JP2000264719A - Porcelain composition, porcelain and circuit board using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a porcelain composition capable of being fired at 800-1,000 deg.C, having a low dielectric constant and a small dielectric loss in a high frequency domain and also having a coefficient of thermal expansion close to that of chip parts and a printed board and high chemical resistance. SOLUTION: A mixture of 30-95 wt.% glass containing SiO2, Al2O3, MgO, ZnO and B2O3, 0.1-35 wt.% multiple oxide of at least one (M) selected from the group consisting of Ca, Sr and Ba, Al and Si, 0-40 wt.% SiO2, 0-30 wt.% ZnO and 0-10 wt.% B2O3 is molded and fired at 800-1,000 deg.C to obtain the objective porcelain containing an SiO2 crystal phase Si, a spinel type crystal phase SP, a Zn2Al4Si5O18 type crystal phase ZL and an MAl2Si2O8 (M=Ca, Sr, Ba) type crystal phase ML.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porcelain composition most suitable for a wiring board applied to a package for storing semiconductor elements, a multi-layer wiring board, etc., and in particular, can be co-fired with copper or silver. The present invention also relates to a porcelain composition and a porcelain suitable as an insulating substrate of a wiring board that can be mounted with high reliability on an external circuit board made of an organic resin such as a printed board, and a wiring board using the same.

[0002]

2. Description of the Related Art Conventionally, as a ceramic multilayer wiring board, a ceramic multilayer wiring board in which a wiring layer made of a refractory metal such as tungsten or molybdenum is formed on the surface or inside of an insulating substrate made of an alumina-based sintered body has been most widely used. I have.

[0003] Also, recently, in the age of advanced information technology, the frequency band used is shifting to higher and higher frequencies. In such a high-frequency wiring board that requires transmission of a high-frequency signal, in order to transmit a high-frequency signal without loss, the resistance of the conductor forming the wiring layer is small, and the dielectric in the high-frequency region of the insulating substrate is low. Low loss is required.

However, conventional tungsten (W),
A high melting point metal such as molybdenum (Mo) has a large conductor resistance and a low signal propagation speed, and it is difficult to propagate a signal in a high frequency region of 30 GHz or more. Therefore, instead of metals such as W and Mo, copper, Low resistance metals such as silver and gold are being used.

[0005] Since it is difficult to sinter such a wiring layer containing a low resistance metal as a main component together with alumina,
Recently, wiring boards using glass or a composite material of glass and ceramics, that is, so-called glass ceramics as an insulating substrate are being developed.

For example, as disclosed in Japanese Patent Application Laid-Open No. 60-240135, a multilayer obtained by simultaneously firing a low-resistance metal using a porcelain composition obtained by adding a filler such as Al ₂ O ₃ or mullite to a zinc borosilicate glass. Wiring board and Japanese Patent Laid-Open No. 5-2
As disclosed in Japanese Patent No. 98919, a glass ceramic material in which mullite or cordierite is precipitated as a crystal phase has been proposed.

In addition, when a wiring board such as a multilayer wiring board or a package for housing a semiconductor element is mounted on a printed board containing an organic resin by an insulating board such as a mother board, the printed circuit board is mounted by a stress generated due to a difference in thermal expansion from the printed board. In order to prevent exfoliation or cracking of a portion, it is desirable that the thermal expansion coefficient of the insulating substrate be close to that of the printed circuit board.

Accordingly, the present applicant has disclosed in Japanese Patent Application Laid-Open No. 11-120.
No. 29, by using a sintered body containing a crystal phase mainly composed of SiO ₂ and a spinel type crystal phase mainly composed of Zn and Al ₂ O ₃ as an insulating substrate of a wiring board,
In addition to increasing the thermal expansion coefficient of the insulating substrate,
It was proposed that the dielectric constant be 6 or less and the dielectric loss be 25 × 10 ^-4 or less.

[0009]

However, the glass ceramics disclosed in JP-A-60-240135 and JP-A-5-298919 can be co-fired with low-resistance metals such as copper, silver and gold. However, the sintered body is
Low thermal expansion coefficient compared to alumina sintered body
ppm / ° C., and when mounted on a printed circuit board, the reliability of mounting was low and was not practically satisfactory.

On the other hand, the sintered body disclosed in Japanese Patent Application Laid-Open No. 11-12029 has a high thermal expansion, so that the mounting reliability is high, and a wiring for transmitting a high-frequency signal such as a millimeter wave. Although useful as an insulating material for a substrate, the chemical resistance is not sufficient, and when performing plating or the like in a manufacturing process of a wiring substrate, there is a possibility that some elements in the insulating substrate may be eluted.

Therefore, the present invention is capable of firing at 800 to 1000 ° C. so as to enable multilayering using gold, silver and copper as wiring conductors, and has a high thermal expansion coefficient close to that of a printed circuit board. It is an object of the present invention to provide a porcelain composition having a low dielectric constant and a low dielectric loss even in a high-frequency region, and having excellent chemical resistance, and a wiring board using the same as an insulating substrate. I do.

[0012]

Means for Solving the Problems The present inventors diligently studied the above problems and found that Si, Al, Zn, Mg and B
And at least one selected from the group consisting of Ca, Sr and Ba as a metal element, and as a crystal phase, S
an iO ₂ crystal phase, a spinel crystal phase containing at least Zn and Al, a composite oxide crystal phase containing at least Zn, Al and Si, and at least one (M) selected from the group consisting of Ca, Sr and Ba. By precipitating a composite oxide crystal phase containing Al, Si and Si as a constituent phase, high thermal expansion can be achieved, and a low dielectric constant can be achieved.
The present inventors have found that low dielectric loss can be realized in a high frequency region and chemical resistance can be improved, and the present invention has been accomplished.

That is, the porcelain composition of the present invention comprises SiO ₂ ,
Al ₂ O _3, MgO, composite oxides containing glass 30-95 wt% containing ZnO and B ₂ O _3, Ca, at least one selected from the group consisting of Sr and Ba and (M) and Al and Si 0 0.1 to 35% by weight, and at least one of SiO ₂ , ZnO, and B ₂ O ₃ is further provided with 0 to 40% by weight of SiO _{2 and} 0 to 30% by weight of ZnO.
Wt%, but it is desirable to include a B ₂ O ₃ 0% by weight.

The glass is made of SiO ₂ 40-52.
Wt%, Al ₂ O ₃ 14~32 wt%, MgO4~24
Wt%, ZnO1～16 wt%, B ₂ O ₃ 5 to 15 that consists of the ratio of weight%, said Ca, complex oxide comprising at least one (M) and Al and Si selected from the group consisting of Sr and Ba Preferably, the object is MAl ₂ Si ₂ O ₈ .

Further, the porcelain of the present invention comprises Si, Al, Z
n, Mg and B, and at least one selected from the group consisting of Ca, Sr and Ba as a metal element, and as a crystal phase, a SiO ₂ crystal phase and at least Zn and Al
, A composite oxide crystal phase containing at least Zn, Al and Si, Ca, Sr and B
a) containing at least one type (M) selected from the group a) and a composite oxide crystal phase containing Al and Si, having a thermal expansion coefficient of 5.5 ppm / ° C. or more from room temperature to 400 ° C., and a dielectric constant of 9 or more. It is characterized by the following.

Here, the SiO ₂ crystal phase is a quartz crystal phase, and at least Zn, Al and S
The composite oxide crystal phase containing i is Zn ₂ Al ₄ Si ₅ O ₁₈
That the composite oxide crystal phase contains at least one type (M) selected from the group consisting of Ca, Sr, and Ba and Al and Si is a MAl ₂ Si ₂ O ₈ type crystal phase. desirable.

Further, the wiring substrate of the present invention comprises an insulating substrate and a wiring layer disposed on the surface and / or inside thereof, wherein the insulating substrate is made of Si, Al, Zn, M
g and B, and at least one selected from the group consisting of Ca, Sr and Ba as a metal element, and as a crystal phase, a SiO ₂ crystal phase, a spinel crystal phase containing at least Zn and Al, and at least Zn, Al and Si
And a composite oxide crystal phase containing at least one (M) selected from the group consisting of Ca, Sr and Ba, Al and Si,
It is characterized by being composed of a porcelain having a thermal expansion coefficient of 5.5 ppm / ° C. or more at 0 ° C. and a dielectric constant of 9 or less.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The porcelain composition of the present invention comprises Si
_{O 2, Al 2 O 3,} MgO, 30~95 wt% glass containing ZnO and B ₂ O _3, in particular 50 to 90 wt%, more preferably a 60 to 85% by weight, Ca, from the group of Sr and Ba 0.1 to 35% by weight, especially 0.5% by weight of a composite oxide of at least one selected from (M) and Al and Si
-25% by weight, more preferably 1-20% by weight.

Further, the porcelain composition of the present invention comprises Si
_{O 2, Al 2 O 3,} MgO, ZnO and B ₂ and the glass 30 to 95 wt% containing O _3, Ca, at least one selected from the group consisting of Sr and Ba (M) and Al and Si
0.1 to 35% by weight of a composite oxide with SiO ₂ 0 to 4
0% by weight, particularly 5 to 35% by weight, more preferably 7 to
30 wt%, ZnO 0-30 wt%, particularly 2-25 wt%, more preferably 4-20 wt%, B ₂ O ₃₀ 0
Preferably, it comprises 10% by weight, especially 0.5 to 5% by weight, more preferably 0.5 to 3% by weight.

The composition of each component was limited to the above range.
If the amount of the glass is less than 30% by weight, it is difficult to densify the porcelain by firing at a temperature of 1000 ° C. or less. Is eluted and the composition of the porcelain is shifted.

The composite oxide of at least one (M) selected from the group consisting of Ca, Sr and Ba and Al and Si is a component which promotes the sintering of the porcelain and increases the chemical resistance. %, The chemical resistance of the porcelain is poor,
Porcelain is deteriorated by plating or the like. Also, 35
If the content is more than 100% by weight, it is difficult to densify the porcelain by firing at a temperature of 1000 ° C. or less.

The composite oxide of at least one (M) selected from the group consisting of Ca, Sr and Ba with Al and Si is CaAl ₂ Si ₂ O ₈ , SrAl ₂ Si ₂
One of composite oxides such as O ₈ and BaAl ₂ Si ₂ O ₈
Desirably more than species.

SiO ₂ and ZnO are optional components for adjusting the coefficient of thermal expansion of the porcelain. Particularly when added, the quartz phase and the spinel-type crystal phase, which are the crystal phases having a high thermal expansion, are added to the porcelain. By precipitating a crystal phase, the coefficient of thermal expansion of the sintered body can be increased.
However, when the added amount of SiO ₂ exceeds 40% by weight and the added amount of ZnO exceeds 30% by weight, the sinterability is reduced, and
It becomes difficult to fire at a temperature of 00 ° C. or less.

Further, B ₂ O ₃ is an optional component. In particular, sinterability can be improved by adding B ₂ O _3. However, if added in excess of 10% by weight, the B component dissolves in a solvent, making it difficult to form a slurry. Or it may be eluted as a liquid phase during firing.

Here, the glass desirably has a softening point of 500 to 800 ° C., and is preferably crystallized glass in order to reduce dielectric loss of porcelain. Furthermore, the composition of SiO ₂ 40 to 52 wt%, especially 42-50 wt%, Al ₂ O ₃ 14 to 32% by weight, in particular 16 to 31 wt%, MgO4～24 wt%, especially 6-20 wt%, ZnO 1-16% by weight, special 3-14
Wt%, B ₂ O ₃ 5 to 15 wt%, it is desirable that the proportion of JP 7-12 wt%.

According to the present invention, by using the above glass composition, even when a substance having a high melting point such as SiO ₂ is contained as a filler, the temperature is 1000 ° C. or lower, particularly 950 ° C. or lower, and further 930 ° C. or lower. As described later, it is possible to simultaneously sinter with copper and / or silver, which is frequently used as a wiring layer of a high-frequency wiring board, as described later.

According to the present invention, at least one kind (M) selected from the group consisting of Ca, Sr and Ba, and Al
Oxide with Si and Si, especially MAl ₂ Si ₂ O
₈ By adding (M = Ca, Ba, Sr), a part of the composite oxide undergoes a decomposition reaction, and the decomposition components dissolve in the glass to improve the chemical resistance of the porcelain. .

To produce porcelain using the porcelain composition of the present invention, the above-mentioned SiO ₂ , Al ₂ O ₃ , MgO, Zn
Crystallized glass containing O and B ₂ O ₃ , at least one (M) selected from the group consisting of Ca, Sr and Ba, and Al
Oxide containing Si and Si, SiO ₂ and ZnO
And, using a mixed powder of the above composition consisting of B ₂ O ₃ , a doctor blade method, a calendar roll method, or a rolling method, after forming a molded body of a predetermined shape by a known molding method such as a press molding method, 800 to 1000 ° C.
By baking in an oxidizing atmosphere or a non-oxidizing atmosphere, a porcelain having a relative density of 97% or more can be manufactured.

The overall composition of the porcelain obtained in this way includes Si, Al, Mg, Zn and B, Ca, S
When the total amount of at least one metal element selected from the group consisting of r and Ba in terms of oxide is 100% by weight,
The SiO ₂ 16~68% by weight, in particular 32 to 62% by weight,
Al ₂ O ₃ is 10 to 33% by weight, especially 12 to 30% by weight, MgO is 3 to 13% by weight, especially 4 to 11% by weight, Z
2 to 38% by weight, particularly 3 to 35% by weight of nO, B ₂ O ₃
2 to 20% by weight, especially 5 to 10% by weight, and at least one oxide selected from the group consisting of Ca, Sr and Ba in an amount of 0.01 to 15% by weight, particularly 0.05 to 13% by weight.
It is desirable to be composed of the ratio of

Further, as shown in FIG. 1 which is a schematic view for explaining the structure of the porcelain, the porcelain of the present invention has a SiO ₂ crystal phase (Si) and a spinel type crystal phase (at least containing Zn and Al). SP), a composite oxide crystal phase (ZL) containing at least Zn, Al and Si, and at least one (M) selected from the group consisting of Ca, Sr and Ba and Al
And a composite oxide crystal phase (ML) with Si.

Here, the SiO ₂ crystal phase (Si) exists as quartz, cristobalite, tridymite, and the like. Cristobalite has a stable thermal expansion behavior because it has a bending point of a thermal expansion coefficient near 200 ° C. Quartz (coefficient of thermal expansion 13 to 20 pp)
(m / ° C.).

The spinel-type crystal phase (SP) containing at least Zn and Al includes, for example, a garnitite crystal phase represented by ZnAl ₂ O _4, which has the effect of increasing the coefficient of thermal expansion of porcelain and reducing dielectric loss. There is.

Further, the complex oxide crystal phase (ML) of at least one kind (M) selected from the group consisting of Ca, Sr and Ba with Al and Si is CaAl ₂ Si ₂ O ₈ , Sr
Desirably, it is made of Al ₂ Si ₂ O ₈ or BaAl ₂ Si ₂ O ₈ , which precipitates as acicular crystals and can increase the transverse strength and toughness of porcelain.

Further, the composite oxide crystal phase (ZL) containing at least Zn, Al and Si is ZnAl
₄ Si ₅ O ₁₈ type crystal phase, which can reduce the amount of Zn in the glass of the porcelain and increase the chemical resistance, but the composite oxide crystal phase is the above-mentioned MAl ₂ Si ₂ O ₈
It is also produced by decomposition of the type composite oxide crystal phase.

In each of the above crystal phases, other than the main constituent metal elements, other metal elements may be dissolved in a solid solution within a range that does not change the crystal structure. For example, ZnAl ₂ O ₄
Has a solid solution of MgAl ₂ O ₄ and (Zn, Mg) Al
It may consist of a spinel-type crystal phase represented by ₂ O ₄ .

According to the present invention, in addition to the above crystal phases, a small amount of a cordierite type crystal phase represented by 2MgO.2Al ₂ O ₃ .5SiO ₂ or an enstatite type crystal phase represented by MgSiO ₃ is present. May be present.

Further, in the porcelain, a glass phase composed of a glass component containing at least Si exists at the grain boundary of the above-mentioned crystal phase, and is selected from the group consisting of Ca, Sr and Ba in the glass. By dissolving at least one kind (M), the chemical resistance of the porcelain can be improved.

According to the present invention, the thermal expansion coefficient of the porcelain from room temperature to 400 ° C. is 5.5 ppm /
° C or more, desirably 7 ppm / ° C or more, particularly 9 ppm /
° C or more, and further 10 ppm / ° C or more, and the difference in the coefficient of thermal expansion between the porcelain and an external circuit board made of organic resin such as a chip component such as GaAs or a printed board can be reduced. When used as an insulating substrate, the reliability of mounting can be improved.

The dielectric constant of the porcelain was measured at a frequency of 1 to 30.
9 below in GHz, in particular 7 or less, further may be a 6 or less, it is possible to reduce the influence of the substrate of the high-frequency signal, measuring the dielectric loss in the high frequency band porcelain frequency 1~30GHz in 30 × 10 ^{- 4} or less, especially 25
Since it can be set to × 10 ⁻⁴ or less, and further to 20 × 10 ⁻⁴ or less, signal transmission characteristics in a high frequency band, particularly, a millimeter wave band are improved.

The porcelain composition of the present invention has a low dielectric loss in a high frequency band, and thus has a dielectric loss of 1 GHz or more, particularly 20 GHz or more, more preferably 50 GHz or more, and even 70 GHz.
It is suitable for forming the insulating layer of the high-frequency wiring board described above.

When the porcelain of the present invention is used as an insulating substrate of a wiring board, the coefficient of thermal expansion of the insulating substrate from room temperature to 400 ° C. is close to that of a chip component such as GaAs or a printed board. As described above, it is desirable to control and appropriately adjust the composition and the structure of the porcelain constituting the substrate.

This is because when the thermal expansion coefficient of the insulating substrate is different from that of the mounted chip component or printed circuit board, the chip component or the printed circuit board is subjected to repeated temperature cycles at the time of solder mounting or by stopping the operation of the semiconductor element. This is because stress due to the difference in thermal expansion between the mounting part and the package causes cracks and the like to occur in the mounting part, which impairs the reliability of the mounting structure. In order to achieve this, the difference in thermal expansion coefficient from the chip component is 2p
pm / ° C. or less, and in order to achieve matching with the printed board, it is desirable that the difference in thermal expansion coefficient with the printed board be 2 ppm / ° C. or less.

Specifically, a method of manufacturing a wiring board having a wiring layer using the porcelain composition of the present invention will be described. A slurry is prepared by mixing a mixed powder of the above-described composition with an appropriate organic solvent and a solvent, and the slurry is formed into a sheet by a conventionally known doctor blade method, calender roll method, or rolling method, press molding method. Mold into Then, after forming a through-hole as desired in the sheet-shaped molded body, copper, gold,
A metal paste containing at least one of silver is filled. Then, on the surface of the sheet-shaped molded body, the metal paste is used to form a high-frequency line pattern or the like that can transmit a high-frequency signal by screen printing, gravure printing, or the like so that the thickness of the wiring layer is 5 to 30 μm. Apply.

Thereafter, a plurality of sheet-like molded bodies are aligned and laminated and pressed, and then fired in a non-oxidizing atmosphere such as a nitrogen gas or a nitrogen-oxygen mixed gas at 800 to 1050 ° C. to produce a wiring board. be able to. Then, a chip component such as a semiconductor element is appropriately mounted on the surface of the wiring board, and connected to the wiring layer so that signals can be transmitted.

As a connection method, a connection is made by mounting directly on the wiring layer, or a resin, Ag
-The chip component is fixed to the surface of the insulating substrate with an adhesive such as a resin such as epoxy, Ag-glass, or Au-Si, a metal, or a ceramic, and the wiring layer and the semiconductor element are connected by wire bonding or TAB tape. In addition,
As this semiconductor element, a chip component such as a Si-based or GaAs-based component can be used, but it is particularly useful for a GaAs-based chip component.

Further, a cap made of the same kind of insulating material as the insulating substrate, another insulating material, or a metal having a good heat radiation property and having an electromagnetic wave shielding property is provided on the surface of the wiring board on which the semiconductor element is mounted, with glass, The semiconductor element may be hermetically sealed by bonding with an adhesive such as a resin or a brazing material.

A specific structure of a package for housing a semiconductor element, which is an example of a high-frequency wiring board in which the ceramic composition of the present invention can be preferably used, and a mounting structure thereof will be described with reference to FIG. FIG. 2 is a schematic sectional view of a semiconductor storage package, particularly a ball grid array (BGA) type package in which connection terminals are formed of ball-shaped terminals.

According to FIG. 2, the package A has a cavity 3 formed by an insulating substrate 1 made of an insulating material and a lid 2, in which a chip component 4 such as GaAs is bonded. Implemented by agent.

Also, on the surface and inside of the insulating substrate 1,
A wiring layer 5 electrically connected to the chip component 4 is formed. The wiring layer 5 is desirably made of a low-resistance metal such as copper, silver, or gold in order to minimize conductor loss when transmitting a high-frequency signal. When transmitting a high-frequency signal of 1 GHz or more to the wiring layer 5, it is necessary to transmit the high-frequency signal without loss. Therefore, the wiring layer 5 includes a known strip line, microstrip line, coplanar line, It is composed of at least one of dielectric waveguide lines.

In the package A of FIG. 2, a connection electrode layer 6 is formed on the bottom surface of the insulating substrate 1 and is connected to the wiring layer 5 in the package A. A ball-shaped terminal 8 is formed on the connection electrode layer 6 with a brazing material 7 such as solder.

The package A is connected to the external circuit board B.
As shown in FIG. 2, a polyimide resin,
An external circuit board B having a wiring conductor 10 formed on the surface of an insulating substrate 9 made of an insulating material containing an organic resin such as an epoxy resin or a phenol resin is mounted via a brazing material. Specifically, the ball-shaped terminals 8 attached to the bottom surface of the insulating substrate 1 in the package A and the wiring conductors 10 of the external circuit board B are brought into contact with each other, and the brazing material 11 such as a solder such as Pb-Sn is used. It is mounted with brazing. Further, the ball-shaped terminal 8 itself may be melted and connected to the wiring conductor 10.

According to the present invention, in a surface mount type package which is mounted on an external circuit board such as a printed board by brazing with the ball-shaped terminals 8 interposed therebetween, the external circuit board is connected to the insulating substrate. Since the difference in thermal expansion can be made smaller than that of a conventional ceramic material, even when a thermal cycle is applied to such a mounting structure,
As a result of suppressing the generation of stress in the mounting portion, the long-term reliability of the mounting structure can be improved.

[0053]

EXAMPLES Two glasses having the following compositions were prepared.

Glass A: SiO ₂ 44% by weight—Al ₂ O
₃ 29% by weight-MgO 11% by weight-ZnO 7% by weight-B
9% by weight of ₂ O ₃ Glass B: 44% by weight of SiO ₂ -26% by weight of Al ₂ O ₃
-MgO19 wt% -ZnO1 wt% -B ₂ O ₃ 10 wt% Then, with respect to the crystallized glass powder, average particle size 3
μm or less silica (quartz) powder and ZnO powder, MA
Using l ₂ Si ₂ O ₈ powder (M is at least one selected from Ca, Sr and Ba) and B ₂ O ₃ powder, the porcelain after firing has the composition shown in Tables 1-4. Compounding,
Mixed.

Then, an organic binder, a plasticizer and toluene were added to the mixture to prepare a slurry.
A μm green sheet was prepared. Then, 20 sheets of the green sheet are laminated, and at a temperature of 50 ° C., 100 kg /
Thermocompression bonding was performed by applying a pressure of ² cm ² . The obtained laminate was subjected to a binder removal treatment in a steam-containing / nitrogen atmosphere at 700 ° C., and then fired in dry nitrogen under the conditions shown in Tables 1 to 4 to obtain a porcelain.

The obtained porcelain was cut into a shape having a diameter of 10 mm and a thickness of 5 mm, and a dielectric constant and a dielectric loss were measured at 20 to 30 GHz by a dielectric cylinder resonator method using a network analyzer and a synthesized sweeper. In the measurement, a dielectric substrate of a sample was sandwiched between φ50 Cu plate jigs. The dielectric constant and the dielectric loss were calculated from the resonance characteristic of the TE011 mode of the resonator.

Further, a thermal expansion curve from room temperature to 400 ° C. was taken to calculate a thermal expansion coefficient.

Further, the crystal phase contained in the porcelain was identified by X-ray diffraction measurement of the porcelain surface. The measurement results are shown in Tables 1-4.
It was shown to.

The above porcelain is 20 mm × 20 mm × 5
After immersing in a 6N hydrochloric acid (HCl) solution for 15 minutes, the porcelain was lifted up, the weight change was determined, and this was eluted into the hydrochloric acid (HCl) solution. Tables 1 to 4 show the chemical resistance.

For some of the samples, sintered bodies were prepared and evaluated in the same manner using Al ₂ O ₃ powder and CaZrO ₃ powder as filler components (Sample Nos. 9, 10 and 10).
44, 45).

Further, the same evaluation was performed using glass C and glass D having the following compositions instead of the crystallized glasses A and B (samples Nos. 71 to 76).

Glass C: SiO ₂ 10.4% by weight-Al
₂ O ₃ 2.5 wt% -B ₂ O ₃ 45.3 wt% -CaO
35.2 wt% -Na ₂ O6.6 wt% Glass D: SiO ₂ 14 wt% -Al ₂ O ₃ 24.7 wt% -B ₂ O ₃ 22.6 wt% -BaO14.2 wt%
-Li ₂ O12.8 weight% -Na ₂ O11.7% by weight

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

As is clear from the results of Tables 1 to 4, all of the porcelains according to the present invention have a thermal expansion coefficient of 5.5 ppm.
/ ° C or higher and a dielectric constant of 9 at a measurement frequency of 20 to 30 GHz.
Hereinafter, it had excellent dielectric properties with a dielectric loss of 30 × 10 ⁻⁴ or less.

On the other hand, in the composition, SiO ₂ −
Sample No. 1 in which the amount of glass containing Al ₂ O ₃ —MgO—ZnO—B ₂ O ₃ was more than 95% by weight. 1, 2, 36, 3
In Sample No. 7, the dielectric loss was as high as 49 × 10 ⁻⁴ or more, and Sample No. less than 30% by weight was used. In Nos. 34 and 69, the porcelain could not be densified even after firing at 1000 ° C.

The amount of SiO _{2, the} amount of ZnO, and the ML (C
L, BL, SL) sample N whose amount exceeds a predetermined amount
o. In Nos. 27 to 31 and 62 to 66, the porcelain could not be densified even when fired at 1000 ° C. 10
It was difficult to bake below 00 ° C. and the coefficient of thermal expansion was low. Further, the sample No. having a B ₂ O ₃ content of more than 10% by weight. In Nos. 35 and 70, the liquid phase component eluted during firing, and a porcelain could not be obtained.

Sample No. Nos. 9, 10, 44 and 45 contain Al ₂ O ₃ or CaZrO ₃ as an additive component to the glass, but crystals such as Al ₂ O ₃ or ZrO ₂ precipitate in the sintered body and the dielectric The loss has increased.

In the case of Sample No. in which the amount of ML (CL, BL, SL) added was less than 0.1% by weight. 1, 2, 9, 1
0, 14, 15, 36, 37, 44, 45, 49, 50
, All have low chemical resistance, and are treated with hydrochloric acid at 0.1%.
2% or more was eluted.

Further, Sample No. 1 using glasses C and D containing no MgO or ZnO was used as the glass. In Nos. 71 to 76, the dielectric loss tended to increase.

[0073]

As described in detail above, according to the porcelain composition of the present invention, since it can be fired at a temperature of 1000 ° C. or less, the wiring layer can be formed using a conductive material mainly composed of a low-resistance metal such as copper. Can be formed, and a porcelain having a low dielectric constant and a low dielectric loss in a high-frequency region of 1 GHz or more can be manufactured. Therefore, high-frequency signal loss can be reduced and transmission can be performed well. In addition, since the thermal expansion coefficient can be controlled to be similar to that of a GaAs chip or the like or a printed board, mounting reliability is high when a GaAs chip or the like is mounted or mounted on a motherboard such as a printed board with a brazing material or the like. It becomes a wiring board.
Furthermore, a wiring board which is excellent in chemical resistance and whose characteristics are not deteriorated even by chemical treatment at the time of manufacturing can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining the structure of porcelain obtained by firing a composition of the present invention.

FIG. 2 is a schematic cross-sectional view illustrating an example of a mounting structure of a package for housing a semiconductor element, which is an example of a high-frequency wiring board using a porcelain obtained by firing the composition of the present invention.

[Explanation of symbols]

Si SiO ₂ crystal phase SP Spinel crystal phase ML MAl ₂ Si ₂ O ₈ crystal phase (M: Ca, S
r, Ba) ZL Zn ₂ Al ₄ Si ₅ O 1 ₈ type crystal phase G amorphous phase A package for storing semiconductor element B external circuit board 1 insulating substrate 2 lid 3 cavity 4 chip component 5 wiring layer 6 connection electrode layer 7, 11 brazing material 8 ball-shaped terminal 9 insulating substrate 10 wiring conductor

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Minoru Yasuhide 1-4 Yamashita-cho, Kokubu-shi, Kagoshima Inside the Kyocera Research Institute (72) Inventor Yoshitake Terashi 1-4-4 Yamashita-cho, Kokubu-shi, Kagoshima F-term in Kyocera Research Institute (reference) 4G030 AA07 AA08 AA09 AA10 AA32 AA35 AA36 AA37 BA09 BA12 BA21 CA01 CA05

Claims (9)

[Claims] A glass containing 30 to 95% by weight of SiO ₂ , Al ₂ O ₃ , MgO, ZnO and B ₂ O ₃ , and Ca,
At least one kind (M) selected from the group consisting of Sr and Ba
And 0.1 to 35% by weight of a composite oxide containing Al and Si. 2. The method according to claim 1, wherein at least one of SiO ₂ , ZnO and B ₂ O _{3 comprises} 0 to 40% by weight of SiO ₂ ,
30 wt%, B ₂ O ₃ according to claim 1 porcelain composition, wherein the in a proportion of 0-10 wt%. 3. The glass has a ratio of 40 to 52% by weight of SiO ₂ , 14 to 32% by weight of Al ₂ O _{3, 4 to} 24% by weight of MgO, 1 to 16% by weight of ZnO and 5 to 15% by weight of B ₂ O _3. The porcelain composition according to claim 1, comprising: 4. The composite oxide containing at least one (M) selected from the group consisting of Ca, Sr and Ba and Al and Si is MAl ₂ Si ₂ O _8. A porcelain composition as described. 5. The method according to claim 1, wherein Si, Al, Zn, Mg and B are combined with C
a, Sr and Ba, at least one selected from the group consisting of metal elements and SiO ₂ as a crystal phase.
A crystal phase, a spinel crystal phase containing at least Zn and Al, a composite oxide crystal phase containing at least Zn, Al and Si, and at least one (M) selected from the group consisting of Ca, Sr and Ba and Al and A porcelain containing a composite oxide crystal phase with Si and having a thermal expansion coefficient of 5.5 ppm / ° C. or more and a dielectric constant of 9 or less from room temperature to 400 ° C. 6. The porcelain according to claim 5, wherein said SiO ₂ crystal phase is a quartz type crystal phase. 7. The porcelain according to claim 5, wherein the composite oxide crystal phase containing at least Zn, Al and Si is a Zn ₂ Al ₄ Si ₅ O ₁₈ type crystal phase. 8. The composite oxide crystal phase of at least one (M) selected from the group consisting of Ca, Sr and Ba and Al and Si is a MAl ₂ Si ₂ O ₈ type crystal phase. The porcelain according to claim 5, wherein 9. A wiring board comprising an insulating substrate and a wiring layer disposed on the surface and / or inside thereof.
The insulating substrate, Si, Al, Zn, Mg and B,
At least one selected from the group consisting of Ca, Sr and Ba is contained as a metal element, and SiO _{2 is used} as a crystal phase.
A crystal phase, a spinel crystal phase containing at least Zn and Al, a composite oxide crystal phase containing at least Zn, Al and Si, and at least one (M) selected from the group consisting of Ca, Sr and Ba and Al and A wiring substrate comprising: a porcelain having a composite oxide crystal phase containing Si and a thermal expansion coefficient from room temperature to 400 ° C. of 5.5 ppm / ° C. or more and a dielectric constant of 9 or less.