JP2003165766A - Glass ceramic and method for making the same and wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass ceramic for an insulating layer of a wiring board which can be sintered at 800 to 1,050°C, exhibit low dielectric loss in a high frequency area, has high strength and a good mounting reliability with chip parts of Si, GaAs or the like or a printed board. <P>SOLUTION: A ceramic having bending strength of 300 MPa or more which is the glass ceramic made by dispersing a ceramic powder with an average particle size of 3 μm or more within a matrix consisting of a glass and/or ceramic phase is characterized by that the average thermal expansion coefficient α1 of the above matrix at from a room temperature to 400°C is larger than the average thermal expansion coefficient α2 of the ceramic particle can be obtained, in particular by that the difference (α1-α2 between the thermal expansion coefficients of the above matrix and the ceramic particle is 0.5×10<SP>-6</SP>/°C or more, crystal phases such as a diopsite type crystal phase or others are present within the above matrix, and open porosity is 1% or less. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable as an insulating substrate for a wiring board such as a package for housing a semiconductor element or a multilayer wiring board, and is particularly capable of being co-fired with copper or silver. Easy adjustment of thermal expansion coefficient,
Further, the present invention relates to a glass ceramics capable of enhancing the strength of a porcelain, a method for manufacturing the same, and a wiring board using the glass ceramics as an insulating substrate.

[0002]

Conventionally, as a ceramic multilayer wiring board,
The most widely used one is one 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 sintered body.

Further, in recent years, with the era of advanced information technology, the frequency band to be used is shifting to higher frequencies. In such a high-frequency wiring board that requires transmission of high-frequency signals, in order to transmit high-frequency signals without loss, the resistance of the conductor forming the wiring layer is small, and the dielectric of the insulating substrate in the high-frequency region is high. Low loss is required.

However, conventional tungsten (W),
Refractory metals such as molybdenum (Mo) have a large conductor resistance, a slow signal propagation speed, and are difficult to propagate signals in a high frequency region of 1 GHz or more. Therefore, instead of metals such as W and Mo, copper is used. , It is necessary to use low resistance metals such as silver.

Since the metallized wiring layer made of such a low resistance metal has a low melting point and cannot be co-fired with alumina, recently, a so-called metal or a composite material of glass and ceramics, that is, a so-called composite material. Wiring boards using glass ceramics as insulating substrates are being developed.

However, since the conventional glass ceramics have low porcelain strength, their mechanical reliability is low, and
When this is used as an insulating substrate, there is a problem that tensile stress is applied to the wiring layer formed on the surface of the insulating substrate, the wiring layer is also peeled off together with the insulating substrate, and the metallization strength cannot be increased.

On the other hand, Japanese Laid-Open Patent Publication No. 10-120436,
In Japanese Patent Laid-Open No. 11-49531, 70 to 100% of glass powder capable of precipitating a diopside crystal phase is used.
A porcelain made by adding 0 to 30% of ceramic powder such as alumina or mullite, mixing and firing is proposed, which can reduce the dielectric loss in the microwave band and the porcelain strength is 2200 kg / cm.
It is disclosed that it can be increased up to ² .

[0008]

However, in Japanese Unexamined Patent Publication No. 10-120436 and Japanese Unexamined Patent Publication No. 11-49531, the porcelain strength is 2200 kg / cm ² or less at most, and porcelain is used from the viewpoint of increasing the metallization strength of the wiring layer. Further improvement in strength was required. Further, in a porcelain to which alumina or mullite is added as a filler, the dielectric constant and the dielectric loss in the high frequency band are high, and it has been required to reduce the dielectric constant and the dielectric loss.

Further, in the method in which cordierite is added as a filler to the glass powder capable of precipitating the diopside crystal phase, the porcelain density cannot be increased due to poor wettability between the two and open pores There has been a problem that the strength of the porcelain is reduced due to the increase in the rate.

Therefore, according to the present invention, silver and copper can be fired by firing at 800 to 1050 ° C., which can be multilayered as conductors constituting the wiring layer, and high bending strength glass ceramics, a method for producing the same, and An object is to provide a wiring board using the same.

[0011]

Means for Solving the Problems The inventors of the present invention have made earnest studies on the above problems, and as a result, 10 to 70% by mass of ceramic particles having an average particle size of 3 μm or more in a matrix composed of a glass and / or a crystalline phase. Glass ceramics dispersedly contained at a ratio of room temperature to 400 ° C., wherein the average thermal expansion coefficient α1 of the matrix is larger than the average thermal expansion coefficient α2 of the ceramic particles. Difference in expansion coefficient (α1-α2) is 0.5 × 1
It is characterized in that it is 0 ^-6 / ° C or higher.

Further, in order to enhance dielectric properties such as dielectric loss, it is desirable that the matrix is crystallized and that the crystal phase thereof contains a diopside type crystal phase.

In order to increase the strength, it is desirable that the ceramic particles have an average particle size of 3 μm or more, further, an open porosity of 1% or less and a bending strength of 300 MPa or more.

Further, according to the method for producing glass ceramics of the present invention, the temperature is from room temperature to 400 after heat treatment at the firing temperature.
The average particle diameter is 3 to 90% by mass of the glass powder having an average coefficient of thermal expansion of α1 at 30 ° C., and the thermal expansion coefficient α2 lower than the coefficient of thermal expansion α1 of the glass powder when heat-treated at the firing temperature is 3
It is characterized in that a ceramic powder having a particle diameter of μm or more is mixed with 10 to 70 mass% and a glass-ceramic mixed powder having a BET specific surface area of 3 m ² / g or less is molded and then fired at a temperature of 800 to 1050 ° C. It is a thing.

Further, the difference (α1-α2) in the coefficient of thermal expansion between the glass powder and the ceramic particles is 0.5 × 10 ^-6.
It is desirable that the temperature is not less than / ° C in order to increase the strength.

Further, in order to enhance dielectric properties such as dielectric loss, it is desirable that the glass be capable of precipitating a diopside type crystal phase, and in order to achieve high densification, the glass powder Softening point of 550-950 ℃
Is preferred.

The glass ceramics of the present invention is most suitable as an insulating substrate in a wiring substrate in which a metallized wiring layer containing Cu or Ag is provided on the surface and / or inside of the insulating substrate.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The glass-ceramic of the present invention is
A ceramic particle having an average particle size of 3 μm or more, particularly 3.2 μm or more is dispersed in a matrix composed of a glass and / or a crystalline phase, and the average thermal expansion coefficient α1 of the matrix at room temperature to 400 ° C. It is important for higher strength that the coefficient of thermal expansion is larger than the average thermal expansion coefficient α2 of the ceramic particles. In particular, the difference in coefficient of thermal expansion (α1−α2) between them is 0.5 × 10 ⁻⁶ / ° C. or more, especially 1 × 1.
It is preferably 0 ⁻⁶ / ° C. or higher, more preferably 2 × 10 ⁻⁶ / ° C. or higher.

As described above, by making the coefficient of thermal expansion of the matrix higher than that of the ceramic particles dispersed in the matrix, the tensile stress from the ceramic particles caused by the difference in thermal expansion can be eliminated and all the compressive stress can be obtained. The strength of the entire glass ceramics can be increased.

Further, in order to increase the strength of ceramics, the presence of a crystal phase in the matrix phase can enhance the strength of the matrix. In addition, in addition, in order to reduce the dielectric loss of ceramics at high frequencies and the transmission loss of the substrate, the crystal phase is diopside, MgAl ₂ O ₄ , ZnAl ₂ O ₄ , cordierite,
Mullite, enstatite, willemite, CaAl ₂
Si ₂ O ₈ , SrAl ₂ Si ₂ O ₈ , (Sr, Ca) Al ₂ S
At least one selected from the group consisting of i ₂ O ₈ , forsterite, celsian, hexacelsian, monticellite, melilite, and akermanite. In particular, it is most desirable to precipitate the diopside type crystal phase from the viewpoint of improving the strength. As the diopside type crystal phase, diopside of Ca (Mg, Al) (Si, Al) ₂ O ₆ or Ca ₂ MgSi ₂ O ₇ (ake) similar thereto is used.
rmanite), CaMgSiO ₄ (montice)
llite), Ca ₃ MgSi ₂ O ₈ (merwinit
e) and the like may be precipitated, and SrO may be solid-dissolved in the diopside type crystal phase.

Specifically, it is desirable that the coefficient of thermal expansion of these matrices is 7 × 10 ⁻⁶ / ° C. or higher and that of the ceramic particles is 6 × 10 ⁻⁶ / ° C. or higher.

Further, it is desirable that the open porosity of the glass ceramics is 1% or less, particularly 0.5% or less in order to further increase the strength and reduce the dielectric loss.

On the other hand, as the ceramic particles, alumina, mullite, forsterite, enstatite, diopside, cordierite, anorthite, slausonite, celsian, hexacelsian, spinel,
Garnite, silica, zirconia, titania, MgTi
O ₃ , (Mg, Zn) TiO ₃ , Mg ₂ TiO ₄ , Zn ₂ T
iO ₄ , CaTiO ₃ , SrTiO ₃ , Si ₃ N ₄ , SiC
And at least one selected from the group of AlN.

In particular, among the above, alumina, mullite, anorthite, slausonite, celsian, hexacelsian, spinel, garnite, zirconia, AlN,
At least one selected from the group of SiC, especially alumina is desirable.

The glass-ceramic of the present invention has a bending strength (three-point bending) of 300 M at room temperature due to the above constitution.
It is desirable that the pressure is Pa or higher, especially 350 MPa or higher.

According to the present invention, by using such a high-strength glass ceramics as an insulating substrate of a wiring board, cracks due to thermal stress generated when mounting electronic components such as semiconductor elements are prevented, and metallization strength is improved. And the mechanical reliability of the wiring board can be improved. Furthermore, it is possible to prevent the occurrence of cracks and peeling due to thermal stress between the two due to repeated temperature cycles during solder mounting and operation stoppage of semiconductor elements, and improve the electrical reliability of the wiring connecting the two. it can. (Manufacturing Method) Next, a method for manufacturing the glass ceramics of the present invention will be described.

First, as a starting material, the average coefficient of thermal expansion at room temperature to 400 ° C. after heat treatment at the firing temperature is α1.
30 to 90% by mass of glass powder, especially 40 to 70
Mass% and a thermal expansion coefficient α lower than the thermal expansion coefficient α1
10 to 70% by weight of ceramic powder with 2, especially 3
It mixes in the ratio of 0-60 mass%.

The ratio of the glass powder to the ceramic powder is limited as described above, because when the glass powder amount is less than 30 mass%, the glass powder cannot be densified at a temperature of 1050 ° C. or less and the glass amount is 90 mass%. This is because if it is more than%, the improvement in strength cannot be expected.

The ceramic powder preferably has an average particle size of 3 μm or more, and particularly 3.2 μm or more. The bending strength can be increased by using a powder having such a relatively large average particle size.

Further, it is also important that the BET specific surface area of the mixed powder of the above glass powder and ceramic powder is 3 m ² / g or less, particularly 2 m ² / g or less. This is B
This is because if the ET specific surface area is larger than 3 m ² / g or less, the sinterability deteriorates, the number of voids increases, and the strength tends to decrease.

Here, the glass powder has a glass softening point of 5 in order to improve the ease of removing the binder and the crystallinity.
50 to 950 ° C, especially 650 to 950 ° C, and further 700
It is desirable to be up to 950 ° C.

Then, using this mixed powder, a shaped body having a predetermined shape is prepared by a well-known molding method such as a doctor blade method, a calender roll method, a rolling method or a press molding method, and then the shaped body is heated to 500 to 750 ° C. It can be manufactured by performing a binder removal treatment in the above step and firing at 800 to 1050 ° C. in an oxidizing atmosphere or an inert atmosphere.

Here, the reason for limiting the firing temperature to the above range is that if the firing temperature is lower than 800 ° C., the porcelain cannot be densified and the crystallinity is low and the proportion of the glass phase in the porcelain is 5% by mass or less. This is because the dielectric loss in the high frequency region increases, and conversely, when the temperature exceeds 1050 ° C., simultaneous firing with a low resistance metal such as Cu or Ag cannot be performed.

In order to densify the porcelain by firing at 1050 ° C. or lower, the temperature rising rate during firing is 1050 ° C. /
It is desirable that the heating time is not more than hr, especially 500 ° C./hr or less, and the firing time is not less than 10 minutes, especially not less than 30 minutes. Further, in order to increase the crystallinity of the crystal phase in the porcelain, the temperature rise during firing Temperature rate of 1050 ° C / hr or less, especially 500 ° C / hr
It is desirable to set it to not more than hr.

The glass-ceramic produced by using the glass-ceramic composition of the present invention is preferably used as an insulating substrate of a wiring board. Such high-strength glass-ceramics, especially strength of 300 MPa or more, especially 3
By using glass ceramics having a pressure of 50 MPa or more, cracks due to thermal stress that accompanies the mounting of electronic components such as semiconductor elements can be prevented, and metallization strength can be increased.
In addition, the mechanical reliability of the wiring board can be improved. In addition, it is possible to prevent the occurrence of cracks and peeling due to thermal stress between the two due to repeated temperature cycles due to solder mounting or operation stoppage of the semiconductor element, and improve the electrical reliability of the wiring connecting the both. .

To prepare a wiring board using the glass-ceramic composition of the present invention, a slurry is prepared by mixing the mixed powder of the glass powder and the ceramic powder with a suitable organic solvent and solvent, and preparing a slurry. Is molded into a sheet by a conventionally known doctor blade method, calender roll method, rolling method, or press molding method. Then, after forming a through hole in this sheet-shaped molded body as desired, the through hole is filled with a conductor paste containing at least one of copper, gold, and silver. Then, on the surface of the sheet-shaped molded product, a high-frequency line pattern capable of transmitting a high-frequency signal is printed by using the conductor paste by a screen printing method, a gravure printing method, or a metal foil such as a copper foil is patterned. Then, a wiring pattern having a thickness of 5 to 30 μm is formed by a method such as bonding and pasting.

After that, a plurality of sheet-shaped compacts are aligned, laminated and pressure-bonded, and fired under the above-mentioned conditions in a non-oxidizing atmosphere such as nitrogen gas or a nitrogen-oxygen mixed gas to obtain a high-frequency wiring board. Can be made. Specifically, for example, when a conductor such as copper which may be oxidized by firing is used as the conductor, the binder removal treatment is performed in a weakly oxidizing atmosphere such as a steam-containing atmosphere, and firing is performed in nitrogen, nitrogen-hydrogen or nitrogen-non-oxidizing atmosphere. It is desirable to perform firing in a non-oxidizing atmosphere such as an active gas.

Then, a chip component such as a semiconductor element is appropriately mounted on the surface of the wiring board and is connected to the wiring layer so that signals can be transmitted. As a connection method, a chip component is directly mounted on a wiring layer for connection, or a chip component is made of a resin, a resin such as Ag-epoxy, Ag-glass, Au-Si or the like, an adhesive having a thickness of about 50 μm such as metal or ceramics. Sticking to the surface of the insulating substrate, wire bonding,
The wiring layer and the semiconductor element are connected by a TAB tape or the like. As the semiconductor element, it is effective for mounting a chip component such as Si-based or Ga-As-based.

Further, on the surface of the wiring substrate on which the semiconductor element is mounted, a cap made of an insulating material similar to that of the insulating substrate, another insulating material, a metal having a good heat dissipation property, or the like and having an electromagnetic wave shielding property is made of glass, They may be joined by an adhesive such as a resin or a brazing material, whereby the semiconductor element can be hermetically sealed.

A concrete structure of a package for accommodating a semiconductor element, which is an example of a high-frequency wiring board for which the glass ceramic composition of the present invention can be preferably used, and its mounting structure will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view of a package for accommodating semiconductor elements, particularly a ball grid array (BGA) type package in which connection terminals are ball-shaped terminals. According to FIG. 1, the package A has a cavity 3 formed by an insulating substrate 1 made of an insulating material and a lid body 2, and the chip component 4 such as Si or Ga-As is contained in the cavity 3. It is mounted with an adhesive or the like.

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 preferably made of a low resistance metal such as copper, silver or gold in order to reduce conductor loss as much as possible when transmitting a high frequency signal. Further, 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 is a well-known strip line, microstrip line, coplanar line, It is composed of at least one of the dielectric waveguide lines.

Further, in the package A of FIG. 1, a connection electrode layer 6 is deposited on the bottom surface of the insulating substrate 1 and connected to the wiring layer 5 in the package A. The ball-shaped terminals 8 are formed on the connecting electrode layer 6 by a brazing material 7 such as solder.

Further, the package A is connected to the external circuit board B.
To mount on, as shown in Figure 1, polyimide resin,
It is mounted via a brazing material on 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 epoxy resin or phenol resin. Specifically, the ball-shaped terminal 8 attached to the bottom surface of the insulating substrate 1 in the package A and the wiring conductor 10 of the external circuit board B are brought into contact with each other and brazed with solder 11 such as Pb-Sn. To be implemented. Alternatively, 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 in which a chip component 4 such as Ga-As is mounted by brazing or an adhesive, the chip component 4 such as Ga-As or the like is used.
Since the difference in thermal expansion from the insulating substrate 1 can be made smaller than that of the conventional ceramic material, it is possible to suppress the occurrence of stress in the mounting portion even when a thermal cycle is applied to the mounting structure. The long-term reliability of the mounting structure can be improved. The ball-shaped terminal 8 of FIG.
Column terminals instead of (land grid array (L
GA)) is also possible.

[0045]

Examples Glass composition A having the following composition: 50% by mass of SiO ₂ -5.5% by mass of Al ₂ O ₃
-MgO18.5 wt% -CaO26 wt% Glass B: SiO ₂ 50.2 wt% -Al ₂ O ₃ 5.0 wt% -MgO16.1 wt% -CaO15.1 wt% -
SrO13.6 wt% Glass C: SiO ₂ 10.4 wt% -Al ₂ O ₃ 2.5 wt% -ZnO35.2 wt% -B ₂ O ₃ 45.3% by mass -
Crystallized glass (A, B) in which a diopside crystal phase composed of Li ₂ O 6.6 mass% was deposited and non-crystallized glass C were prepared.

Then, the ceramic filler (purity 99%) shown in Table 1 was added to the above glass. The average thermal expansion coefficient α2 of the ceramic powder at room temperature (25 ° C) to 400 ° C was determined by TMA / TG-DTA and is shown in Table 1.

Further, an organic binder, a plasticizer, and toluene are added to this mixture to prepare a slurry, and the slurry is used to obtain a thickness of 300 μm by a doctor blade method.
m green sheet was produced. Then, 10 to 15 of these green sheets are laminated and 10MP at a temperature of 50 ° C.
The pressure of a was applied and thermocompression bonding was performed. The obtained laminate was subjected to binder removal treatment at 700 ° C. in a water vapor-containing / nitrogen atmosphere, and then fired in dry nitrogen under the conditions shown in Table 1 to obtain a porcelain for an insulating substrate. The temperature raising rate and the temperature lowering rate were 300 ° C./hr.

The dielectric constant and the dielectric loss of the obtained porcelain were evaluated by the following methods. Measurement is shape, diameter 2-7mm,
Cut out into a shape with a thickness of 1.5 to 2.5 mm, 60 GHz
The measurement was performed by a dielectric cylinder resonator method using a network analyzer and a synthesized sweeper. In the measurement, the NRD guide (non-radiative dielectric line) was used to excite the dielectric resonator, and the dielectric constant and dielectric loss (tan δ) were calculated from the resonance characteristics of the TE ₀₂₁ and TE ₀₃₁ modes.

The open porosity was measured by the Archimedes method. Further, the crystal phase in the sintered body was identified from the X-ray diffraction chart, the content ratio of each crystal phase was obtained by the Rietveld method, and the thermal expansion coefficient α1 of the matrix was calculated from the ratio of the precipitated crystal phase of the matrix phase. ,
The results are shown in Table 1. Further, the three-point bending bending strength of the glass ceramics was measured based on JIS-R1601.

Further, using the composition shown in Table 1, a green sheet having a thickness of 500 μm was prepared by a doctor blade method, and a Cu metallizing paste having a thickness of 10 μm was applied to the surface of the sheet by a screen printing method to form a metallized wiring layer. Formed. In addition, through holes were formed at predetermined locations on the green sheet, and Cu metallizing paste was also filled in the through holes. Then, six green sheets coated with the metallizing paste were laminated between the through holes and pressure-bonded. This laminated body was co-fired with the metallized wiring layer and the insulating substrate under the above-mentioned firing conditions to produce a wiring board having a metallized wiring layer formed on the surface.

The surface of the metallized wiring layer of 2 mm square on the surface of the obtained wiring board was plated with nickel and gold, and a copper lead wire was soldered on the plated film, and then the lead wire was perpendicular to the metallized wiring layer. The tensile load (F) at which the metallized wiring layer is peeled off or damaged by pulling at a speed of 10 mm / sec is measured, and F / S (MPa), which is the ratio to the formation area (S) of the metallized wiring layer, is calculated as the metallized strength. did. The results are shown in Table 1.

[0052]

[Table 1]

As is clear from the results of Table 1, the sample N in which the coefficient of thermal expansion α1 of the matrix and the coefficient of thermal expansion α2 of the ceramic particles dispersed are in the relationship of α1 <α2
o. Compared to 13, 14, 15, 23, 24, α1>
Sample No. of the present invention in which the ceramic particles were selected so as to have the relationship of α2. Nos. 3 to 12 and 16 to 22 all exhibit high strength, and in particular have an open porosity of 1% or less and a bending strength of 300.
It had excellent properties of at least MPa and a metallization strength of at least 30 MPa. Moreover, the sample No. with a filler amount of less than 10% by mass. In Nos. 1 and 2, the bending strength and the metallization strength were low.

[0054]

As described in detail above, according to the glass ceramics of the present invention, since it can be fired at a low temperature of 1050 ° C. or less, a wiring layer made of a low resistance metal such as copper can be formed, and a porcelain strength of 300 MPa or more, Metallization strength is 2
Since it is as high as 0 MPa or more, it is possible to provide a highly reliable wiring board having excellent thermal cycle resistance when Si and Ga-As chips are mounted.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view for explaining an example of a mounting structure of a semiconductor element housing package 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]

A Semiconductor element storage package B External circuit board 1 Insulation board 2 lid 3 cavities 4 chip parts 5 wiring layers 6 Connection electrode layer 7 brazing material 8 ball terminals 9 insulating substrate 10 wiring conductors 11 Solder

Claims (10)

[Claims] 1. A glass-ceramic comprising a glass and / or crystal phase matrix containing ceramic particles having an average particle size of 3 μm or more dispersed in an amount of 10 to 70% by mass, wherein the matrix has a room temperature. ~ 400
A glass-ceramic having an average coefficient of thermal expansion α1 at 0 ° C larger than an average coefficient of thermal expansion α2 of ceramic particles. 2. The glass-ceramic according to claim 1, wherein the difference (α1-α2) in the coefficient of thermal expansion between the matrix and the ceramic particles is 0.5 × 10 ⁻⁶ / ° C. or more. 3. The glass ceramic according to claim 1, wherein the crystal phase in the matrix contains a diopside type crystal phase. 4. The glass ceramic according to claim 1, which has an open porosity of 1% or less. 5. The glass-ceramic according to any one of claims 1 to 4, which has a bending strength of 300 MPa or more. 6. Room temperature to 400 ° C. after heat treatment at firing temperature
In the glass powder having an average thermal expansion coefficient of α1 in α1, a ceramic powder having a thermal expansion coefficient α2 lower than the thermal expansion coefficient α1 and an average particle size of 3 μm or more is mixed at a ratio of 10 to 70% by mass, BET specific surface area of 3 m ² / g
800-1 after molding the following glass-ceramic mixed powder
A method for producing glass ceramics, which comprises firing at a temperature of 050 ° C. 7. The difference (α1-α2) in the coefficient of thermal expansion between the glass powder and the ceramic powder is 0.5 × 10 ⁻⁶ /
7. The method for producing a glass-ceramic according to claim 6, wherein the temperature is not lower than ° C. 8. The method for producing a glass ceramic according to claim 6, wherein the glass precipitates a diopside type crystal phase by the firing. 9. The softening point of the glass powder is 550 to 950.
9. The method for producing a glass-ceramic according to claim 6, wherein the temperature is 0 ° C. 10. The surface and / or the inside of the insulating substrate,
The wiring board provided with a metallized wiring layer containing Cu or Ag, wherein the insulating substrate is the insulating board.
A wiring board comprising the glass-ceramic according to any one of 1.