KR20040025177A - Low temperature cofired ceramic composition, and its use - Google Patents

Abstract

PURPOSE: Provided is a low temperature co-firing dielectric ceramic composition, which has a high dielectric constant, low dielectric loss and excellent stability of dielectric constant against temperature so as to reduce the volume of multilayer ceramic module-type electronic components and to improve the characteristic property of the component. CONSTITUTION: The ceramic composition comprises: (a) x(Ba,Sr)O·y(Ti,Zr)O2·z(Nb,Ta)2O5 as a main component, (b) a firing aid, and (b) a bonding modifier, wherein the main component is represented by the formula of x(aBaO,(1-a)SrO)·y(bTiO 2,(1-b)ZrO2)·z(cNb2O5,(1-c)Ta2O5), in which 0.15<=x<=0.3, 0.15<=y<=0.3 and 0.4<=z<=0.7, and 0<a<=1, 0<b<=1, and 0<c<=1; the firing aid comprises one or more compounds selected from the group consisting of B2O3, ZnO, CuO, V2O5, Sb2O5 , Bi2O3 and Ag2O; and the bonding modifier is represented by the formula of αXβYγ(SiO2), in which 0.01<=α<=1, 0.1<=β<=4 and 0.1<=γ<=8, and X is a substance comprising one or more elements selected from the group consisting of Na, K, Mg, Ca and Ba, and Y is one or more elements selected from the group consisting of B and Al.

Description

LOW TEMPERATURE COFIRED CERAMIC COMPOSITION, AND ITS USE

[Technical Field]

The present invention provides a ceramic composition comprising a main component of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ , a sintering aid, and a bonding regulator, a heterogeneous ceramic assembly using the same, And passive integrated devices. More specifically, a multilayer device is formed by bonding and co-firing with metals such as silver, copper, nickel, gold, silver-palladium alloys, silver-platinum alloys as well as heterogeneous low-temperature co-fired ceramics based on glass. Or it relates to a dielectric ceramic composition capable of making a ceramic printed circuit board of a multi-layer structure and its use.

[Private Technology]

With the rapid development of the information and telecommunications industry, electronic and mobile communication devices are also becoming smaller, more versatile, and more specialized. Accordingly, such demands are rapidly increasing in the electronic components constituting them, and components using dielectrics are no exception. Silicon-based (Si) and gallium-arsenic (GaAs) -based semiconductor active devices have already met the above requirements through thinning and stacking. Passive devices using dielectrics are also responding to MLCCs or chip inductors through thickening and multilayering, but the small size and high characteristics of these products cannot keep up with the development of higher technology.

In order to solve this problem of passive devices, integration of passive devices using low temperature cofired ceramics (LTCC). This is accomplished by wiring the electrode circuit, which constitutes two or more capacitors, inductors, and resistors, onto an unfired dielectric ceramic called a green sheet, laminating them in three dimensions, and then firing the electrodes and ceramics simultaneously. It is a technology that implements a passive device in the form of one chip. As passive integrated devices using such low-temperature cofired ceramics, chip antennas, couplers, stacked LC filters, diplexers, and chip baluns are widely used.

In addition, ceramic multi-chip modularization (MCM-C, Multi Chip Module-Ceramic) technology is commercialized, which enables surface-mounting of multiple semiconductor active devices on a low-temperature, co-fired ceramic substrate with a large number of passive devices to perform one independent function. It is becoming. Such module components include an antenna switch module, a front end module (FEM), and a power amplifier module (PAM).

Low-temperature co-fired dielectric ceramics that can be used for the above purposes are: i) Metals such as silver (Ag) and copper (Cu), which have excellent electrical characteristics due to their low resistance loss, should be used as circuit electrodes. Firing should be completed at low temperatures, ii) the coefficient of thermal expansion with silicon or gallium arsenide semiconductor devices should be boiling, iii) the dielectric properties should be suitable for the application, and iv) the change in dielectric constant with temperature It should be small.

The low temperature co-fired ceramics, which are widely used in accordance with the above requirements, are made of silicate-based glass as the main phase. The composition to be baked below is dominant. Depending on their form, they are 1) glass ceramic based on recrystallized glass, 2) glass-ceramic compound based on the reaction crystal phase produced through the reaction between a known phase glass and a ceramic filler. And 3) glass-ceramic mixture systems using non-reactive liquid phase sintering (NLPS) without reaction between base glass and ceramic filler (Ceramic Filler).

However, commercially available silicate glass-based low temperature cofired ceramics have their advantages and disadvantages. Its advantages include easy firing, low dielectric constant of less than 10, and low signal delay when mounting active elements that process digital signals. The coefficient of thermal expansion is similar to that of silicon or gallium arsenide-based semiconductors, and the cost is low. will be. However, low capacitance permits the implementation of capacitors with high capacitance, which requires increasing the number of stacked layers, and incorporating a TE mode resonator has a limitation in size reduction. In addition, due to the large dielectric loss (Dielectric Loss), it is difficult to implement the circuit of the characteristic, the temperature stability of the dielectric constant has a disadvantage that the characteristic change with temperature is severe.

In order to solve the problems of the prior art as described above, in order to overcome the disadvantages of the low-temperature co-fired glass-based ceramic by controlling the densification behavior by adding an adhesive modifier (Adhesive Modifier), it is inserted or bonded to the low-temperature co-fired glass-based ceramic The present invention provides a low-temperature co-fired ceramic composition capable of co-firing with metal electrodes such as silver (Ag) and copper (Cu).

It is still another object of the present invention to provide a heterogeneous ceramic assembly which is stable to temperature changes inside a part and has excellent characteristics.

It is another object of the present invention to provide a passive integrated device which is stable to temperature changes inside a component and has excellent characteristics.

It is still another object of the present invention to provide a multi-chip module which is capable of miniaturization, high characterization, and multifunctionality of electronic components by embedding a passive integrated device that is stable to temperature changes inside a component and has excellent characteristics.

1 is a view showing a multi-chip module of a glass-based low-temperature co-firing ceramic and a high dielectric constant low-temperature co-firing ceramic, provided with an inductor layer, a resonator, and a semiconductor active element, according to a preferred embodiment of the present invention.

FIG. 2 is a diagram showing shrinkage behavior of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ compounds and a borosilicate glass system to which a bonding regulator is added.

3 is a low-temperature co-fired ceramic having a high dielectric constant x (Ba, Sr) O.y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O ₅ compound and a reactive glass-ceramic mixture added with a bonding regulator Is a diagram showing a cross-sectional microstructure after simultaneous sintering bonding.

4 is a view showing an increase in capacitance C according to the structure of the MLCC according to Example 7 and the thickness of the inserted high dielectric constant layer.

* Drawing symbol *

1: low dielectric constant glass ceramic

2: high dielectric constant low temperature co-fired ceramic

3: built-in capacitor layer

4: built-in inductor layer

5: resonator

6: semiconductor active device

11: glass based ceramic of dielectric constant 6.5

12: x (Ba, Sr) O.y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O ₅ -based ceramics having a dielectric constant of 42.5 co-fired

13: Ag internal electrode cofired

14: Ag external electrode for input and output

15: Thickness of x (Ba, Sr) O.y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O ₅ -based ceramic layer with co-fired dielectric constant of 42.5

In order to achieve the above object, the present invention

(1) a low dielectric constant containing a main component of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ , (2) a sintering aid, and (3) a bonding regulator. A dielectric ceramic composition for co-sintering by inserting or bonding into a glass-based low temperature co-fired ceramic,

The main component (1) is represented by the following formula (1),

x (aBaO, (1-a) SrO) .y (bTiO ₂ , (1-b) ZrO ₂ ) .z (cNb ₂ O ₅ , (1-c) Ta ₂ O ₅ )

(Wherein 0.15≤x≤0.3, 0.15≤y≤0.3, 0.4≤z≤0.7, and 0 <a≤1, 0 <b≤1, and 0 <c≤1)

(2) the sintering aid comprises at least one compound selected from the group consisting of B ₂ O ₃ , ZnO, CuO, V ₂ O ₅ , Sb ₂ O ₅ , Bi ₂ O ₃ , and Ag ₂ O,

Wherein (3) the bonding regulator is represented by the following formula (2),

αXβYγ (SiO ₂ )

(In the above formula, 0.01≤α≤1, 0.1≤β≤4, 0.1≤γ≤8, X is a compound containing at least one element selected from the group consisting of Na, K, Mg, Ca, and Ba, Y includes at least one element selected from the group consisting of B and Al).

The present invention also relates to a bonded body of low-temperature co-fired dissimilar ceramics, which is bonded or inserted by co-firing with the dielectric ceramic composition and a glass-based low-temperature co-fired ceramic.

The present invention also relates to a passive integrated device manufactured by co-firing the heterogeneous ceramic assembly and the low melting electrode at a temperature of 800 to 950 °.

Hereinafter, the present invention will be described in detail.

The present invention provides a ceramic composition comprising a main component of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ , a sintering aid, and a bonding regulator, a heterogeneous ceramic assembly using the same, And passive integrated devices.

The constituent elements of the main component may be substituted with other elements or may form a solid solution composed of two or more elements, and may contain a small amount of an additive for improving sintering properties. X (Ba, Sr) O · y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O which can be improved by bonding and co-firing with heterogeneous glass-based low temperature cofired ceramics according to the present invention _{The five-} based composition is described in Korean Laid-Open Publication No. 2001-110577. Specifically, in the xBaO.yTiO ₂ .zNb ₂ O ₅ -based composition, as a member to be substituted for improving dielectric properties, Ba is substituted with Sr and / or Ca, Ti is replaced with Sn and / or Zr, and Nb is substituted with Ta. A solid solution can be formed with these. It is preferable that the said main component is a compound represented by General formula (1).

[Formula 1]

x (aBaO, (1-a) SrO) .y (bTiO ₂ , (1-b) ZrO ₂ ) .z (cNb ₂ O ₅ , (1-c) Ta ₂ O ₅ )

(Wherein 0.15 ≦ x ≦ 0.3, 0.15 ≦ y ≦ 0.3, 0.4 ≦ z ≦ 0.7, and 0 <a ≦ 1, 0 <b ≦ 1, and 0 <c ≦ 1). It is more preferable that the constants are 0.5 ≦ a ≦ 1, 0.5 ≦ b ≦ 1, and 0.5 ≦ c ≦ 1, wherein 0.01 to the cation substitution amount of SrO and CaCO ₃ , SnO ₂ and ZrO ₂ , or Ta ₂ O ₅ . Most preferably, it is in the range of 50 mol%, because the substitution loss outside the above range increases the dielectric loss and the temperature coefficient.

Since the ceramic composition composed of the main component according to the present invention is sintered at a temperature of 1150 ° C. or more, it cannot co-fire with low melting metal electrodes such as silver, copper, and silver / palladium alloys. Since the sintering aid can be added and sintered at 1,000 ° C. or lower, sintering can be performed simultaneously with a low melting point metal electrode such as pure silver. In addition, since the dielectric constant is particularly high and the resonant frequency thermometer has a value of 10 ppm / ° C or less, it can be used for components requiring temperature stability, for example, a temperature stable laminated capacitor (NPO MLCC).

The sintering aid that can be used in the present invention may be at least one compound selected from B ₂ O ₃ , ZnO, CuO, V ₂ O ₅ , Sb ₂ O ₅ , Bi ₂ O ₃ , and Ag ₂ O, preferably B ₂ O ₃ , ZnO and CuO. In the present invention, the addition amount of the sintering aid is preferably included in the range of 0.01-7% by weight of the total ceramic composition. If the addition amount of the sintering aid is within 0.01-7 parts by weight, it is possible to promote the sintering of the composition and at the same time improve the dielectric properties of the aid, but when it is out of the range can not be expected to increase the sintering properties and dielectric properties.

In the present invention, an adhesive modifier is a compound that controls bonding with heterogeneous glass-based low-temperature co-fired ceramics, and when added to the ceramic composition and fired with the heterogeneous ceramic composition, deterioration of sintering characteristics or dielectric properties is not achieved. Compound, an example of which is an amorphous glassy compound. Examples of the amorphous glassy compound are compounds having the formula

[Formula 2]

αXβYγ (SiO ₂ )

In the above formula, 0.01≤α≤1, 0.1≤β≤4, 0.1≤γ≤8, X is a substance containing at least one element selected from the group consisting of Na, K, Mg, Ca, and Ba, Y is at least one element selected from the group consisting of B and Al. In addition, in a preferred example of Formula 2, X is a compound of (dNa, (1-d) K). (EMg, (1-e) Ba). (FCa, (1-f) Ba), wherein d, e , f are constants in the range of 0≤c≤1, 0≤d≤1, 0≤c≤1, except that d, e and f are all 0, and Y is (gAl, (1 -g) is a compound of B) wherein g is a constant having a range of 0≤g≤1.

The content of the bonding regulator added to the ceramic composition of the present invention is 0.01 to 10% by weight based on the total ceramic composition. When the bonding regulator is added over the above range, it is difficult to control the sintering shrinkage behavior of the main component, which may cause an increase in dielectric loss and a decrease in dielectric constant. The ceramic composition of the present invention comprises a bonding regulator, thereby controlling the densification behavior of the low temperature co-fired ceramic, and inserting or bonding the main component into the low-temperature co-fired glass-based ceramic, such as silver (Ag), copper (Cu), and the like. Provides the ability to co-fire with metal electrodes. 2 shows the shrinkage behavior according to temperature between the two different ceramic materials as shown in FIG. 2, and it is necessary to select and add a bonding regulator that can control the variation of the shrinkage behavior during simultaneous firing between the two different ceramic materials.

2 is a x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substituted compound and a crystallized glass-based low temperature to which a bonding regulator according to the present invention is added. The shrinkage behavior of the heterojunction between cofired ceramics is shown. It is particularly important in the present invention to control and control the interfacial reactivity between the dissimilar materials by the bonding regulator added to the shrinkage deviation and the stress caused by the difference in the sintering behavior between the dissimilar materials, which will be described in detail below.

Co-silicate glass and x (Ba, Sr) O.y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O ₅ -based substituted composition at the glass transition point (600 ~ 650 ℃) Solid phase diffusion reaction between the bonding modifier and the dissimilar material at the bonding interface forms a SIO ₂ -B ₂ O ₃ -Al ₂ O ₃ -Nb ₂ O ₅ -BaO-based reactant, and the reactants are mutually compatible at the bonding interface between the dissimilar materials. It has a stable network structure and shows strong bonding force.

Simultaneous sintering step 2 is in the range of 750 ~ 800 ℃ and densification of x (Ba, Sr) O · y (Ti, Zr) O ₂ · z (Nb, Ta) ₂ O ₅ system with high dielectric constant begins. At this time, the matching reaction layer formed at the junction interface acts as a diffusion barrier that completes densification and suppresses further diffusion reactions, and at the same time buffers the stress due to the difference in shrinkage between the dissimilar materials. It will play the role of. If the bonding force of the SiO ₂ -B ₂ O ₃ -Al ₂ O ₃ -Nb ₂ O ₅ -BaO-based interfacial reaction layer having the consistency formed by the bonding regulator in this section is weaker than the stress due to the difference in shrinkage, peeling from the bonding surface Delamination occurs. In the second step, the borosilicate glass-based low temperature co-fired ceramic shows only shrinkage due to densification in the Z-axis direction due to the constraint of the matched interface reactant.

The simultaneous sintering step 3 is a section in which simultaneous sintering is completed and is a section of 825 ~ 875 ° C., which is a temperature above the softening point. Shrinkage of x (Ba, Sr) O.y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O ₅ system with high dielectric constant in this temperature range continues and is completed. The calcined ceramic exhibits a rapid shrinkage behavior in the XY axis direction, but since the viscosity of the glass system is already lowered, densification between the different materials is completed without the influence of residual stress due to the difference in shrinkage between the different materials.

The present invention also provides a silicate glass using a ceramic composition comprising a main component of x (Ba, Sr) O.y (Ti, Zr) O ₂ · z (Nb, Ta) ₂ O ₅ , a sintering aid, and a bonding regulator. A heterogeneous ceramic joined body with a low temperature calcined ceramic composition.

Low-temperature co-fired ceramics capable of dissimilar bonding are glass-based low-temperature co-fired ceramics capable of co-firing by bonding with a high dielectric constant composition. Examples include compositions that are silicate-based glass (main phase) and fired at 900 ° C. or lower, depending on the form: 1) glass-ceramic, 2) matrix using recrystallized glass. Non-reactive liquid phase sintering of glass-ceramic compounds based on the reaction crystal phase produced by the reaction between merchant glass and ceramic filler, and 3) non-reaction between the known glass and ceramic filler. Three types of glass-ceramic mixture systems using NLPS, Non-Reactive Liquid Phase Sintering. These are compounds known to those skilled in the art to which the present invention pertains.

Recrystallized glass-based low-temperature co-fired ceramic composition, 1 selected from the group consisting of wollastonite (CaSiO ₃ ), loose graphite (Enstatite, MgSiO ₃ ), and goto olivine (Forsterite, Mg ₂ SiO ₄ ) precipitated during firing Low-temperature co-fired ceramics based on glass ceramics based on more than one type of recrystallized glass. The recrystallized glass-based low temperature co-fired ceramic composition can be fired at a temperature of 950 ° C. or lower, and in particular, a crystal phase such as CaSiO ₃ , MgSiO ₃ , or Mg ₂ SiO ₄ is formed through a recrystallization reaction during firing. . Their density is between 2.5 and 3.5 g / cc and has a dielectric constant between 5.3 and 6.7.

As a glass-ceramic compound-based low-temperature co-fired ceramic, a compound selected from the group consisting of amorphous glassy feldspar (Feldspar, (K, Na, Ca, Ba) (AlSi) ₄ O ₈ ), and a solid solution thereof Is a glass-crystalline ceramic composite containing 30 to 99% by volume as a main component and 1 to 70% by volume of crystalline ceramic as a filler, and BaAl ₂ SiO _{8 is} precipitated by the reaction of glass and the filler during co-firing. In addition, a glass-based low temperature co-fired ceramic containing an annealite (Anorthite, CaAl ₂ SiO ₈ ) can be used. The crystalline ceramics include, but are not limited to, alumina, TiO ₂ , or ZrO ₂ . The glass-ceramic compound-based low temperature co-fired ceramic composition can be fired at a temperature of 950 ° C. or lower, and in particular, when the crystalline ceramic added as the filler is Al ₂ O ₃ , BaAl ₂ SiO ₈ is formed through the reaction between glass and ceramic during firing. Or a reaction crystal phase such as CaAl ₂ SiO ₈ is formed. Their density is between 2.9 and 3.5 g / cc and has a dielectric constant between 6.0 and 8.5.

Glass-ceramic mixture-based low temperature co-fired ceramics include at least one member selected from the group consisting of amorphous borosilicate glass, lead borosilicate glass, and borosilicate glass containing alkali or alkaline earth metals. It includes 30 to 99% by volume, containing 1 to 70% by volume of the crystalline ceramic as a filler (Filler), and can be used a non-reactive glass-based low-temperature co-fired ceramic that does not react with the glass during the co-firing. The crystalline ceramics include, but are not limited to, alumina, TiO ₂ , or ZrO ₂ . The glass-ceramic mixture-based low temperature co-fired ceramic composition may be fired at a temperature of 950 ° C. or lower, and the glass and the crystalline ceramic added as a filler do not react during firing. Their density is 2.7 ~ 3.7g / cc, has a dielectric constant value of 7.0 ~ 40 depending on the type of filler.

In a specific example of the present invention, the method for producing a heterogeneous ceramic conjugate is a mixture of the above-mentioned composition with a solvent such as ethanol, toluene, pulverized and mixed to form a slurry, and then added with an organic binder, a dispersant and a plasticizer After mixing, it is manufactured as a ceramic green sheet using tape casting. The ceramic green sheets of the compositions thus prepared are cut and laminated to a desired size, and then the different types of laminates are bonded or inserted into each other to be hot pressed at a temperature of 60 to 80 ° or warm hydrostatic pressure (WIP). By warm isostatic press). The produced molded body may be cut to a desired size, and then heat treated at a temperature of 250 to 450 ° C. to remove the organic binder, and then fired at a temperature of 800 to 950 ° C. to form a bonded body between dissimilar ceramics.

The present invention also relates to a passive integrated device that manufactures the hetero-ceramic ceramic assembly, co-fired with a low melting point metal electrode, and a multi-chip module including the passive integrated device and an active device. Preferably, it provides a passive integrated device manufactured by co-firing the low melting point metal electrode at a temperature of 800 ~ 950 ℃.

The low melting metal electrode may be selected from the group consisting of silver (Ag), copper (Cu), nickel (NI), silver-palladium alloy (Ag-Pd Alloy), and silver-platinum alloy (Ag-Pt Alloy) electrode. It may be, but is not limited thereto.

In a specific example of the present invention, a method for manufacturing a passive integrated device or a multi-chip module by the method of bonding-simultaneous firing between dissimilar low temperature simultaneous ceramics is as follows. On the ceramic green sheet of each composition produced as described above, the silver (Ag), copper (Cu), nickel (NI), silver-palladium alloy (Ag-Pd Alloy), And a silver-platinum alloy (Ag-Pt Alloy) printed by screen printing to implement a circuit or a passive device designed. After aligning and stacking each of the green sheets in which the circuit is implemented, heat treatment is performed in the same manner as in the manufacturing method of the hetero-ceramic ceramic body, and simultaneously baking the electrode and the ceramic to manufacture a passive integrated device. In addition, a multi-chip module can be manufactured by mounting a plurality of active devices on a heterogeneous ceramic bonded substrate having a passive integrated device manufactured by the same method.

The junction-simultaneous firing between dissimilar low-temperature co-ceramics of the present invention enables the fabrication of high-quality multi-layer dielectric composite devices and ceramic multi-chip modules that could not be realized by glass-based low-temperature co-fired ceramics having low dielectric constant (less than 10 dielectric constant). Can be.

The structure of a multi-chip module, which is a specific example of the present invention, is shown in FIG. 1, where a capacitor or a resonator is formed in a patent composition having a high dielectric constant and a high characteristic to minimize the size and the number of stacked layers. Is characteristic. Semiconductor active devices mounted on low dielectric constant glass based low temperature cofired ceramics can minimize signal delay due to the low dielectric constant of the glass substrate and have similar thermal expansion coefficients (about 3 to 5 ppm / ° C). It has an advantage of achieving thermal stability.

The present invention will be described in more detail with reference to the following illustrative examples, but the protection scope of the present invention is not intended to be limited to the following examples.

Example 1

Preparation of Bonding Regulators

At this time, manufacture of a junction regulator was performed by the method of following description. First, raw materials such as SiO ₂ , B ₂ O ₃ , NaCO ₃ , BaCO ₃ , CaCO ₃ , KOH, MgO, and Al ₂ O ₃ having a purity of 99% or more are weighed to a desired composition, and then mixed in the same manner as described above. After drying, charged into a platinum crucible and melted by heat treatment at 1350 ~ 1500 ℃ for 2 hours. The molten molten metal was quenched to give an amorphous glass. The amorphous glass thus prepared was coarsely pulverized with an alumina mortar pestle, and then pulverized and dried in the same manner as above to prepare an amorphous glass-like bonding regulator. Table 1 shows the final composition and sintering properties of the bonding regulator having an amorphous glass phase prepared as described above.

Composition and Sintering Properties of Bonding Regulators with α (K, Na, Ca, Ba, Mg) β (B, Al) γ (SiO) ₂ Amorphous Glass Phases No. Castability Sintering Temperature (℃) Sintered Density (g / cc) Na K Mg Ca Ba B Al Si A1 11.0 - - - - 13.5 1.0 75.5 875 2.55 A2 - 11.0 - - - 13.5 1.0 75.5 875 2.68 A3 - - 11.0 - - 13.5 1.0 75.5 875 2.65 A4 - - - 11.0 - 13.5 1.0 75.5 875 2.72 A5 - - - - 11.0 6.5 1.0 75.5 875 3.05 B1 11.0 - - - - 13.5 37.5 45.0 875 3.05 B2 - 11.0 - - - 13.5 37.5 45.0 875 3.12 B3 - - 11.0 - - 13.5 37.5 45.0 875 3.23 B4 - - - 11.0 - 13.5 37.5 45.0 875 3.28 B5 - - - - 11.0 13.5 37.5 45.0 875 3.31

Example 2

x (Ba, Sr) Oy (Ti, Zr) O ₂ Z (Nb, Ta) ₂ O ₅ Low Temperature Cofired Ceramics with Sintering Aid and Bonding Regulator Added to System-Based Substitution Compositions

BaCO ₃ , TiO ₂ , ZrO ₂ , and Nb ₂ O ₅ with a purity of 99.9% are weighed so that the molar ratio of Ba: (Ti, Zr): Nb is 1: 1: 4, and the polyethylene bottle is diluted with distilled water and weight ratio. 1 to 1% by weight of dispersant was added for smooth mixing, followed by mixing for 24 hours using stabilized zirconia balls (Yttria Stabilized Zirconia). The mixed slurry was heated to 100 ° C. in an oven to remove moisture, and then placed in an alumina crucible and calcined at 1100 ° C. for 2 hours.

B ₂ O ₃ , ZnO, and CuO are added to the calcined powder as a sintering aid and mixed, and 0 to 10 wt% of the adhesive modifier prepared in Example 1 is added to the mixing process of the main components. After milling for 24 hours in the same manner as, and dried in the same manner. Table 2 shows B ₂ O ₃ , ZnO as a sintering aid in a representative composition selected from the x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based compositions prepared as described above. And the composition of the low temperature co-fired ceramic to which CuO and the bonding regulator shown in Table 1 were added.

sample Castability Sintering Aid (wt%) Bonding regulator (wt%) BaO TiO ₂ ZrO ₂ Nb ₂ O ₅ B ₂ O ₃ CuO ZnO A1 A2 A3 A4 A5 B1 B2 B3 B4 B5 One 25 12.5 12.5 40 One One One - - - - - - - - - - 2 3 2 - - - - - - - - 3 5 - - - - - - - - - 4 - 3 2 - - - - - - - 5 - 5 - - - - - - - - 6 - - 3 2 - - - - - - 7 - - 5 - - - - - - - 8 - - - 3 2 - - - - - 9 - - - 5 - - - - - - 10 - - - - 5 - - - - - 11 25 25 - 40 One One One - - - - - - - - - - 12 - - - - - 3 2 - - - 13 - - - - - 5 - - - - 14 - - - - - - 3 2 - - 15 - - - - - - 5 - - 16 - - - - - - - 3 2 - 17 - - - - - - - 5 - - 18 - - - - - - - - 3 2 19 - - - - - - - - 5 - 20 - - - - - - - - - 5

Thus prepared raw material was ethyl alcohol (Ethyl Alcohol) and toluene (Tolunene) to 80% by weight of the powder was mixed in the same way for 2 hours. At this time, the weight ratio of the mixed ethyl alcohol and toluene was 36:64, and 0.5 to 2% by weight of Menhaden Fish Oil was added as a dispersant to prepare a slurry. To the slurry was added 7 to 9% by weight of polyvinyl butyral (PVB, Polyvinyl Butyral) as a binder, 2 to 4% by weight of dioctyl phthalate (DOP, Dioctyl Phthalate) as a plasticizer, followed by mixing for 24 hours. The mixed slurry was applied onto a PET film to which a silicone release agent was applied using a tape casting device, and then dried at 60 to 90 ° C. to produce a green sheet required for bonding.

The green sheet was laminated cut to a size of 15 × 15 × 1 mm, sintered at 850 to 900 ° C. for 2 hours, and dielectric properties were measured using a Hewlett Packard HP4194 impedance analyzer. The sintering and dielectric properties of the ceramic composition are shown in Table 3 below. It can be seen from Table 3 that the change in properties due to the addition of the bonding regulator is not large.

Sample number Sintering Temperature (℃) Sintered Density (g / cc) Dielectric loss (Qxf) Permittivity (Er) Resonance Frequency Temperature Coefficient (Tcf, ppm / ℃) One 875 5.0 5 x 10 ^-5 42.5 0 2 875 4.8 7 x 10 ^-5 42.0 +15 3 875 4.5 6 x 10 ^-5 42.0 +15 4 875 4.5 5.5 x 10 ^-5 41.5 +10 5 875 4.5 5.5 x 10 ^-5 41.5 +10 6 875 4.6 6 x 10 ^-5 42.5 +18 7 875 4.5 6 x 10 ^-5 41.5 +16 8 875 4.7 6.5 x 10 ^-5 41.0 +5 9 875 4.5 7 x 10 ^-5 41.0 +28 10 875 4.8 7 x 10 ^-5 40.5 -25 11 890 5.9 4.5 x 10 ^-5 40.5 -25 12 890 5.6 5 x 10 ^-5 39.5 -35 13 890 5.5 5 x 10 ^-5 39.5 +30 14 890 5.6 5 x 10 ^-5 40.5 +15 15 890 5.6 5 x 10 ^-5 40.5 +15 16 890 5.5 5.5 x 10 ^-5 39.0 +10 17 890 5.3 5.5 x 10 ^-5 39.0 +5 18 890 5.3 5.5 x 10 ^-5 39.5 0 19 890 5.8 6 x 10 ^-5 39.0 -15 20 890 5.7 6 x 10 ^-5 39.5 -10

Example 3

Heterogeneous Ceramic Joint of Recrystallized Glass System Low Temperature Cofired Ceramic

3-1: Recrystallized Glass System Low Temperature Cofired Ceramic

A glass-based low-temperature co-fired ceramic that can be co-fired by bonding to a high-k dielectric composition, and is known as wollastonite (CaSiO ₃ ), loose graphite (Enstatite, MgSiO ₃ ), or goto olivine (Forsterite, Mg ₂ SiO _4). Recrystallized glass-based low temperature co-fired ceramics containing, as a main component, recrystallized glass) were prepared in substantially the same manner as in the bonding control agent of the amorphous glass phase described in Example 1.

After producing the green sheet of the recrystallized glass-based low-temperature co-fired ceramic using the organic compound combination and the tape casting method described in Example 2, laminated cut to a size of 15x15x1mm, sintered at 850 ~ 900 ℃ 30 minutes It was. The dielectric properties of the sintered body were measured using Hewlett Packard's HP4194 impedance analyzer. Table 4 shows the final composition of the prepared amorphous glass. In addition, Table 5 is a result of analysis by EDS (Energy Dispersive Spectroscopy) of the ceramic prepared according to the present embodiment, showing the sintering characteristics and dielectric properties.

Chemical Composition of Recrystallized Glass-based Low Temperature Cofired Ceramic Composition Example Chemical composition (mole%) Si Ca K Mg Zn Ti B Al R 3-1 48 47 1.5 1.0 0.5 0.5 - 0.5 1.0 3-2 45 48 1.5 - 0.2 1.0 1.0 1.8 1.5 3-3 45 2.0 1.5 46.5 0.5 1.5 0.5 1.5 - 3-4 47 1.5 - 48 0.5 1.0 - 2.0 - 3-5 29 3.0 3.0 61 0.5 0.5 1.0 2.0 - 3-6 30 1.5 - 60 1.5 1.0 1.0 5.0 -

Sintering and Dielectric Properties of Recrystallized Glass Ceramic Low Temperature Cofired Ceramics Example Sintering Temperature (℃) Sintered Density (g / cc) Dielectric loss (Tanδ) Permittivity (Er) Recrystallization 3-1 850 2.90 2 x 10 ^-3 5.6 CaSiO ₃ 3-2 850 2.85 2 x 10 ^-3 5.3 CaSiO ₃ 3-3 875 3.15 4 x 10 ^-3 5.8 MgSiO ₃ 3-4 875 3.20 5 x 10 ^-3 6.0 MgSiO ₃ 3-5 875 3.27 1 x 10 ^-3 6.5 Mg ₂ SiO ₄ 3-6 875 3.30 0.5 x 10 ^-3 6.7 Mg ₂ SiO ₄

3-2: heterogeneous ceramic assembly

X (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substitution type having a high dielectric constant to which the bonding regulator is added at 5 wt% in the same manner as in Example 2 A green sheet of the compound was produced.

As a dissimilar ceramic to be bonded to the green sheet of the substituted compound, a green sheet of the recrystallized glass-based low temperature co-fired ceramic prepared in Example 3-1 was prepared.

The two green sheets were cut and bonded to a size of 15 mm x 5 mm x 5 mm, respectively, and then joined and molded by warm hydrostatic pressure (WIP, Warm Isostatic Press) at a pressure of 10 to 50 Mpa. The bonded molded product thus obtained was heat treated at 350 ° C. for 2 hours to remove the organic binder, and then heated at 5 ° C. per minute and sintered at 875 ° C. for 2 hours. Sintering and densification behaviors were analyzed by TMA and DSC.

Recrystallized glass-based low temperature calcined ceramics exhibited a glass transition point (Tg, Glass Transition Temperature) at 600 to 650 ° C., softened at 825 to 850 ° C. and rapidly contracted by a viscous flow sintering mechanism. On the other hand, x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substitution compositions having high dielectric constants started sintering through volume diffusion at 750 ° C. It was densified at a slow rate compared to the recrystallized glass-based low temperature cofired ceramics. 2 shows the shrinkage behavior according to the temperature between the two materials. FIG. 2 shows shrinkage behavior of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ based substituted compounds and recrystallized glass-based ceramics to which a bonding regulator is added.

Example 4

Heterogeneous Ceramic Joint of Glass-Ceramic Compound Low Temperature Cofired Ceramic

X (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substitution type having a high dielectric constant to which the bonding regulator is added at 5 wt% in the same manner as in Example 2 A green sheet of the compound was prepared.

Glass-ceramic compound-based low-temperature co-fired ceramics to be co-fired with the green sheet of the substituted compound include amorphous glassy Feldspar, (K, Na, Ca, Ba) (Al.Si) ₄ O ₈ ) and a glass-crystalline ceramic composite having one of its solid solutions and containing 1 to 70 parts by volume of crystalline ceramic as a filler, and BaAl ₂ SiO ₈ or glass which reacts and precipitates when co-fired. A glass-based low temperature co-fired ceramic containing feldspar (Anorthite, CaAl ₂ SiO ₈ ) was selected.

In substantially the same manner as in Example 3-2, the green sheet of the substituted compound according to Example 2 and the green sheet of the glass-ceramic compound-based low temperature cofired ceramic were bonded and sintered, and the characteristics thereof were analyzed. .

Table 6 and Table 7 show the results of analyzing the composition of the borosilicate glass and the crystalline composite used in the prepared experiments and show the sintering characteristics and dielectric properties of the heterojunction. The heterozygote of the present invention has excellent bondability without deterioration in properties due to mutual reaction.

Composition of Glass-Ceramic Compound Low Temperature Cofired Ceramics Sample Number Chemical composition of glass (mole%) Crystalline ceramics (vol%) Reaction crystal phase Si Ca K Mg Ba Ti B Al α-Al ₂ O ₃ Mg ₂ SiO ₄ 3Al ₂ O ₃ -2SiO ₂ A1 58.4 5.0 1.6 5.6 8.6 9.6 8.8 2.4 15 - - Al ₈ B ₂ O ₁₅ -BaAl ₂ Si ₂ O ₈ A2 25 - - A3 35 - - B1 58.4 8.0 1.6 5.6 5.6 9.6 8.8 2.4 - 15 - Mg ₂ Al ₄ Si ₆ O ₁₈ B2 - 25 - B3 - 35 - C1 55.4 11.0 1.6 5.6 5.6 9.6 8.8 2.4 - - 15 CaAl ₂ SiO ₈ C2 - - 25 C3 - - 35

Sintering and Dielectric Properties of Heterostructures Sample Number Sintering Temperature (℃) Sintered Density (g / cc) Dielectric loss (Tanγ) Permittivity (Er) A1 875 3.1 4 X 10 ^-3 6.5 A2 875 3.2 2.5 X 10 ^-3 7.1 A3 875 3.3 1.0 X 10 ^-3 7.8 B1 875 2.9 5 X 10 ^-3 5.9 B2 875 3.0 5 X 10 ^-3 6.2 B3 875 3.15 4.5 X 10 ^-3 6.5 C1 875 2.9 5 X 10 ^-3 6.1 C2 875 3.27 4.0 X 10 ^-3 6.5 C3 875 3.33 4.0 X 10 ^-3 6.7

The glass-ceramic compound-based low temperature co-fired ceramics listed above are characterized in that the crystalline ceramic added as a filler during sintering reacts with the glass to form a secondary reaction crystal phase. x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substituted compounds and crystalline ceramics added as fillers to the glass-based low-temperature cofired ceramics at sintering temperature There was no mutual reactivity, and the added sintering behavior resulted in sound co-sintering bondability with the same sintering behavior as in Example 3 above.

3 is a low-temperature co-firing type of a high dielectric constant x (Ba, Sr) O.y (Ti, Zr) O ₂ ㆍ z (Nb, Ta) ₂ O ₅ -based substituted compound and a glass-ceramic compound added with a bonding regulator A cross-sectional microstructure after co-sintering of ceramics. 3 is a specimen co-fired by inserting x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based composition to which 5 wt% of the bonding regulator B5 is added into the A3 specimen. The cross section of the microstructure was shown by scanning electron microscopy (SEM). Where A is a high dielectric constant material inserted, B is a glass-based cofired ceramic having a low dielectric constant, and C is a reaction product layer that acts as a diffusion barrier and a junction buffer layer formed by a junction regulator.

Example 5

Heterogeneous Ceramic Joints of Glass-Ceramic Mixture-based Low Temperature Cofired Ceramics

X (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substitution type having a high dielectric constant to which the bonding regulator is added in an amount of 5% by weight in the same manner as in Example 2 A green sheet of the compound was prepared,

Glass-based low temperature co-fired ceramics to be bonded by co-firing include at least one of amorphous borosilicate glass, lead borosilicate glass, borosilicate glass including alkali or alkaline earth metal as a main component. As a filler, a glass-ceramic mixture-based low temperature co-fired ceramic containing 1 to 70 parts by volume (vol%) of crystalline ceramics and in which the glass and the filler do not react at the time of co-firing was selected.

In substantially the same manner as in Example 3-2, the green sheet and the glass-ceramic mixture-based low temperature cofired ceramic green sheet of the substituted compound according to Example 2 were bonded and sintered, and the characteristics thereof were analyzed.

Table 8 shows the results of analyzing the composition of the glass-ceramic mixture-based low temperature co-fired ceramics used in the prepared experiments, and Table 9 shows the sintering characteristics and the dielectric properties of the dissimilar ceramic joints manufactured using the same. The heterozygote of the present invention has excellent bondability without deterioration in properties due to mutual reaction.

Composition of Glass-Ceramic Mixture-based Low Temperature Cofired Ceramics Sample Number Chemical composition of glass (mole%) Crystalline ceramics (vol%) Si Ca K Pb Co Ti B Zn Al α-Al ₂ O ₃ (MgCa) TiO ₃ A1 69.3 8.5 1.7 - 0.5 - 11.5 - 8.5 15 - A2 25 - A3 35 - B1 8.5 16.5 1.5 - 0.5 13.5 9.5 - 50 15 - B2 25 - B3 35 - C1 68.5 6.5 2.0 6.5 0.5 3.0 9.5 1.5 2.0 15 - C2 25 - C3 35 - D1 58.5 6.5 2.0 1.5 0.5 3.5 11.0 15.0 1.5 - 55 D2 - 65 D3 - 75

Sintering and Dielectric Properties of Heterostructures Sample Number Sintering Temperature (℃) Sintered Density (g / cc) Dielectric loss (Tanδ) Permittivity (Er) A1 860 2.7 4.0 X 10 ^-3 7.1 A2 860 2.9 3.5 X 10 ^-3 7.5 A3 860 3.1 2.5 X 10 ^-3 7.9 B1 875 3.2 3.0 X 10 ^-3 7.8 B2 875 3.2 2.5 X 10 ^-3 7.9 B3 875 3.3 1.5 X 10 ^-3 8.1 C1 875 2.9 4.0 X 10 ^-3 7.8 C2 875 3.1 4.0 X 10 ^-3 8.0 C3 875 3.2 5.0 X 10 ^-3 8.2 D1 850 3.5 3.5 X 10 ^-3 16 D2 850 3.6 4.0 X 10 ^-3 17.5 D3 850 3.7 5.0 X 10 ^-3 19

The glass-ceramic mixture-based low temperature co-fired ceramics listed above are characterized in that the crystalline ceramic added as a filler during sintering does not react with the glass. x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based substituted compounds and crystalline ceramics added as fillers to the glass-based low-temperature cofired ceramics also at sintering temperatures There was no mutual reactivity and the same sintering behavior as in Example 3 described above showed sound co-sintering bonding.

Example 7: Multilayer Ceramic Capacitor

Samples of Table 2 as x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ -based compositions to which the bonding regulator shown in Example 2 was added as a specific application of the present invention After bonding No. 6 and the A1 samples shown in Table 6 of Example 4, co-firing was performed to produce a multilayer ceramic capacitor (MLCC), and the characteristics thereof were evaluated.

The structure of the MLCC used in this experiment is shown in FIG. 4, and the increase in capacitance (C) according to the thickness change 15 of the high dielectric constant layer inserted into the MLCC is measured and shown in Table 10.

e (mm) 0 0.12 0.24 0.36 0.48 0.60 C (pF) 0.961 6.114 7.538 8.253 8.845 9.571

As can be seen from Table 10, when only glass-based low-temperature co-fired ceramics having a dielectric constant of 6.5 were used (thickness = 0), the high dielectric constant composition was co-fired by inserting at a thickness of 0.12 mm, which is 10% of the total thickness of the entire sample. Without increasing the size, high-performance MLCCs with capacitances of about 6.4 times could be fabricated.

The present invention provides a ceramic composition comprising a main component of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ , a sintering aid, and a bonding regulator, a heterogeneous ceramic assembly using the same, And passive integrated devices, which increase the dielectric constant of materials to be inserted or bonded, and have excellent dielectric properties and temperature stability, which could not be realized with glass-based low temperature co-fired ceramics having low dielectric constants (below 10). Multi-layer dielectric composite devices such as high-performance filters, MLCCs, couplers, and ceramic multi-chip modules such as antenna switch modules and front end modules can be manufactured in a compact size.

Claims (13)

A ceramic composition comprising (1) a main component of x (Ba, Sr) O.y (Ti, Zr) O ₂ .z (Nb, Ta) ₂ O ₅ , (2) sintering aid, and (3) junction regulator. , The main component (1) is represented by the following formula (1), [Formula 1] x (aBaO, (1-a) SrO) .y (bTiO ₂ , (1-b) ZrO ₂ ) .z (cNb ₂ O ₅ , (1-c) Ta ₂ O ₅ ) (Wherein 0.15≤x≤0.3, 0.15≤y≤0.3, 0.4≤z≤0.7, and 0 <a≤1, 0 <b≤1, and 0 <c≤1) (2) the sintering aid comprises at least one compound selected from the group consisting of B ₂ O ₃ , ZnO, CuO, V ₂ O ₅ , Sb ₂ O ₅ , Bi ₂ O ₃ , and Ag ₂ O, Wherein (3) the bonding regulator is represented by the following formula (2), [Formula 2] αXβYγ (SiO ₂ ) (In the above formula, 0.01≤α≤1, 0.1≤β≤4, 0.1≤γ≤8, X is a substance containing at least one element selected from the group consisting of Na, K, Mg, Ca, and Ba, Y is at least one element selected from the group consisting of B and Al) Low temperature cofired dielectric ceramic composition. The dielectric ceramic composition of claim 1, wherein the main component is a compound of Formula 1, wherein 0.5 ≦ a ≦ 1, 0.5 ≦ b ≦ 1, and 0.5 ≦ c ≦ 1. The dielectric ceramic composition of claim 1, wherein the content of the sintering aid is 0.01 to 7 wt%. The dielectric ceramic composition of claim 1, wherein the sintering aid is a mixture of B ₂ O ₃ , ZnO, and CuO. The dielectric ceramic composition of claim 1, wherein the content of the bonding regulator is 0.01 to 10 wt%. 2. The compound of claim 1, wherein X represented by Chemical Formula 2 is a compound represented by (dNa, (1-d) K) · (eMg, (1-e) Ba) · (fCa, (1-f) Ba) ( Here, d, e, f is a constant having a range of 0≤c≤1, 0≤d≤1, 0≤c≤1, except when the d, e and f are all 0), Y Is a compound represented by (gAl, (1-g) B), where g is a constant having a range of 0 ≦ g ≦ 1. A low-temperature co-fired hetero-ceramic ceramic body according to any one of claims 1 to 6, wherein the dielectric ceramic composition according to any one of claims 1 to 6 is bonded or inserted by co-firing a silicate glass-based low-temperature co-fired ceramic. The low temperature cofired heterogeneous ceramic according to claim 7, wherein the silicate glass low temperature cofired ceramic is a recrystallized glass low temperature cofired ceramic, a glass-ceramic compound low temperature cofired ceramic, or a glass-ceramic mixture low temperature cofired ceramic. Ceramic junction. The method of claim 8, wherein the recrystallized glass-based low-temperature co-fired ceramic is a wollastonite (CaSiO ₃ ), loose graphite (Enstatite, MgSiO ₃ ), and Goto olivine (Forsterite, Mg ₂ SiO) through the recrystallization reaction during co-firing _At least one member selected from the group consisting of ₄ ) is a heterogeneous ceramic assembly. 9. The method according to claim 8, wherein the glass-ceramic compound-based low temperature co-fired ceramic is composed of amorphous glassy feldspar (Feldspar, (K, Na, Ca, Ba) (Al.Si) ₄ O ₈ ), and It contains 30 to 99% by volume of at least one selected from the group consisting of a solid solution, 1 to 70% by volume of crystalline ceramics as a filler, and BaAl ₂ SiO reacts with glass and filler during co-firing ₈ and at least one member selected from the group consisting of feldspar (Anorthite, CaAl ₂ SiO ₈ ) is a different ceramic assembly. The method of claim 8, wherein the glass-ceramic mixture-based low temperature co-fired ceramic is a borosilicate glass containing amorphous borosilicate glass, lead borosilicate glass, and alkali or alkaline earth metal as main components. One or more selected from the group consisting of Al ₂ O ₃ and (MgCa) TiO ₃ as a crystalline ceramic which does not react upon co-firing with the glass as a filler (Filler) is 30 ~ 99% by volume The heterogeneous ceramic joined body is contained in 1 to 70% by volume or more. The passive integrated device manufactured by co-firing the heterogeneous ceramic assembly according to claim 7 and the low melting electrode at a temperature of 800 ~ 950 ℃. The method of claim 12, wherein the low melting electrode comprises silver (Ag), copper (Cu), nickel (NI), silver-palladium alloy (Ag-Pd Alloy), and silver-platinum alloy (Ag-Pt Alloy) electrode. Passive integrated device is selected from the group consisting of.