JPH02172106A - Material with composition for dielectric ceramic, dielectric ceramic sintered member and multilayer wiring board - Google Patents

Abstract

PURPOSE:To obtain a miniaturized multilayer wiring board with improved characteristics and large capacity having a dielectric layer consisting of a sintered member by causing a dielectric ceramic composition material to contain a predetermined composite oxide composition material and obtaining a ceramic sintered member with an improved temperature characteristic through sintering this composition material at about 800-950 deg.C. CONSTITUTION:In a Pb(Mg1/3Nb2/3)O3PbTiO3 series dielectric ceramic composition material, for the composition of 56.1-59.9mol% when converted into PbO, 12.1-19.8mol% when converted into MgO, 12.2-19.8mol% when converted into Nb2O5, 0.6-19.7mol% when converted into TiO2, 0.1-1.0mol% copper compound when converted into CuO is contained. This dielectric ceramic composition material is sintered at about 800-950 deg.C to obtain a dielectric ceramic sintered member, and a multiwiring board is obtained by using this sintered member as a dielectric layer, and the dielectric loss and the insulating resistance of this multiwiring board can be improved and miniaturization thereof can be achieved.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a dielectric ceramic composition, a dielectric ceramic sintered body, and a multilayer wiring board.

<Prior art> Pb (Mg+/s N
bxys ) Ox PbTiOs system composition is known (Japanese Patent Publication No. 61-28619). Also, a system in which MgO is added in excess of the stoichiometric composition is also known (Japanese Patent Publication No. 61-5427). <Problem to be solved by the invention> However, these Pb (Mg+zs Nbxis)O
In the s-PbTiOs system, it is said that sintering is possible in a low temperature range, but in reality, good properties cannot be achieved unless sintering is performed at a temperature of about 1050 to 1150°C. At that time, the insulation resistance is also small (insufficient).

Sintering at temperatures above 1000° C. requires a lot of energy and has the disadvantage that the firing furnace, setter, firing sagger, plywood, etc. are severely deteriorated.

Furthermore, such a dielectric ceramic composition is used to fabricate a multilayer wiring board having a dielectric layer and a conductor layer in a predetermined pattern by co-firing it with an insulating layer material and a conductor layer material.

However, when a sintering temperature of 1000° C. or higher is required, there is a disadvantage that a noble metal such as Au%pt%Pd must be used as the conductor layer material.

On the other hand, materials containing ceramic aggregates such as alumina and glass are known as insulating layer materials that can be sintered at temperatures below about 1000°C.

However, the above P b (M g r7s N b a
ys )Os -P b TiOs system is 1000
If it is simultaneously sintered with these insulating layer materials for low-temperature firing at a temperature of about 100° C., curling, warping, cracking, etc. will occur because the shrinkage ratios of the two are different.

By the way, as a composite dielectric ceramic of titanate, the above-mentioned P b (M g +/3 N b mis
)Os-P b T i Os and various other types are known.

In these titanate composite derivative ceramics,
It has been proposed to reduce the sintering temperature to a certain extent by adding CuO (Japanese Patent Laid-Open Nos. 62-31906, 62-37802, 62-37804, 62-
(No. 37805, etc.) However, these methods are still insufficient in terms of sintering temperature, and the heat shrinkage characteristics are different when simultaneously integrated with the insulating layer material for low-temperature firing, causing curling, warping, cracking, etc. There is an inconvenience.

The main purpose of the present invention is to reduce the sintering temperature to 1000℃
It is possible to perform low-temperature firing with the following materials, and at the same time, it has good electrical properties such as good dielectric constant and dielectric loss, and also has good heat shrinkage characteristics and an insulating layer material for low-temperature firing that contains ceramic aggregate and glass. p b (M g +/s N bi
zs) An object of the present invention is to provide an Os-PbTiOs-based dielectric ceramic composite oxide, a dielectric ceramic sintered body obtained by sintering this composition, and a multilayer wiring board having this sintered body as a dielectric layer. .

Means for Solving the Problems> These objects are achieved by the following inventions (1) to (9).

(1) Pb (Mg+zs Nbtys) Ox
- A composition for a PbTiOs-based dielectric ceramic, comprising 56.1 to 59.9 mol% in terms of PbO, M
12.1 to 19.8 mol% in terms of gO, N b t
12.1 to 19.8 mol% in terms of Os, Ti
For a composition of 0.6 to 19.7 mol% in terms of Ox,
0. in terms of CuO. A dielectric ceramic composition containing 1 to 10 mol% of a copper compound.

(2) Furthermore, for the above composition, 1.7 in terms of MnO
The dielectric ceramic composition according to (1) above, containing a Mn compound in an amount of mol % or less.

(3) Pb (Mg+, Nb, x)
Os - PbT L Os-based solid solution, in which Pb
O56.1-59.9 mol%, MgO12.1-19.
8 mol%, Nbz ox 12.1-19.8 mol%,
For a solid solution composition of Ti0-0.6 to 19.7 mol%,
A dielectric ceramic sintered body characterized by containing 0.1 to 10 mol% of CuO.

(4) The dielectric ceramic sintered body according to the above (3), further containing 1.7 mol% or less of MnO with respect to the solid solution composition.

(5) In a multilayer wiring board in which an insulating layer, a conductor layer, and a dielectric layer are laminated, the dielectric layer is formed from the dielectric ceramic sintered body described in (3) or (4) above. A multilayer wiring board characterized by:

(6) The multilayer wiring board according to (5) above, wherein the insulating layer is made of ceramic and glass.

(7) The multilayer wiring board according to (6) above, wherein the insulating layer contains 30 to 50 volume % alumina and 50 to 70 volume % glass.

(8) The glass is SLo, 37-65% by weight, B20
．． 0.5-10% by weight, A12zOs6-17.
The multilayer wiring board according to (6) or (7) above, containing 5% by weight of MO and 25 to 45% by weight of divalent metal oxide MO.

(9) Heat the insulating layer, conductor layer and dielectric layer to 1000°C.
The multilayer wiring board according to any one of (5) to 8) above, which is formed by simultaneous integral firing in the following steps.

According to the present invention, by adding CuO, Pb (Mg+
z*Nb,,-s) The sintering temperature of Os-PbTiOh system is lowered, and moreover, it is lower than 1000℃, especially 800-95
At a sintering temperature of 0°C, good properties such as a large dielectric constant, small dielectric loss, and high insulation resistance can be obtained.

Moreover, since the heat shrinkage characteristics are very similar to those of the insulating layer material for low-temperature firing containing ceramic aggregate and glass, curling and warping will be extremely rare even when simultaneously fired together.

<Specific configuration> Hereinafter, the specific configuration of the present invention will be explained in detail.

The dielectric ceramic composition of the present invention has Pb (Mg+
ziNbazs)Os-PbTiOs-based composite oxide.

That is, the composition contains the following composite oxide composition.

PbO: 56.1 to 59.9 mol%, especially 59.0 to 59.7 mol% MgO: 12.1 to 19.8 mol%, especially 18.1 to 19.3 mol% Nb, O,: 12 .1 to 19.8 mol%, especially 18.1
~19.3 mol% Ti0a:O16~19.7 mol%, especially 1.7~4.8 mol% Even if these are contained as a mixture of each oxide, a part of them dissolves in solid solution and forms a composite oxide. The oxides may be contained as a solid solution or may be contained as a composite oxide having a perovskite structure.

In addition, in the composition, it is sufficient that the oxides are contained as described above in terms of each of the above oxides (the oxidation states thereof may be various).

Furthermore, each oxide may be contained as a compound that becomes an oxide upon firing of an oxalate, carbonate, hydroxide, nitrate, organic compound, or the like.

Such a composite oxide composition has the following composition:
iOio, corresponds to the stoichiometric composition of 65≦X≦0.99, especially 0.92≦X≦0.97. Such a composition can change desirable values in terms of properties such as dielectric constant, dielectric loss, and insulation resistance.

These are generally included in the composition as particle sizes of the order of 0.2-4.

The composition of the present invention contains an oxide Pb (Mg+zx Nb*za) OsP b T having such a composite oxide composition.
The copper compound is contained in an amount of 0.1 to 10 mol%, preferably 0.5 to 5 mol%, particularly 0.5 to 3 mol%, based on 1 mol of iOs.

The copper compound to be used may be copper oxide or any compound that becomes copper oxide, especially CuO, upon firing (for example, in addition to copper oxide, copper oxalates, carbonates, hydroxides, Examples include nitrates, acetates, and organic compounds.

These copper compounds may have a particle size of about 0.2 to 2-2.

Note that the copper compound may be dissolved in solid solution with the above-mentioned composite oxide in advance as a copper plating.

The addition of such a copper compound improves its heat shrinkage properties.
It can be matched with the insulating layer material for low-temperature firing,
Furthermore, the sintering temperature can be lowered while maintaining good electrical properties.

Note that such an effect will not occur unless copper oxide is contained in the sintered body, and instead of Cu, Fe, Ni,
When using W, Zn, etc., the thermal shrinkage characteristics do not match those of the insulating layer material for low-temperature firing, resulting in disadvantages such as deterioration of electrical properties and inability to perform firing in air.

In addition, the amount of copper compound added is 10 mol% in terms of CuO.
If it exceeds , insulation resistance will deteriorate.

In addition, from the viewpoint of shrinkage characteristics, it is preferable to pre-calcine the composite oxide so that the copper compound is contained in the form of copper oxide.

Furthermore, it is preferable that the composition of the present invention contains a Mn compound.

By containing the Mn compound, the insulation resistance of the sintered body becomes even higher.

The Mn compound is contained in an amount of 1.7 mol % or less, particularly 0.04 to 1.7 mol %, in terms of MnO, per 1 mol of the composite oxide.

The Mn compound used may be a compound that becomes manganese oxide upon calcination, such as manganese oxide, such as MnO, as well as carbonates, oxalates, hydroxides, nitrates, acetates, organic compounds, and the like.

These particles are used with a particle size of about 0.2 to 2.5 mm, or they can be used by being included in the composite oxide.

The above-mentioned compounds may be mixed and used as they are, but more preferable results can be obtained by calcining the mixture at 650 to 800° C. and pulverizing the mixture.

In addition to these, the composition of the present invention also contains binders such as polyvinyl alcohol, polyvinyl butyral, polyacrylate, and polymethacrylate, alcohols such as toluene and methanol, solvents such as ketones such as acetone, and further plasticizers and dispersants. It is made into a base containing agents, surfactants, etc.

Such a composition is formed into a film by a printing method, a transfer method, a green sheet method, etc., and then fired. The sintering temperature is 1000°C or less, especially 800-950°C, and even 80°C.
The temperature is 0 to 900°C.

Further, the sintering time can be about 0.5 to 5 hours, and the sintering atmosphere can be performed in air.

Through such sintering, 56.1 to 59.9 mol% in terms of PbO, 12.1 to 19.8 mol% in terms of MgO, 12.1 to 19.8 mol% in terms of Nb, O, 0.6 to 0.6 in terms of TiO□ 19.7 mol%, XPb(Mg+zsNbazs)Os-(1~X)Pb
A composite oxide having a stoichiometric composition of TiO20,65≦X≦0.99 or a composition slightly biased from the stoichiometric composition. M n of .7 mol% or less
A sintered body of the present invention containing O is obtained.

In addition, in such a sintered body, the above-described composite oxide composition usually exhibits a perovskite structure, CuO is segregated at the grain boundaries, and M n O is dissolved in the grain boundaries.

The composite oxide usually has a grain size of about 2 to 8 microns.

Note that the sintered body may contain a trace amount of other oxides.

Such a sintered body is particularly suitable for application to a dielectric layer of a multilayer wiring board.

The dielectric layer generally has a thickness of about 10 to 200 mm.

In such a case, a material for low-temperature firing made of ceramic and glass is suitable as the material constituting the insulating layer.

In this case, the ceramic is preferably alumina, cordierite, mullite, forsterite, silica, etc., and alumina is particularly preferred. The particle size may be about 0.6 to 5.

In addition, the content of these ceramics is 30 to 50% by volume,
The content of glass is preferably 50 to 70% by volume.

On the other hand, as the glass used, aluminoborosilicate glass containing a divalent metal oxide MO is suitable.

In this case, M constituting the divalent metal oxide MO is as follows:
Those other than pb are suitable, especially Ca%Ba, Sr%Mg
One or more of these are preferred.

and, SiO□25-75% by weight B, 0.　0.5-15% by weight Al2zOs4-20% by weight MO24-59% by weight Preferably.

Among these, SIO* 37-65% by weight B, 0. Those containing 85 to 10% by weight of O, 6 to 17.5% by weight of Al2O, and 25 to 45% by weight of MO give more favorable results in terms of consistency in shrinkage characteristics.

These insulating layer materials for low-temperature firing are made into a paste in the same manner as described above, and are made into a paste using the green sheet method, printing method, transfer method, etc. It is integrated with the patterned dielectric ceramic composition as a certain thickness.

Furthermore, the conductor layer materials used include Ag, Ni%Pd
, AgPd, Cu, etc. can be applied.

Among these, Ag, Pd, and AgPd in particular have many characteristics that match the dielectric ceramic sintered body of the present invention, and are particularly suitable for firing in air.

Note that, depending on the case, Au, Pt, etc. may be used, and these conductor layer materials are also made into a paste, and the layers are formed in a pattern having a thickness of about 10 to 200Q in the same manner as described above.

After these are integrated, they are simultaneously fired at the above temperature to produce a multilayer wiring board with a built-in capacitor.

Note that the structure of the multilayer wiring board may be of various known types.

<Example> Hereinafter, the present invention will be explained in further detail by referring to specific examples of the present invention.

Example 1 Each has a nearly stoichiometric composition. PbO with an average particle size of 1.2 mm, MgO with an average particle size of 0.5- Nb1Os with an average particle size of 0.7- As an additive, CuO with an average particle size of 0,4- and MnCOs with an average particle size of 0.2P was prepared.

These materials were mixed in the ratio shown in Table 1 and calcined at 700°C. Thereafter, water was added using zirconia balls, and the mixture was ground in a ball mill and dried.

To this was added toluene/alcohol as a solvent, polyvinyl butyral as a binder, and n-butyl phthalate as a plasticizer, and mixed in a ball mill using zirconia balls to form a slurry into a paste.

This is made into a green sheet using the doctor blade method.
This was cut and heated in air at the temperature shown in Table 1.
A sample with a diameter of 30 mm and a thickness of 1 mm was obtained by firing for a period of time.

For each of these samples, the dielectric constant ε and dielectric loss Tan δ at 25° C. were measured at a frequency of 1 kHz and a voltage of 1 μ. The results are shown in Table 1.

Further, the specific resistance Ω·cta at 25° C. and 50V is also listed in Table 1.

In Table 1, PMN is P b (M g +/3Nb
zzs)Oa, PT indicates P bT i O, and the composition of the sintered body was stoichiometric as the charging composition.

From the results shown in Table 1, it can be seen that the samples of the present invention improve Tan δ and specific resistance while maintaining the dielectric constant even when fired at low temperatures.

Furthermore, the results of thermomechanical analysis of each sample No. 3 (comparison) and No. 5 are shown in FIG.

Also shown in FIG. 1 are the results of the thermomechanical analysis of the insulating layer material for low-temperature firing described below.

Glass (average particle size 1.7JjJl) 60% by weight Si
O5 2.0% by weight BaO4.2% by weight Aβ0 11.0% by weight MgO2.0
Weight% CaO 12.6% by weight SrO 0.2% by weight BaO 16.5% by weight Others 0.5% by weight AJ2. O,
(Average particle size: 1.5 Pm) 4Q% by weight From the results shown in FIG. 1, it can be seen that the thermal shrinkage characteristics of the sample of the present invention are very similar to those of the insulating layer material for low-temperature firing.

The heat shrinkage characteristics of each sample are also listed in Table 1 based on the evaluation below.

O: The difference in thermal contraction rate at 800°C with the above insulating layer material is ±
Within 1% ○: Within ±2% ×: Greater than ±2% Next, each sample and the insulating layer material for low temperature firing,
Average particle size 1. Using OpAg-Pt paste, 880℃
This was sintered for 0.5 hours to produce a multilayer wiring board.

The structure consists of a dielectric layer of the same thickness formed in a pattern between four 150% thick insulating layers, a 10μ thick conductor layer arranged in a pattern, and through holes formed in a predetermined pattern. be.

Further, the overall size was 5.6 x 6.5 mm.

When the sample of the present invention was used, no warping, bending, or cracking occurred at all, whereas when using the comparative sample, warping, bending, or cracking of up to about 3 mm occurred.

Example 2 A multilayer wiring board was produced in the same manner as in Example 1 except that the material for the insulating layer for low-temperature firing was changed to the following.

Glass (average particle size 2.2M) 50% by weight 5iOz
54.2% by weight B, 03
3.9 wt% Al2a O@9
．． 3% by weight CaO 1.6% by weight BaO 1.6% by weight Sr0 29.3% by weight Aβ 20. (
Average particle size: 3.2) 50% by weight As a result, the results were the same as in Example 1.

It has been confirmed that such effects can be equally achieved in the insulating layer material for low-temperature firing containing the above-mentioned glass.

Effect> The composition of the present invention can be
It is sintered at a temperature of 800 to 900°C, and a dense sintered body can be obtained.

Also, at 25°C, the dielectric constant of 1k)lzte(F) is 1ooo.

The above results are obtained, and the dielectric constant is maintained when CuO is added and fired at high temperature.

Moreover, the dielectric loss is 2.5% or less, particularly 2% or less.

Also, the insulation resistance is 10 Ω・cm or more.

In particular, in the MnO-added system, the resistance is 10''Ω·cm or more.

In this way, the dielectric loss and insulation resistance are improved compared to when CuO is added and fired at a high temperature.

Furthermore, these temperature characteristics are also good and fully satisfy the 25U characteristics.

In addition, the heat shrinkage characteristics can be made very similar to that of the insulating layer material for low-temperature firing containing ceramic aggregate and glass, and the occurrence of curling and warping is extremely reduced when the multilayer wiring board is simultaneously integrated and fired. .

Moreover, it has high characteristics and high capacity, and the substrate can be made smaller.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the heat shrinkage characteristics of the dielectric ceramic composition of the present invention. Patent Applicant TDC Co., Ltd. Procedural Amendment (Voluntary) 1. Indication of the case Patent Application No. 325517 of 1988 2. Name of the invention 3. Person making the amendment Relationship with the case Patent applicant name Title TDC Co., Ltd. Company 4, Agent address: 6, 3rd floor, Tenjin Yaei Kosan Building, 3-23-1 Yushima, Bunkyo-ku, Tokyo 113 Contents of amendment (1) “Titanate” in the third line from the bottom of page 5 of the specification
is corrected to "lead perovskite type". (2) "Titanate composite dielectric ceramic" in lines 2 and 3 of page 6 is corrected to "titanate and lead perovskite composite dielectric ceramic." (3) rAg-P on page 23, lines 10 to 11
Correct "t paste" to "rAg-Pd paste". Proceedings... Official document (spontaneous) 1゜Indication of the case Patent Application No. 325517 of 1988 2, Name of the invention 3゜Relationship with the case by the person making the amendment Patent applicant name Title TDC Co., Ltd. 4, Agent resident Address: 3rd floor, Tenjin Yasaka Kosan Building, 3-23-1 Yushima, Bunkyo-ku, Tokyo 113 6° Correction details

Claims (9)

[Claims] (1) Pb(Mg_1_/_3Nb_2_/_3)O_
3-PbTiO_3-based dielectric ceramic composition containing 56.1 to 59.9 mol% in terms of PbO, M
12.1 to 19.8 mol% in terms of gO, Nb_2O
12.1 to 19.8 mol% in terms of _5, TiO_2
Cu
A composition for dielectric ceramics, characterized in that it contains 0.1 to 10 mol% of a copper compound in terms of O. (2) Furthermore, for the above composition, 1.7 in terms of MnO
The dielectric ceramic composition according to claim 1, containing a Mn compound in an amount of mol % or less. (3) Pb(Mg_1_/_3Nb_2_/_3)O_
3-PbTiO_3-based solid solution, PbO56.
1 to 59.9 mol%, MgO 12.1 to 19.8 mol%
, Nb_2O_312.1-19.8 mol%, TiO_
0.1 for a solid solution composition of 20.6 to 19.7 mol%
A dielectric ceramic sintered body characterized by containing ~10 mol% of CuO. (4) The dielectric ceramic sintered body according to claim 3, further comprising 1.7 mol% or less of MnO based on the solid solution composition. (5) In a multilayer wiring board in which an insulating layer, a conductor layer, and a dielectric layer are laminated, the dielectric layer is as claimed in claim 3 or 4.
A multilayer wiring board, characterized in that it is formed from the dielectric ceramic sintered body described in . (6) The multilayer wiring board according to claim 5, wherein the insulating layer is made of ceramic and glass. (7) The multilayer wiring board according to claim 6, wherein the insulating layer contains 30 to 50% by volume of alumina and 50 to 70% by volume of glass. (8) The glass is SiO_237-65% by weight, B_
2O_30.5-10% by weight, Al_2O_36-17
．． The multilayer wiring board according to claim 6 or 7, containing 5% by weight of MO and 25 to 45% by weight of divalent metal oxide MO. (9) Heat the insulating layer, conductor layer and dielectric layer to 1000°C.
Claims 5 to 8 formed by simultaneous integral firing of the following:
The multilayer wiring board according to any one of the above.