dissipation Factor are required. Therefore, copper metal with superior electrical conductivity is an electrode metal material with potential for development. However, 'in actual process', due to the low melting point of copper metal (< 丨丨〇〇.匚), 5 200900373 'Knife-to-the-square; oxidized under the dish, is not suitable for co-firing at high temperatures in the traditional atmospheric environment. The method is to be produced, and the application of the high-frequency communication terminal is considered in the future. Therefore, the introduction of microwave dielectric materials with low-temperature co-firing characteristics (<1000 °c) to meet the requirements of low-temperature sintering production is also the current The trend of capacitor development. In related domestic and foreign patented towels, it meets the low dielectric constant (K~B2G) and high quality factor (Q value >1_) of the m material, the most widely: W 疋; MgTi 〇 3 material, however, due to magnesium ion (Mg2+) is easily dissociated in the solution, resulting in a multilayer capacitor (ML(:c) is abnormal in the rheological properties of the (4) ribbon process and when more free town ions are added, more dispersant needs to be added. Dispersion also causes the bulk density of the ceramic ribbon to decrease, which in turn increases the number of defects inside the sintered component, affecting its electrical properties. In US Pat. No. 43,944565, the composition of the rare earth element contained in the composition, such as oxidation Convergence (_2〇7), etc., in the production of MLCC, the etched ions (Nd) also have similar dissociation conditions with the above-mentioned magnesium ions. When the addition amount is increased, the q value of the sintered component and the temperature coefficient of the resonance frequency will also be apparent. In the early research of microwave dielectric materials, the ceramic oxide composed of Mg_Zn_Ti can be sintered at a lower temperature (about US 4, 453, 974 and the Republic of China No. 12,364,462). ), there are also researchers who want Try to make the lower (four) point of the glass phase composition, (4) the condition of co-firing with the Ag internal electrode, but the sinterability and electrical properties of the obtained material are obviously reduced. ^ US Pat. No. 6,309,995.) In addition, MgTi〇3_CaTi〇3 It is also a material system with low dielectric loss and low resonance frequency temperature coefficient (Republic of China Announcement No. 00245806), replaced by an equivalent element, that is, replaced by ^ 6 200900373

Zr replaces T" to obtain the composition of xSrZr (V(Bu x)CaTi〇3, which can be added by a suitable glass formula, which can be reduced from the original 丨3〇 (the sintering temperature of rc is greatly reduced to 1 〇〇 (TC below). It is produced by co-firing at a low temperature, and the related research is shown in the content of U.S. Patent No. 63,353,10.

As described in U.S. Patent No. 5,599,757, it is based on a relatively low cost microwave dielectric material BaTi4〇9 as a main phase component, and with suitable glass addition yttrium, it can achieve a sintering temperature of less than 1100 ° C and is superior. Microwave dielectric properties, but still not co-fired with silver or copper, the lead added in the formulation also affects its electrical properties. Japanese 帛2000_281442 patent uses BaTi4〇9 as the main component, adding the equivalent element of the substituted Ti element component, D, 钇(Zr) 'sub, Zn〇, n, Li2C〇3, Ca〇 and si〇2 The composition of the glass phase successfully reduced the sintering temperature of the ceramic to 93 〇, however, its glass phase separation formula contends that the added clock element, which is prone to ion conduction in the glass structure, affects the insulating properties of the ceramic.盥 2 US Patent No. 6,949,487, further explores the glass phase composition of the modified shelling agent formulation, and obtains the composite formulation of Dingshao ceramic··glass with both low-temperature sintering and dielectric properties. 49 Because of Ba〇_Ti〇2 The series has low-cost characteristics, and also adds Nb2〇5' to the BaTi〇3 composition to obtain Baf4Nb4〇2 with better quality factor (Q value about _, κ value about 55) (such as US (10) state ^: No) and high temperature microwave dielectric phase enthalpy formula for 〇2s (Q value about side, κ value about 41) (as shown in the patent of Guodi 63 16376) can effectively reduce the sintering temperature... retain its high frequency Si .... There are also related patents published in China, such as the Republic of China application No. 7 200900373 2005 02993 patent and the Republic of China No. I227558 ; patent; in addition, BaTi03-CaZr03 composition (Republic of China Announcement No. 57786 专利 patent), BaO -T]〇2-Bi2〇3-Ln2〇3 (Ln is La or Nd) composition (Republic of China Announcement No. 00234766) and (ca-Sr-Nd-Cd) Ti03 material composition (Republic of China Bulletin No. 00426864) Patent), all patents are published, but the materials with BaTi〇3 as the main phase are more Dielectric properties, but the dielectric loss at high frequencies is large, and the sintering temperature is high (1100~115〇°c). In other low-temperature microwave material formulation development, such as Ca〇_Zr〇2 system (such as U.S. Patent No. H09-3 15 859), Bi2〇3_Ca〇_Nb2〇5 series (such as the patent of U.S. Patent No. 5,350,639 and Japanese Patent No. H11-34231)

The LaNb〇4 series (as described in U.S. Patent No. 6,620,750) emphasizes that its formulation conforms to the sintering process characteristics at low temperatures and has a high quality factor. It is also worth mentioning that, as mentioned in the U.S. Patent No. 5,350,639, the ceramic formulation can improve the dielectric loss caused by sintering under low oxygen partial pressure after appropriate addition (Cu0, VA5). Co-fired with copper metal (Cu) under a reducing atmosphere. The earliest patent for the production of copper-baked metal co-firing is the patent of H05-1 82524, which is based on Tl〇2_Zr〇2_Sn〇2. Although it does not get the ideal Q value, it is suitable. A glass additive that can be co-fired with copper. It is known from the above related patent documents that most of the metals co-fired by microwave dielectric materials are mainly low-oxidation silver (Ag) metals, and only a few patents mention co-firing with copper (Cu) metals. Production results. However, the ceramic material in the reducing atmosphere (NO and copper metal co-firing may increase the oxygen vacancy in the material, resulting in local semi-conductivity, but reduce the original dielectric properties of the ceramic body 8 200900373. In view of the problems of the conventional dielectric ceramic materials having high manufacturing cost and high electrical characteristics, the object of the present invention is to provide a temperature-compensated capacitor crying which can be applied to high-frequency applications, and is suitable for low-temperature reducing atmosphere. In the sintering process, the manufacturing process can be reduced. In order to achieve the above object, the dielectric ceramic composition of the present invention is a main phase composed of barium titanate (BaO-Ti〇2); The glass phase additive is selected from the group consisting of boron oxide (BA., zinc oxide (5) 0), dioxo (Si〇2), oxidized pot (Ba〇), oxidized (Al2〇3) and oxidized (Βι2〇). 3) at least one material of the constituent materials; and a modified additive selected from the group consisting of cerium oxide (Ge02), antimony trioxide (Dy2〇3), and dimanganese dioxide (Mn2) 〇3), barium carbonate (BaC〇3), carbon S夂 catch (Ca At least one of a group of materials composed of CQ3) and copper oxide (CuC). Preferably, the molar ratio of the main phase such as 0 to D1 is between 3 and 75 to 46. Preferably, the body phase accounts for 88 to 9 secrets of the overall composition. Preferably, the glass phase additive comprises Μ% to % of the overall composition. Preferably, the glass phase additive comprises 〇. (H~2.5wt% oxidized stone, 0.3~5.5wt 〇/〇 zinc oxide, 〇2~2 2wt/〇_emulsified 矽, 14~55wt% oxidized lock, 0.01~〇.5wt% alumina 盥〇〇1 ^ υ ϋ·ϋ1~〇, 2wt% gasification 铋, the above ratio is the weight percentage of each material as a whole composition. 9 200900373 Preferably, change,兵1上上, the small additive accounts for 0.01~2wt% of the whole composition. Preferably, the change; the mussel 4 addition includes 〇·〇1~〇·5wt0/oxidation '0.01~0.5wt% three g 儿 ^ ^ 二镝, 0_01~lwt% dimanganese oxide, 0.01~1.5'^% carbon brewing phase', 〇·〇1~lwt% calcium carbonate and 〇.〇〗 〖% oxygen copper, the above ratio The oxidation of Q is the weight percentage of each material as a whole composition. Due to the composition of the dynasty 1 Maotao enamel of the present invention, it can also co-fire with copper metal, low dielectric damage pseudo && ^ ^ - ϋ - ^ F#! ^ Characteristics of electric valley / temperature coefficient, can be widely used in low temperature co-fired ceramics ^ v 〇w Temperature Co-fired Ceramic > LTCC)

Process or laminating ceramics D ^ ^ ^ (Multi-layer Ceramic Capacitor -

The production of MLCC), w μ μ μ P and significantly reduce manufacturing costs. [Embodiment] The preferred embodiment of the material composition of the ceramics of the present invention is a package of 3 glassy phase additives and a modified additive; wherein the main phase is made of titanic acid The composition of the sulfhydryl group (Ba〇_Ti〇2); in the preferred embodiment, the bulk phase accounts for 88~97wt°/ of the positive composition. (% by weight),

The molar ratio of Ba〇 to Tl〇2 is between 1:3.75 and 1:4.6; — is distant from boron oxide (B2〇3), zinc oxide n, and one emulsified stone (Sl〇2). At least one of the materials in the group consisting of yttrium oxide (Ba〇), oxidized yttrium (ai2〇3), disk oxygen (4), (9), 2〇3), in the preferred palladium case, the glass phase additive occupies the overall composition 2·9~i〇wt%, which may include 〇. (M~2.5wt% oxidation code, Q 3~5 5wt% ^ ^ 0.2~2wt% dioxane, 14~5 5_% yttrium oxide, g qi ~g wall oxidation Shao and 〇.01~〇 the oxidation money, the above ratio is the whole material of the material, and the weight percentage of the product; 10, 200900373 The modified additive is selected from the second oxidation (Ge〇2 ), i-oxidized steel (Dy2〇3), bismuth trioxide (Mn2〇3), carbonated lock (BaC〇3), carbonated feed (CaC〇3) and copper oxide (Cu〇) At least one material 'in the preferred embodiment' is a modified additive comprising 0.01 2 wt/〇 of the total composition, preferably 〇〇i~〇5 wt% ceria, 0.01~0.5 wt% dioxide. Two 镝, 〇〇 1 ~ lwt% three oxidation, fierce, " Bu 1 $ Wt% cesium carbonate, 0.01~1wt% carbonate and 〇i~iwt% copper oxide, the above ratio is the weight percentage of each material as a whole composition. Example 1: Preparation process of bulk phase powder

The main phase powder is prepared by using barium carbonate (BaC〇3) and titanium dioxide (Ti〇2) as the starting material of barium oxide (Ba〇), and the molar ratio of Ba〇 to η% is 1:3.75~1. After weighing in the range of 4.6, place it in a ball milled jar made of polyvinyl chloride, add deionized water and Toughened ZirConia, YTZ) and grind the ball for 2 hours. After mixing, Drying in an 80t oven; after that, the dried main body phase is heated to 12 ° C at a heating rate of 5 ° C / miri, and calcined at atmospheric conditions (Calcinatl〇n), and held for 5 hours. After the calcination is completed, the main phase, the YTZ grinding ball and the alcohol solvent after calcination are ground in an ball mill for a small hour to obtain a bulk phase powder having an average particle diameter of less than 1 μη (micrometer). Example 2: Preparation of glass phase additive powder The preparation of glass phase additive is made of boron trioxide (Be3), zinc oxide 11 200900373 (μ), dioxide dioxide (Sl〇2), oxidation rhyme 〇) 'San Oxide II (4) Office) /, yttrium oxide (b) 2 〇 3) 'According to the weight ratio of τ list one, weighed and placed in the ball mill tank of the gas-rich ethylene material' and added deionized Water Shaw ζ ζ = = · 'Double ball mixing for 20 hours, after the completion of the mixing, after the dry wood knock in the force step oven, 'the glass phase additive after the chess is dried at a heating rate of 5 ° C / min followed by force: (4) 'Asian Melting was carried out for 5 minutes (heart (four) treatment, = tt cooling. After drying, the glassy phase additive and the granules were ground in a ball mill for 24 hours, and the glass phase additive powder was uniformly granulated.

Table 1 Unit: %) B, Wide Example 3: Preparation process of dielectric ceramic composition The main phase powder and the glass phase are added. The bulk powder and the glass-filled additive powder are mixed, and then the main mixture is mixed. Change Cao, Tian 4 P and modified shellfish additions to the Wenbei additive system, bismuth dioxide 7'7 (Dy2〇3), trioxide _ cooking r 2), dioxide dioxide (CaC〇3) and oxidative meaning钡(BaC〇3), carbonic acid, ritual copper (CU〇), according to the second table, the proportion of the relationship between the mixed warehouse 12 200900373. Table 2, Group weight percent composition of the mass additive ABCD GeO? 38.5 : Dy) CK 23 23 75 Μη, Ο, 77 38.5 25 1 1 BaCO, CaCO, • _ -------- --- --- CuO . A 5 6 E 33 11 56

F ratio (unit: %)

G Η -1L ^27_ 56 100 21 21 7 7 72 72- The mixing ratio of the bulk phase, the glass phase additive and the modifier is shown in Table 3 below. Each group of 忐8 kg and +, Chengdaoyi formula is weighed and placed in a ball mill jar, and added to the honing ball and the alcohol solvent, and then ground and dried in a ball mill tank for further drying to obtain a dielectric ceramic composition. powder. Add force

ν Formula body phase composition number - BaO and Ti02 Molar ratio wt% 1 1:3.75 89.6 __2 1:4.5 89.6 3 --- 1:4 89.6 1:4 88.7 13 200900373 5 1:4 88.7 B 1.3 A, 10 6 1:4 95.6 C 0.4 A, 4 7 1:4 91.25 G 1.25 C, 7 5 8 1:4 91.6 D 0.9 B, 7 5 9 1:4 91.6 E 0.9 B, 7 5 10 1:4 90.7 F 1.8 B, 7 5 11 1:4 91.1 Η 1.4 B, 7 5 12 1:4 91.1 I 1.4 B, 7.5 Add the powder of the dielectric ceramic composition obtained in the above formula to a trace amount of polyvinyl alcohol (Polyviny) Alcohol) Granulation (Pelletizatlon), the powder was sieved, and the powder was tableted into a 5 mm thick, 20 mm diameter test piece by a uniaxial molding machine at a uniaxial pressure of 9 psi; subsequently, the test piece was The side is coated with a copper paste (Copper Paste) and co-fired with copper metal (c〇_firing). On the co-firing treatment, the copper metal paste is applied first. The test piece of the electric ceramic composition is subjected to degreasing reaction at 60 (TC high purity nitrogen gas (99.999% NO environment with a temperature of 4 small 4; subsequently, further heating to 9 〇〇 to 95 〇 its pure hydrazine or nitrogen / hydrogen The mixed atmosphere (hydrogen in the volume ratio of the mixed gas is between 〇1 and 1.5%) is subjected to a sintering reaction for 2 hours. The dielectric ceramic composition and the copper metal are co-sintered in a reducing atmosphere, and the sintering is measured. The bulk density and the dielectric constant, the dissipation coefficient, and the dielectric constant temperature coefficient of the co-fired material were measured by a Cavity method in conjunction with a network analyzer (Agilent 8722ES) to measure the sintered body at high frequency (4 GHz). OD quality factor 14 200900373 sub (Q). The temperature coefficient of the dielectric constant is calculated by the formula. Temperature coefficient (ppmrc): KCi25_C25)/C25]*[l/(125-25)]*l〇6 Related measurement results Table 4 below is shown in Table 4. Table 4: Electrical properties of sintered body after co-sintering of ceramic dielectric composition and copper metal

Quality factor 氺4

1065 1202 <1000 <1000 1200 1 168 1006 1186 1014 1137 2102 1531 1271 15 200900373 14 10 15 11 16 12 945 0 — 33.3 2.7* 1 0'4 4.21 32.7 1412 0 — 35.1 2.1*1 Ο'4 4.37 31.5 1496 0 ----- 35 3.1*1〇-4 4.39 29.5 1135, w this ginseng bottle < basket ratio. *2· It is measured at a resonance frequency of 1 MHz. *3· It is measured at a temperature of 25 to ~125. It was measured at a resonance frequency of 4 GHz. The results of the measurement of the sample °〇5 show that when the molar ratio of the main phase BaO盥Ti〇 is about i.4 士 π „ 4 ' after the sintering process under the original atmosphere, the degree of one limb is 4.27g/cm3, the dielectric constant is 32 4, and the dispersion coefficient measured under low frequency condition is 4χ iQ 4, (2). The temperature coefficient is 27.5ρρχη/°〇, and the phase 7 is under the condition of μ The Q value measured by (4 GHz) is 12 〇〇. At the same sintering temperature, the Müller number ratio is about 1:3.75 (sample υ, less 兀', and the dissipation coefficient of the limbs is extravagant. JU (4.3*10-4); and the molar ratio is about 1:4.5 T (sample m 2)' The density of the sintered body material is 4 3 and often increases to 34.6. 1 "Number of books ^ and below ( I milk accounts for 0.2~0_6% of the total volume of the mixed gas. The percentage of the molar ratio is 4, the molar ratio is 4 (the mouth 6 and 7) is 4.5 (molar 3 and 4). The formulation is clearly resistant to reduction. In the study of the modified additives, the strong, the Luo language... The addition of the Ge, Mn and Dy in the Jiuzhong, ^ the dielectric properties of the sintering under the original gas, Xu Shi., several primitives are helpful, It also enhances the nature of the sample as shown in Table 4, which is the result of the data of the 盥 ϊ ϊ 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表Electrical characteristics and temperature coefficients, such as r 僳 12, 13 and 4, are not. However, when the amount of addition is too much, 16 200900373 'Gentry, Cu, plagiar J, mouth star greater than 1 wt% and Ca addition amount greater than 1 wt〇 / 士, ratio = high frequency dielectric properties of the material, such as The sample data in Table 4 is two-two-off: in the test results of the target additive, it can be seen that the amount of glass phase added in the dream, Wt/°, the sintered density and dielectric properties of the material are all reduced to A. , Shi Shengqi white "Wen to shirt (a) ^ Table 4 in the sample 1 〇 data, the material is insufficiently sintered, and decreased (4.16g / em3), the dielectric constant also dropped to 3G.5. In the glass::Γ:(Βι) ′ is beneficial to reduce the melting of the glass phase formulation, which can improve the effect of liquid phase sintering during sintering, as shown in the data of sample 1 in Table 4. Production I II above the composition of the pottery pottery developed in this case, can be at a sintering temperature of less than 95 ° ° C and please name Tai Ding 譬 ^ C original milk chaos 'such as high purity nitrogen or nitrogen / hydrogen mixed atmosphere: brother , copper metal is co-sintered and not semiconductorized, can reduce the cost of two?1, and has a low temperature coefficient (<±3〇ppm/t), low dispersion) 1=vibration frequency is 1MHz' The 〇 and mussel factors with a dissipative system of less than 4 tubes (having a higher than the capsule at a resonance frequency of 4 GHz) have a dielectric constant of 30 to 40 Å, which can improve the ceramic-free capacitor (ΝΡΟ-type ΜΙΧ) (:) Φ$ M w, 曰陶竞 composition. 败) "Characteristic temperature-compensated dielectric, the above is only the preferred embodiment of the present invention, not used for the day ^ this = Ming implementation Scope, the general scope of the patent application and the technical idea of the invention disclosed in the Ming Dynasty are still within the scope of the patent of the present invention. For example, the starting point of (4) may be BaC. 〇3'BaC2〇4, Ba(C2H5CO)H〇3 starting material\1 200900373 can be h3bo3 or b2o3, etc. [Simplified illustration] 0' > [Main component symbol description

Claims (1)

200900373 X. Patent application scope: 1 _ A dielectric ceramic composition, which includes: - the main phase ' is composed of barium titanate (Ba0_Ti〇2); the B-phase phase additive is selected from oxidation At least one of a group of materials consisting of boron (b2o3), zinc oxide (Gn〇), emulsified cerium (Si〇2), cerium oxide (Bao), aluminum oxide (Al2〇3) and oxidized secret (Bi2Q3) And Dan you are selected from f and shell additives At least one material selected from the group consisting of dysprosium (Dy2〇3), dimanganese dioxide (Μη203), barium carbonate (BaC03), cadmium (CaC〇3) and copper oxide (Cu〇). [2] The dielectric ceramic composition according to Item 1, wherein the main phase comprises cerium oxide (Bao) and titanium dioxide (Ding 〇2), and cerium oxide (Ba 〇) and titanium dioxide (Ti 〇 2) The molar ratio is between 1:3.75 and 1:4.6. 3. The dielectric ceramic composition according to claim 2, wherein the main phase accounts for 88 to 97% by weight of the total composition. 4. The dielectric ceramic composition according to claim 3, wherein the glass phase additive accounts for 29 to 1% by weight of the total composition. 5. The dielectric ceramic composition according to claim 4, wherein the glass phase additive comprises 〇.〇y boron oxide, 0.3~zinc oxide, 0.2~2wt% cerium dioxide 'μ~5·5νη % yttrium oxide, 0.01~0.5wt% oxidation and 〇〇i~〇.2wt% oxidation grade, the above ratio is the weight percentage of each material as a whole composition. 6. The dielectric ceramic composition according to the fifth application of the patent application, 19 200900373 wherein the additive is G.G1~2wt% of the overall composition. Lizhong I changed ^ please refer to the dielectric composition described in item 6 of the patent scope, :^ "Additives include 〇_01~〇.5wt% cerium oxide, 〇·(Η~0 domain 镝, _〜1wt % barium strontium carbonate, 0 · 0 1~1 wt% sodium carbonate Λ Λ, 社八效触弓和〇·01~1Wt% copper oxide, the above ratio is the weight percentage of each component of the i limb composition f 8 ·"Please refer to the dielectric ceramic composition described in item 1 of the patent scope, the main phase of the occupant is 88~97wt0/〇 of the whole composition. 9. The dielectric as described in the application of the patent scope In the ceramic composition, the glass phase additive accounts for 2 9 to 1% of the total composition. 1 〇 · The dielectric ceramic composition according to claim 9 of the patent application, wherein the glass phase additive包肖〇_〇1~2 cut oxidized, 〇-3^.5wt〇/0^, bl, . lock, 〇_〇1~0.5wt% oxidized and 〇〇1~〇2wt% yttrium oxide, above The ratio is the weight percentage of each material as a whole composition. 1 1 The dielectric ceramic composition as described in claim 1 wherein the modified additive accounts for 0.01 to 2% by weight of the total composition. [12] The dielectric additive composition of the dielectric ceramic composition according to Item 1 of the claim patent includes 〇.〇!~〇.5 wt% cerium oxide, 〇.01 〇'5Wt% bismuth dioxide 0.01~lwt% dimanganese trioxide, ^1.5Wt/°^ acid bismuth, 0·01~1 Wt°/. The ratio of calcium carbonate to 0.01~1 wt% copper oxide is the weight of each material as a whole composition. Percentage. 1 3 · The dielectric ceramic composition according to claim 1 of the invention, wherein the bulk composition is 88 to 97 wt%, the glass phase is added 20 200900373, and the addition constitutes 0.01~ of the total composition. 2wt%, above 2-9~】〇wt%, the modified additive accounts for 100% of the composition of the whole composition. 14 The dielectric ceramic composition as described in claim 13 of the patent scope, The main phase comprises cerium oxide (Ba〇) and titanium oxide (Ti〇2), and the molar ratio of barium oxide (BaO) to titanium oxide (Ti〇2) is between 1:3.*75~1:4.6 XI. Schema·· f/ as the next page / \ 21