JP2002362937A - Glass composition, glass sintered compact and wiring board obtained by using the sintered compact - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wiring board which can be burned at <=1,000 deg.C, and in which a wiring layer containing low resistance metal can simultaneously be formed by burning, and which has a thermal expansion coefficient suitable for the packaging of GaAs chips, and a low Young's modulus, and ensures the long term reliability of connecting pats can. SOLUTION: In the wiring board provided with a wiring layer 2 containing low resistance metal provided on the surface and/or the inside of an insulation board 1, as the insulation board 1, a glass sintered compact is used which is obtained by molding glass powder containing, by weight, 10 to 40% SiO2 , 1 to 30% Al2 O3 , 10 to 40% BaO, 1 to 20% Y2 O3 , 0 to 30% B2 O3 , 0 to 25% ZnO, 0 to 20% of at least one kind selected from the group consisting of MgO, CaO and SrO, and 0 to 10% of at least one kind selected from the group consisting of ZrO2 , SnO2 and TiO2 , and >=90% the total content of the above components, and thereafter performing burning thereto at <=1,000 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass composition and a glass sintered body which are most suitable for a wiring board or the like applied to a package for housing a semiconductor element, a multilayer wiring board, and the like. More particularly, the present invention relates to a wiring board most suitable for mounting a GaAs chip.

[0002]

2. Description of the Related Art In recent years, with the era of advanced information technology, information communication technology has been rapidly developed, and accordingly, the speed and size of semiconductor elements have been increased, and signal transmission loss has been reduced even in a wiring layer. Above, a reduction in the resistance of the wiring layer is required.

Hitherto, the mainstream wiring substrate has an insulating substrate formed of, for example, alumina ceramics, and a surface of the insulating substrate and / or a metallized wiring layer co-fired on the surface.

Here, since the firing temperature of alumina ceramics is as high as about 1600 ° C., high melting point metals such as W and Mo have been used as metallized wiring layers formed inside an insulating substrate.

[0005] However, the alumina ceramics constituting the conventional insulating substrate as described above has a high dielectric constant,
The signal delay time becomes long and the signal cannot be propagated at high speed. Further, since the high melting point metal constituting the metallized wiring layer has a high electric resistance, a signal cannot be similarly propagated at high speed.

Therefore, the dielectric constant is low and the firing temperature is 10
A glass ceramic that can be fired at a low temperature of 00 ° C. or less is used as an insulating substrate, and Cu, Ag, and Au having low electric resistance are used as conductors.
It has been proposed to use such as.

For example, as disclosed in Japanese Patent Application Laid-Open No. Sho 60-240135, there has been proposed a glass obtained by adding a filler such as alumina, zirconia, or mullite to a zinc borosilicate glass and co-firing it with a low-resistance metal. . Others
JP-A-5-298919 also proposes a glass ceramic material in which mullite or cordierite is precipitated as a crystal phase.

Further, when a semiconductor chip is mounted on a wiring board (primary mounting), and when the wiring board is mounted on a printed board made of an organic resin such as a motherboard (secondary mounting), power is turned on and off. A rise in temperature that occurs at times,
Due to the thermal stress generated by the difference in thermal expansion with the lowering,
In order to prevent the mounting portion from peeling or cracking, it is desirable that the thermal expansion coefficient of the insulating substrate be similar to that of a semiconductor element or a printed circuit board.

On the other hand, in a semiconductor device, a conventional Si
Instead of chips, devices using GaAs chips having more excellent high-frequency characteristics are increasing.

[0010] In particular, a GaAs chip is brittle and susceptible to breakage as compared with a Si chip, and is inferior in moisture resistance and the like.
As a requirement for the wiring substrate, it is required that the thermal expansion coefficient of the insulating substrate is close and that the hermetic sealing be possible. When the thermal expansion coefficient of the wiring substrate is large, compressive stress acts on the chip, and the GaAs chip is relatively unlikely to break. Therefore, the thermal expansion coefficient of the wiring substrate is substantially equal to that of the GaAs chip. Slightly higher is required.

Further, in order to reduce the thermal stress of the mounting portion, it is required that the insulating substrate has a small Young's modulus.

[0012]

However, the above-mentioned conventional glass ceramic can be co-fired with a low-resistance metal such as gold, silver or copper, but has a thermal expansion coefficient of 3-5.
ppm / ° C, GaAs chip (Coefficient of thermal expansion: 6 ~
(7.5 ppm / ° C.) or when a wiring board was mounted on a printed circuit board, the long-term reliability of the mounting portion was low and was not practically satisfactory.

Furthermore, in the conventional glass ceramic, since alumina or mullite having a high Young's modulus is used as a filler, the Young's modulus often exceeds 100 GPa, and the thermal stress in the mounting portion is not sufficiently relaxed. This was a factor that reduced the long-term reliability of the department.

When an insulating substrate is made of a material containing an organic resin typified by a printed circuit board, the insulating substrate itself can be made to have the low-resistance wiring, the coefficient of thermal expansion and the Young's modulus within the above ranges. Hermetic sealing was not possible due to its hygroscopicity.

Therefore, according to the present invention, it is possible to co-fire with a low-resistance metal such as silver, copper, or gold, and to have a thermal expansion coefficient of GaAs.
Provided are a glass composition and a glass sintered body which are close to a chip, have a low Young's modulus, improve the long-term reliability of a mounting portion, and can be hermetically sealed, and provide a wiring substrate using the sintered body as an insulating substrate. With the goal.

[0016]

The glass composition of the present invention contains 10 to 40% by weight of SiO ₂ and 1 to 30% of Al ₂ O ₃ .
Wt%, a BaO 10 to 40 wt%, a Y ₂ O ₃ 1 to 20
Wt%, the B ₂ O ₃ 0 to 30 wt%, ZnO 0 to 25 wt%, MgO, at least one 0-20% by weight selected from the group consisting of CaO and SrO, ZrO _2, of SnO ₂ and TiO ₂ 0-10 at least one selected from the group
% By weight and the total amount of the above components is 90%.
It is a major feature that the amount is not less than% by weight.
According to the present invention, the glass powder made of the above composition is molded and then fired at 1000 ° C. or less to reduce the open porosity of the sintered body to 1.0% or less, and further has a thermal expansion coefficient close to that of a GaAs chip. And a low Young's modulus can be achieved at the same time.

Here, Pb is contained in the glass composition.
It is desirable that the contents of O and As ₂ O ₃ be 1% by weight or less, respectively, and that the content of R ₂ O (R: alkali metal) be 1% by weight or less.

Further, the glass composition has a glass transition point of 550 ° C. or higher, is a surface crystallized glass, and a glass powder having an average particle diameter of 100 μm or less is heated to an arbitrary temperature of not less than the glass transition point and not more than 1000 ° C. It is desirable to precipitate at least a BaAl ₂ Si ₂ O ₈ crystal phase when heat treatment is performed.

Further, the glass sintered body of the present invention is made of SiO ₂
10 to 40 wt%, Al ₂ O ₃ 1-30 weight%, Ba
O 10 to 40 wt%, a Y ₂ O ₃ 1 to 20 wt%, B ₂
O ₃ 0 to 30 wt%, 0-25 wt% of ZnO, Mg
0 to 20% by weight of at least one selected from the group consisting of O, CaO and SrO, ZrO ₂ , SnO ₂ and TiO ₂
A glass powder containing at least one member selected from the group consisting of 0 to 10% by weight and having a total amount of the above components of 90% by weight or more is molded and fired at 1000 ° C or less. This is a major feature.

Here, the glass sintered body is made of PbO, A
It is desirable that the content of s ₂ O ₃ be 1% by weight or less, and that the content of R ₂ O (R: alkali metal) be 1% by weight or less.

Further, the glass sintered body desirably contains at least a BaAl ₂ Si ₂ O ₈ crystal phase as a crystal phase, and has an open porosity of 1.0% or less and a temperature of 40 to 400 ° C.
Thermal expansion coefficient in the temperature range of 6.0 to 9.0 ppm
/ ° C. and a Young's modulus of 100 GPa or less.

The wiring board according to the present invention comprises a wiring layer containing a low-resistance metal disposed on the surface and / or inside of the insulating substrate. It is characterized by being made of a sintered body. The low-resistance metal is desirably one of gold, silver, and copper.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The glass composition of the present invention comprises SiO 2
₂ 10 to 40 wt%, the Al ₂ O ₃ 1 to 30 wt%, B
The aO-10 to 40 wt%, a Y ₂ O ₃ 1 to 20 wt%, B
₂ O ₃ 0 to 30 wt%, 0-25 wt% of ZnO, Mg
0 to 20% by weight of at least one selected from the group consisting of O, CaO and SrO, ZrO ₂ , SnO ₂ and TiO ₂
Characterized in that at least one selected from the group consisting of 0 to 10% by weight is contained, and the total amount of the above components is 90% by weight or more, particularly 93% by weight or more, and optimally 95% by weight or more. It is to be.

Further, the glass sintered body of the present invention is obtained by molding a glass powder comprising the above glass composition,
It is obtained by firing below.

The reason that the content of each component in the glass composition and the glass sintered body to be used is limited to the above range is that SiO ₂ , Al ₂ O ₃ , and BaO, which are essential components, contain BaAl ₂ Si in the sintered body. Necessary for precipitating a ₂ O ₈ crystal phase and for enhancing the properties of the glass sintered body,
If the ratio is outside the above range, the open porosity of the glass sintered body cannot be reduced to 1.0% or less, and the coefficient of thermal expansion thereof also deviates from the desired range.

Further, when the content of SiO ₂ and Al ₂ O ₃ among the above components is less than the above ranges, the glass transition point is lowered and the binder removal property at the time of firing is deteriorated,
Conversely, if the amount exceeds the above range, the open porosity of the sintered body tends to increase when firing at 1000 ° C. or lower. Also, B
When the content of aO is smaller than the above range, the open porosity of the glass sintered body is increased to 1.0% by firing at 1000 ° C. or lower.
On the other hand, if it is too large, the softening point of the glass decreases, the binder removal property during firing deteriorates, and the open porosity tends to increase.

A more desirable range of the above-mentioned SiO ₂ , Al ₂ O ₃ and BaO is that SiO ₂ is in particular 13 to 35% by weight,
Ideal for 15-30 wt%, Al ₂ O ₃ is particularly 3 to 25
%, Optimally between 5 and 20% by weight, BaO is in particular 15%
３７37% by weight, optimally 20-35% by weight.

Also, another essential component, Y ₂ O ₃
Acts to raise the softening point of the glass and keep the glass transition point within the range described below, and at the same time, increases the amount of the BaAl ₂ Si ₂ O ₈ crystal phase precipitated as a crystallization agent, This makes it possible to control the amount of BaAl ₂ Si ₂ O ₈ crystal phase precipitated. Further, Y ₂ O ₃ is a component for improving the Young's modulus of the glass, and it is possible to control the Young's modulus of the glass sintered body described later in a desired range according to the content, thereby improving the bending strength. I can do it.

Therefore, if the content of Y ₂ O ₃ is less than the above range, the amount of the BaAl ₂ Si ₂ O ₈ crystal phase precipitated becomes insufficient. At the same time when the porosity exceeds 100 GPa, the glass transition point is improved, and the open porosity increases by firing at 1000 ° C. or lower, and exceeds 1.0%. The more preferable range of Y ₂ O _3, in particular 2 to 18%, optimally from 3 to 15
% By weight.

Further, MgO, CaO and SrO contained as optional components in the glass composition and the glass sintered body
At least one member selected from the group consisting of B ₂ O ₃ and ZnO is
It is possible to control the softening behavior of the glass and to set the firing conditions in a desirable range,
Other crystals such as l ₂ Si ₂ O ₈ crystal phase, SrAl ₂ Si ₂ O ₈ crystal phase or solid solution thereof, particularly needle-like crystals, and further ZnAl ₂ O ₄ crystal phase, MgAl ₂ O ₄ crystal phase or solid solution thereof, etc. The phase can be precipitated from the glass, and there is an effect that the coefficient of thermal expansion, bending strength, Young's modulus, dielectric properties, and the like of the glass sintered body can be controlled. However, Mg
If the amount of at least one selected from the group consisting of O, CaO and SrO, B ₂ O ₃ , and ZnO is larger than the range of each content, the glass transition point is lowered, and the binder removal property during firing is deteriorated. And / or the open porosity increases.

The desirable range of the B ₂ O ₃ is, in particular, 0 to 20% by weight, optimally 0 to 14.5% by weight,
The desirable range of nO is particularly 0 to 20% by weight, optimally 0 to 15% by weight, and at least one desirable range selected from the group of MgO, CaO and SrO is particularly 0%.
-18% by weight, optimally 0-15% by weight.

Further, ZrO ₂ , SnO ₂ and TiO ₂
At least one selected from the group has an effect of promoting the precipitation of the above-mentioned specific crystal phase. However, when the content is more than 10% by weight, the open porosity of the sintered body becomes large, and 1.0%
Will be exceeded. At least one desirable range selected from the group of ZrO ₂ , SnO ₂ and TiO ₂ is 0 to 8
%, Optimally between 0 and 6% by weight.

In the present invention, the glass composition and the glass sintered body are characterized in that the total amount of the above components is 90% by weight or more. In other words,
In producing glass, a fining agent, an antifoaming agent, or a coloring agent can be contained in the glass composition within a range not exceeding 10% by weight. However, if the total amount of the above components is less than 90% by weight, it is difficult to make the properties of the glass sintered body within a desirable range. A desirable range for the total amount of the above components is 93% by weight or more, optimally 95% by weight or more. The fining agent, defoaming agent or coloring agent is not limited to these, but may be, for example, S
b ₂ O ₃ , Nd ₂ O ₃ , NiO, CoO, Cr ₂ O ₃ , Mn
At least one selected from the group consisting of O and La ₂ O ₃ is exemplified.

In the present invention, the content of PbO and As ₂ O ₃ widely used in conventional glasses is 1% by weight in the glass composition and the sintered glass in view of environmental resistance. It is desirable that the value be
It is desirable that these components are not substantially contained except for the amount by weight or less, and further, except for inevitable impurities.

Further, in the present invention, R ₂ O (R: alkali metal of Li, Na, K, Rb) in the glass composition and the glass sintered body in terms of chemical resistance, hygroscopicity and the like.
Is preferably not more than 1% by weight, particularly not more than 0.1% by weight, and further substantially free of these components except for inevitable impurities.

In the glass composition of the present invention,
It is desirable that the glass transition point is 550 ° C. or higher. When the glass transition point is lower than 550 ° C., the binder removal property is deteriorated, carbon remains in the sintered body, and the properties of the glass sintered body are deteriorated. Since the resistance metal cannot be sufficiently sintered and the specific resistance increases, the advantage of using a low resistance metal is lost. A desirable range of the glass transition point is, in particular, 580 ° C. or higher, and more preferably 600 ° C. or higher.

Further, in the glass composition of the present invention,
Desirably, the glass composition is a surface crystallized glass. Here, the surface-crystallized glass means that crystallization does not proceed from the bulk glass by uniform nucleation but proceeds from the surface or the interface due to heterogeneous nucleation.

Thus, in the above glass composition,
Since the crystallization proceeds by heterogeneous nucleation, the crystallization behavior of the glass can be controlled by the particle size of the glass powder and the like, and an arbitrary degree of crystallinity can be obtained in a glass sintered body described later. Therefore, it becomes easy to obtain desired characteristics.

Further, in the glass composition of the present invention, when a glass powder having an average particle size of 100 μm or less is subjected to a heat treatment at an arbitrary temperature between the glass transition point and 1000 ° C.,
It is desirable to precipitate at least a BaAl ₂ Si ₂ O ₈ crystal phase. In the present invention, it is desirable that the Young's modulus of the glass sintered body is low, but the BaAl ₂ Si ₂ O ₈ crystal phase can be precipitated as needle-like crystals from the glass, and the bending strength can be increased. It can achieve both low Young's modulus and high strength. Furthermore, the thermal expansion coefficient can be controlled by the BaAl ₂ Si ₂ O ₈ crystal phase.

Further, in the present invention, the glass powder
BaAl_TwoSi_TwoO₈Crystal phase other than crystal phase precipitates
And may be present in the glass sintered body, and
At least one selected from the group of phases may precipitate.
Examples of other crystal phases include ZnAl_TwoO_Four, MgAl_TwoO_Four
And its solid solution, CaAl_TwoSi_TwoO₈, SrAl_TwoSi
_TwoO₈And its solid solution, SiO_Two, YAlO_Three, Y_FourAl_TwoO
₉, BaY_TwoO_Four, Ba_FourY _TwoO₇, BaSiO_Three, BaSi_Two
O_Five, Sr_TwoMgSi_TwoO₇, MgSiO_Three, Mg_TwoSi
O_Four, CaSiO_ThreeAnd the like.

In the production of the glass sintered body of the present invention, if the sintering temperature is higher than 1000 ° C., it exceeds the melting point of the low-resistance wiring described later, making it difficult to form a wiring layer by simultaneous sintering. The baking temperature is preferably 1000 ° C. or less, particularly 980 ° C. or less when copper is used for wiring, and is 900 ° C. or less, particularly 850 ° C. or less when gold and silver are used for the wiring layer.

Further, the glass sintered body of the present invention, wherein at least BaAl ₂ Si ₂ O ₈ crystal phase of glass is intended to be deposited, the thermal expansion coefficient by precipitation of the BaAl ₂ Si ₂ O ₈ crystal phase Can be controlled, but since it precipitates as needle-like crystals from the glass, the transverse rupture strength of the glass sintered body can be increased.

Further, in the glass sintered body of the present invention,
It is desirable that the open porosity is 1.0% or less. When the open porosity is smaller than 1.0%, the bending strength of the glass sintered body is reduced, and at the same time, when a chemical treatment such as plating is performed, the chemical solution may cause traps or the like in the open pores. . The desirable range of the open porosity is particularly preferably 0.5% or less.

Further, the glass sintered body of the present invention has a coefficient of thermal expansion in the temperature range of 40 to 400 ° C. of 6.0 to 9.0 ppm / ° C. and a Young's modulus of 10 to 10.
It is desirable that the pressure be 0 MPa or less. If the coefficient of thermal expansion deviates from the above range, in the wiring substrate using the glass sintered body described later as an insulating substrate, Ga
When the As chip is primarily mounted, the thermal stress caused by the difference in the thermal expansion coefficient increases, and the long-term reliability of the primary mounting part cannot be maintained. The preferable range of the thermal expansion coefficient of the glass sintered body is, in particular, 6.5 to 8.5 ppm.
/ ° C.

On the other hand, when the Young's modulus exceeds 100 GPa, when the GaAs chip is first mounted on the wiring substrate, the thermal stress caused by the difference in the thermal expansion coefficient cannot be reduced by the insulating substrate. Therefore, the long-term reliability of the primary mounting part cannot be maintained. Further, even when the above-mentioned wiring board is secondarily mounted on a printed board, thermal stress caused by a difference in thermal expansion coefficient between the printed board and the above-mentioned wiring board can be reduced at the same time, so that the long-term reliability of the secondary mounting portion is improved. Can be kept at the same time. It is particularly desirable that the glass sintered body has a Young's modulus of 90 GPa or less.

According to the present invention, it is possible to form a wiring substrate having the above-described sintered glass as an insulating substrate and a wiring layer formed on the surface thereof. A description will be given based on FIG. 1 which is a schematic sectional view of a semiconductor element housing package A housing and mounting a semiconductor element which is a preferred example of the wiring board.

According to FIG. 1, a wiring layer 2 is formed on the surface and / or inside of an insulating substrate 1 composed of 1a to 1e. Further, according to FIG. 1, a via-hole conductor 3 for electrically connecting the wiring layer 2 formed between the insulating layers 1a to 1e is formed.

Further, a plurality of connection electrodes 4 are arranged on the lower surface of the package A, a cavity 7 is formed in the center of the upper surface of the package A, and an element 5 such as a semiconductor element is made of glass, brazing material or the like. The element 5 is electrically connected to the wiring layer 2 containing a low-resistance metal via a wire bonding 6 or the like. Further, the element 5 and the plurality of connection electrodes 4 formed on the lower surface of the insulating substrate 1 are electrically connected via the wiring layer 2 and the via-hole conductor 3.

Further, on the upper surface of the package A, a lid 8 made of metal, ceramic, glass or the like is adhered to the upper part of the cavity 7 with glass, brazing material or the like (not shown), so that airtight sealing is achieved. It has been done.

At this time, it is desirable to use a material having a coefficient of thermal expansion close to that of the glass sintered body of the present invention as the material of the lid 8 in order to ensure long-term reliability of hermetic sealing. For example, Fe— having a thermal expansion coefficient of about 7 × 10 ⁻⁶ / ° C.
Ni alloys are mentioned.

Further, the package A is a printed circuit board B
The connection electrodes 4 and 9 are placed on top of each other and bonded by a brazing material represented by solder, a conductive adhesive or the like (not shown). The layer (not shown) and the element 5 are electrically connected.

According to the present invention, the above-described glass sintered body is used as the insulating substrate 1 in a wiring substrate such as a package for housing a semiconductor element, whereby the open porosity of the insulating substrate 1 and the heat The expansion coefficient and the Young's modulus can be within desired ranges, the long-term reliability of the primary mounting and the secondary mounting of the package A can be simultaneously improved, and hermetic sealing can be performed.

Further, in the wiring board of the present invention, it is preferable that the low-resistance metal is one of gold, silver, and copper. Here, since the wiring layer 2 contains a low-resistance metal of gold, silver, or copper, particularly as a main component,
The resistance of the wiring layer 2 can be reduced, and in particular, the signal delay of a high-frequency signal can be reduced.

Although only one element 5 is shown in FIG. 1, a multi-chip module in which a plurality of chips are mounted may be used. Although the element 5 is connected to the wiring layer 2 via the wire bonding 6, the present invention is not limited to this.
May be directly connected to the wiring layer 2 formed or exposed on the surface of the insulating substrate 1 by soldering or the like.

Further, the element 5 may be sealed using a sealing resin without using the lid 8.
However, when a sealing resin is used, it is difficult to completely block ingress of moisture and the like, so that a sealing structure using the lid 8 is preferable.

The package A for housing the semiconductor element
In order to manufacture the wiring board of the present invention as described above, an appropriate organic binder, a dispersant, and a solvent are added to the above-mentioned glass powder and mixed to prepare a slurry. It is formed into a sheet by a calender roll method, a rolling method, or a press forming method.

After a through hole is formed in the sheet-like molded product as required, a conductive paste containing a low-resistance metal is filled in the through hole. Then, an evaluation pattern is printed and applied on the surface of the sheet-shaped molded body using a metal paste by using a known printing method such as a screen printing method or a gravure printing method so that the thickness of the wiring layer is 5 to 30 μm. Alternatively, a metal foil is pasted and processed into a pattern, or a pattern processed is pasted.

Then, after a plurality of sheet-shaped molded bodies are aligned and laminated and pressed, a binder is removed in an oxidizing atmosphere or a low-oxidizing atmosphere, and then an oxidizing atmosphere of 1000 ° C. or less or a non-oxidizing atmosphere is used. By firing in a neutral atmosphere, a wiring substrate can be manufactured.

The firing atmosphere is appropriately determined according to the type of the low-resistance metal used. For example, when a metal such as copper which is oxidized by firing in an oxidizing atmosphere is used, the firing atmosphere may be a non-oxidizing atmosphere. Need to be fired,
For gold and silver, baking in an oxidizing atmosphere is also possible.

An element such as a semiconductor element is mounted on the surface of the wiring board, and connected to the wiring layer so that signals can be transmitted. Connection methods include mounting directly on the wiring layer for connection, wire bonding,
A flip chip is suitable.

Further, the semiconductor element 5 can be hermetically sealed by bonding the lid 8 to the insulating substrate 2 using glass, brazing material, or the like, thereby producing a semiconductor element housing package. be able to.

[0062]

EXAMPLES (Example 1) A glass powder having the composition shown in Table 1 and having an average particle size of 2 µm was prepared. In addition, the content of PbO and As ₂ O ₃ in each glass powder was 1 in total.
The content of R ₂ O (R: alkali metal) is 100 ppm or less in total.

Then, an organic binder is added to this glass powder.
A plasticizer and toluene were added to prepare a slurry, and then the slurry was used to have a thickness of 30 by a doctor blade method.
A 0 μm green sheet was produced. Further, a plurality of the green sheets are laminated so as to have a desired thickness.
Thermocompression bonding was performed at a temperature of 0 ° C. by applying a pressure of 10 MPa.

The obtained laminate was subjected to a binder removal treatment at 500 ° C. in the air, heated at a rate of 200 ° C./hour, and fired in the air under the conditions shown in Table 1 to obtain a glass sintered body. .

The obtained sintered body was subjected to differential thermal analysis measurement to determine the glass transition point. The open porosity was measured by the Archimedes method. The Young's modulus was measured by the ultrasonic pulse method. Further, a thermal expansion curve at 40 ° C. to 400 ° C. was measured, and a thermal expansion coefficient was measured. Further, the crystal phase in the sintered body was identified by X-ray diffraction measurement, and is shown in Table 1 in descending order of peak intensity.

Example 2 The above green sheet was prepared for each glass powder shown in Table 1, a via hole was formed at a predetermined position, and a conductive paste containing silver as a main component was filled, followed by screen printing. A wiring layer was formed on the surface of the green sheet using the conductor paste by the method. further,
Five of these green sheets are laminated, and at a temperature of 60 ° C., 10
The sample was thermocompressed by applying a pressure of MPa and cut into 15 mm square. In addition, about the sheet of the uppermost layer, 10 mm square hole processing was performed and it was set as the cavity.

The obtained laminate was subjected to a binder removal treatment at 500 ° C. in the air, heated at a rate of 200 ° C./hour, baked in the air under the conditions shown in Table 1, and subjected to a 15 mm square wiring board (semiconductor). An element storage package A) was prepared. The pitch of the connection electrodes was 1.27 mm, which was arranged in a matrix on the lower surface of the wiring board.

The specific resistance of the wiring layer of the obtained sample was measured.
4 μΩcm or less was accepted. Then, an Au-Sn paste is applied to the chip mounting portion of this wiring board, and four GaAs chips having a thermal expansion coefficient of 6.8 × 10 ⁻⁶ / ° C. and 3 mm □ are aligned and placed in a matrix. , 320
A heat treatment was performed at 10 ° C. for 10 minutes to mount the GaAs chip on the wiring board.

Further, Au is connected to the lid connecting portion on the upper surface of the wiring board.
-Applying Sn paste and having a coefficient of thermal expansion of 7.0 × 10 ^-6
A lid made of an Fe-Ni alloy at a temperature of / ° C was positioned and mounted, and heat treatment was again performed at 320 ° C for 10 minutes to produce an airtight sealing structure.

Subsequently, Pb is formed on the lower surface of the connection electrode.
A eutectic solder paste having a composition of 63-Sn 63% by weight was printed, and Pb37-S was similarly formed on the wiring conductor of the printed circuit board.
A eutectic solder paste having a composition of n63% by weight was printed. After the wiring board is positioned on the printed board and placed thereon, it is treated at 230 ° C. in a reflow furnace to melt the eutectic solder and adhere to the wiring conductor on the printed board, and The board was mounted on a printed board. The thermal expansion coefficient of the printed circuit board used here is 14 ppm / ° C.

Next, as a heat cycle test, these mounting structures were alternately arranged in a constant temperature bath controlled at −40 ° C. and 125 ° C. in the atmosphere, respectively, and both of them were placed in a thermostat.
A temperature cycle test was performed up to a maximum of 500 cycles, where one cycle was held for 5 minutes. And 50
The electric resistance between the wiring conductor of the printed circuit board B and the electrode of the wiring board 1 was measured for each cycle, and the number of cycles until the change in the electric resistance became 10% or more is shown in Table 1.

Further, as an airtight sealing test, the above 50
He pressurized the package after 4 cycles to 4 atm
After leaving in the gas for 2 hours, He adsorbed on the surface in the exhaust duct was removed, and the amount of He released from the inside of the cavity was measured using a He detector.
× 10 ^-8 atm / cc / sec. The following items were evaluated as acceptable (〇), and the rejects were evaluated as (X).

[0073]

[Table 1]

As is clear from the results shown in Table 1, based on the present invention, sample No. 1 using the specific glass composition of the present invention was used.
In Examples 1 to 11, the glass transition point was 550 ° C. or higher, the open porosity was 1.0% or less, and the thermal expansion coefficient was 6.0 to 9.0 p.
pm / ° C, Young's modulus is less than 100 GPa,
Even when the package in which the chip is mounted and hermetically sealed is further mounted on a printed circuit board, no change in resistance is observed even after 500 cycles of the temperature cycle test, and hermetic sealing is also maintained. The long-term reliability of the connection was ensured.

On the other hand, Sample No. using a glass composition which deviates from the range of the glass composition of the present invention. In the case of 12 to 15, the thermal expansion coefficient and the Young's modulus cannot be simultaneously within the predetermined range, and a resistance change is observed in 500 cycles or less in a temperature cycle test, and the long-term reliability of the connection cannot be maintained. Met.

[0076]

As described above in detail, the glass sintered body of the present invention has an open porosity of 1.000 when fired at 1000 ° C. or lower.
Since it can be reduced to 0% or less, the wiring layer can be formed using a conductive material mainly composed of a low-resistance metal such as gold, silver, and copper, and the thermal expansion coefficient and the low Young's coefficient suitable for mounting a GaAs chip can be reduced. Since the ratio characteristics are simultaneously satisfied, it is possible to obtain a wiring board excellent in long-term reliability of the connection portion.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view for explaining an example of a semiconductor element housing package using a wiring board of the present invention.

[Explanation of symbols]

 A Package for element storage B Printed circuit board 1 Insulating substrate 2 Wiring layer 3 Via hole conductor 4 Connection electrode 5 Semiconductor element 6 Wire bonding 7 Cavity 8 Lid 9 Connection electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 35/03 C04B 35/14 35/14 H01B 3/08 A H01B 3/08 H05K 1/03 610B H01L 23 / 12 3/46 H H05K 1/03 610 T 3/46 C04B 35/02 Z H01L 23/12 B F term (reference) 4G030 AA07 AA08 AA09 AA10 AA11 AA12 AA16 AA17 AA22 AA28 AA32 AA35 AA36 AA37 AA39 AA42 BA12 CA01 GA14 GA15 GA17 GA20 GA25 GA27 4G062 AA15 BB01 DA04 DA05 DB03 DB04 DC01 DC02 DC03 DC04 DD01 DE01 DE02 DE03 DE04 DF01 DF02 EA01 EA02 EB01 EB02 EC01 EC02 ED01 ED02 ED03 ED04 EE01 EE02 EF03 EF03 EF03 EF03 EF01 EF03 EF04 EF03 EF04 EF01 EF03 EF04 EF01 EF04 EF03 EF01 EF03 FC03 FD01 FE01 FE02 FE03 FF01 FG01 FH01 FJ03 FJ04 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ0 1 JJ03 JJ04 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM27 NN29 NN33 QQ17 5E346 AA02 AA12 AA15 AA22 AA32 AA51 BB01 CC16 CC32 CC38 CC39 DD02 DD13 DD34 EE21 EE24 EE29 GG06 AGC12H17 CB12 CB35 CB38 CB39 CB40 CB43 CD01 CD04 CD06 DA05

Claims (14)

[Claims] The present invention relates to the following: 1. SiO ₂ is 10 to 40% by weight, Al ₂ O ₃ is 1 to 30% by weight, BaO is 10 to 40% by weight, Y ₂ O ₃ is 1 to 20% by weight, and B ₂ O ₃ is 0%. ~ 30 wt%, ZnO is 0
-25% by weight, at least one selected from the group consisting of MgO, CaO and SrO in an amount of 0-20% by weight, ZrO ₂ , Sr
at least one was contained in an amount of 0 to 10 wt%, and the glass composition the total amount of said components is equal to or less than 90% by weight selected from the group of nO ₂ and TiO _2. 2. The glass composition according to claim 1, wherein the contents of PbO and As ₂ O ₃ are each 1% by weight or less. 3. The glass composition according to claim 1, wherein the content of R ₂ O (R: alkali metal) is 1% by weight or less. 4. The glass composition according to claim 1, wherein the glass transition point is 550 ° C. or higher. 5. The glass composition according to claim 1, which is a surface crystallized glass. 6. A glass powder having an average particle diameter of 100 μm or less is subjected to heat treatment at an arbitrary temperature not lower than the glass transition point and not higher than 1000 ° C. to precipitate at least BaAl ₂ Si ₂ O ₈ crystal phase. The glass composition according to any one of the above. 7. The SiO ₂ 10 to 40 wt%, the Al ₂ O ₃ 1 to 30 wt%, a BaO 10 to 40 wt%, a Y ₂ O ₃ 1 to 20% by weight, the B ₂ O ₃ 0 ~ 30 wt%, ZnO is 0
-25% by weight, at least one selected from the group consisting of MgO, CaO and SrO in an amount of 0-20% by weight, ZrO ₂ , Sr
After molding a glass powder containing at least one selected from the group consisting of nO ₂ and TiO ₂ at a ratio of 0 to 10% by weight and a total amount of the above components of 90% by weight or more, 100%
A glass sintered body obtained by firing at 0 ° C. or lower. 8. The glass sintered body according to claim 7, wherein the contents of PbO and As ₂ O ₃ are each 1% by weight or less. 9. The glass sintered body according to claim 7, wherein the content of R ₂ O (R: alkali metal) is 1% by weight or less. 10. The glass sintered body according to claim 7, which contains at least BaAl ₂ Si ₂ O ₈ crystal phase. 11. The glass sintered body according to claim 7, wherein the open porosity is 1.0% or less. 12. A thermal expansion coefficient in a temperature range of 40 to 400 ° C. is 6.0 to 9.0 ppm / ° C., and a Young's modulus is 100 GPa or less.
A glass sintered body according to any one of claims 11 to 11. 13. A wiring board comprising a wiring layer containing a low-resistance metal disposed on a surface and / or inside of an insulating substrate, wherein the insulating substrate is any one of claims 7 to 12. A wiring substrate comprising the glass sintered body according to any one of the preceding claims. 14. The wiring board according to claim 13, wherein said low-resistance metal is one of gold, silver and copper.