JP2000327428A - Low temperature sintering glass ceramic and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain low temperature sintering glass ceramics capable of being fired at <=1,000 deg.C, capable of incorporating a low resistance conductor such as Au, Ag or Cu by simultaneous firing and suitable for the insulating layer of a multilevel interconnection board for mounting with a high-frequency analogue circuit having a low dielectric constant and a small dielectric loss in a frequency domain of microwaves and millimeter waves. SOLUTION: A glass having a composition consisting of 10-45 wt.% SiO2, 20-50 wt.% CaO, 20-45 wt.% Al2O3, 0.1-5 wt.% MgO, 0.1-5 wt.% SrO, 0.1-5 wt.% BaO, 0.1-5 wt.% TiO2, 0.1-5 wt.% ZnO, 0.1-5 wt.% ZrO2 and 0-3 wt.% oxide of a group IA element (expressed in terms of oxides) has a low softening point, can be fired at <=1,000 deg.C in the form of a composite with various ceramics, deposits crystals in a firing process and forms the objective glass ceramics having a low dielectric constant and a small dielectric loss, capable of multilevel interconnection with a low resistance conductor and giving a multilevel interconnection board excellent in high-frequency characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-temperature fired inorganic composition which can be fired simultaneously with low-resistance conductors such as Au, Ag, and Cu. The present invention relates to a low-temperature fired glass ceramic having a dielectric constant and a low dielectric loss and suitable as an insulating layer of a multilayer wiring board for microwave and millimeter wave circuits.

[0002]

2. Description of the Related Art A low-temperature fired glass-ceramic multilayer wiring board is capable of multi-layer wiring, high-density wiring, and miniaturization by fine wiring, and is capable of selecting a conductor having low resistance, such as Au, Ag, or Cu, as a wiring material. Since signal propagation can be accelerated by lowering the dielectric constant of the insulating layer, development has been promoted as an effective means for improving the performance of electronic devices. Furthermore, since the high-frequency analog circuit can be electromagnetically shielded by the cavity structure and the high-density arrangement of via holes, it is possible to reduce the size and performance of the module in which a plurality of MMICs are mounted. Development of communication equipment modules including high-frequency analog circuits has been carried out.

[0003]

In the field of communication equipment including high-frequency analog circuits, use of systems in the millimeter-wave band, which is not only the microwave region but also in the high-frequency region, has been expected. In a module equipped with an analog circuit in such an ultra-high frequency range, it is essential to suppress signal transmission loss. Therefore, a glass ceramic multilayer wiring board is required to further reduce the dielectric loss of the insulating layer material and to reduce the conductor loss. There is a demand for low resistance materials.

An object of the present invention is to enable firing at a temperature of 1000 ° C. or lower, that is, simultaneous firing of low-resistance conductors such as Au, Ag, and Cu for interiorization and multi-layering, and for frequencies in the microwave and millimeter wave regions. Another object of the present invention is to provide a low-temperature fired glass ceramic suitable for an insulating layer of a multilayer wiring board for mounting a high-frequency analog circuit having a low dielectric constant and a low dielectric loss.

[0005]

The present inventors have SUMMARY OF THE INVENTION As a result of in order to solve the above problems of the conventional low-temperature firing glass-ceramic was investigated of various glass compositions, SiO _2
-CaO-Al 2 _{O 3} based glass in certain composition range, a complex with various ceramics or by itself, 100
It has been found that sintering can be carried out at a firing temperature of 0 ° C. or less, and that the crystallization takes place during the firing process to show a low dielectric constant and a low dielectric loss.

That is, the gist of the present invention is as follows.
(1) 10 to 45% by weight of SiO _{2 in} terms of oxide;
CaO20~50 _{wt%, Al} 2 O 3 20 to 45 wt%, MgO0.1～5 wt%, SrO0.1～5 wt%, BaO0.1～5 _wt%, TiO 2 0.1 to 5% by weight, ZnO0.1~5 _wt%, a _SiO 2 _-CaO-Al 2 _{O 3} based glass having ZrO 2 0.1 to 5 wt%, and a composition comprising a group 1A element oxide 0-3% by weight, 800 low-temperature firing glass-ceramic, characterized in that the densification in the firing process of firing temperature to 1000 ° C., a composite ceramic particles are dispersed in _{(2) SiO 2 -CaO-Al} 2 O 3 based glass, The glass is 10 to 45% by weight of SiO _{2 in} terms of oxide, Ca
O _{20 to} 50% by weight, Al ₂ O ₃ 20 to 45% by weight, M
gO 0.1-5% by weight, SrO 0.1-5% by weight, Ba
O 0.1-5% by weight, TiO ₂ 0.1-5% by weight, Zn
O0.1~5 _wt%, ZrO 2 0.1 to 5 wt%, and which has a composition consisting of Group 1A element oxide 0-3% by weight, densification in the firing process of firing temperature 800 to 1000 ° C. (3) the group 1A element oxide is Na ₂ O,
The low-temperature fired glass ceramic according to the above item (1) or (2), wherein the ceramic is at least one selected from K ₂ O and Li ₂ O, (4) the ceramic in the composite The ratio of the particles is 10 to 5 by weight.
(5) the low-temperature fired glass ceramic according to the above (2) or (3), which is 0% by weight.
The ceramic particles are Al ₂ O ₃ (Alumina),
SiO ₂ (Silica), Mg ₂ Al ₄ Si ₅ O ₁₈ (Cord
ierite), Mg ₂ SiO ₄ (Forsterite) and Al ₆ S
The low-temperature fired glass ceramic according to any one of the above (2), (3) to (4), wherein the glass ceramic is at least one selected from i ₂ O ₁₃ (Mullite).
(6) CaAl ₂ SiO ₆ , C
a ₃ Si ₂ O ₇ (Rankinite), CaSiO ₃ (Wollast
onite) and Al ₆ Si ₂ O ₁₃ (Mullite)
The low-temperature fired glass ceramic according to any one of the above (1), (2), (3), (4) to (5), wherein one or more types of crystals are precipitated.
(7) (A) SiO ₂ —CaO—Al in weight percentage
A film forming step of producing a green sheet from a mixed powder composed of 50 to 100% by weight of ₂ O ₃ glass powder and 0 to 50% by weight of a ceramic powder; and (B) laminating the green sheets and hot pressing. (C) laminating the laminated body obtained through the laminating step to 800
A method of manufacturing a low-temperature firing glass-ceramic having a firing step of preparing a baked sintered body in a temperature range of ~1000 ℃, SiO ₂ 10 the glass is in the oxide equivalent
45 wt%, CaO20~50 _wt%, Al _{2 O} 3 ₂
0 to 45% by weight, 0.1 to 5% by weight of MgO, 0.
1 to 5% by weight, 0.1 to 5% by weight of BaO, TiO ₂ .
1 to 5% by weight, ZnO 0.1 to 5% by weight, ZrO ₂ 0.
1 to 5% by weight, and a method of manufacturing low-temperature firing glass-ceramics and having a composition consisting of Group 1A element oxide 0-3% by weight, (8) the Group 1A element oxides, _Na 2 O, and characterized in that K ₂ O, and one or more selected from Li ₂ O, (7) the method of manufacturing low-temperature firing glass-ceramic according to terms, (9) the ceramic _particles, Al 2 _{O 3} (Alumina), SiO
₂ (Silica), Mg ₂ Al ₄ Si ₅ O ₁₈ (Cordierit
e), Mg ₂ SiO ₄ (Forsterite), CaAl ₂ Si
O ₇ , Ca ₃ Si ₂ O ₇ (Rankinite), CaSiO ₃
(Wollastonite), and Al ₆ Si ₂ O ₁₃ (Mullit
e) one or more types selected from the group consisting of:
(7) The method for producing a low-temperature fired glass ceramic according to the above (7) or (8), (10) In the firing step, C is used.
aAl ₂ SiO ₆ , Ca ₃ Si ₂ O ₇ (Rankinite),
CaSiO ₃ (Wollastonite) and Al ₆ Si ₂ O
₁₃ (Mullite), wherein one or more kinds of crystals are precipitated, and the low-temperature fired glass ceramics according to any one of the above (7), (8) to (9) is characterized in that Manufacturing method.

According to the low-temperature fired glass ceramics of the present invention, it is possible to obtain a multilayer wiring board excellent in high frequency characteristics using a low-resistance conductor as a wiring material.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The low-temperature fired glass ceramic of the present invention has a SiO ₂ content of 10 to 45% by weight,
aO20~50 _{wt%, Al} 2 O 3 20 to 45 wt%,
MgO 0.1-5% by weight, SrO 0.1-5% by weight, B
aO 0.1 to 5% by weight, TiO ₂ 0.1 to 5% by weight, Z
nO0.1~5 _wt%, S having a composition consisting of ZrO 2 0.1 to 5 wt% and a Group 1A element oxide 0-3 wt%
iO _{2 -CaO-Al 2 O 3} based glass or is characterized by comprising a composite ceramic particles are dispersed in the glass. The SiO ₂ —CaO—Al ₂ O ₃ system glass having the composition is 800 alone or in a composite with ceramic particles.
It can be fired at a temperature of １０００1000 ° C., and Au,
It is possible to manufacture a multilayer wiring board using a low-melting-point low-resistance conductor such as Ag or Cu as an inner wiring material. Also,
The SiO ₂ —CaO—Al ₂ O ₃ system glass having this composition has both low dielectric constant and low dielectric loss characteristics, and is suitable for an insulating layer of a multilayer wiring board for mounting a high-frequency circuit.

Further, the composition will be described in detail. Glass having this composition can be fired at a temperature of 1000 ° C. or less in the above-mentioned composition range, and in particular, MgO, SrO, Ba
0.1~ _O, TiO _2, ZnO and ZrO _2, respectively
Addition of 5% by weight lowers the softening point, lowers the sinterable temperature range, and is suitable for low-temperature sintering. However, these large amounts impair the low dielectric loss, which is one characteristic of the low-temperature fired glass ceramics of the present invention, and increase the dielectric loss. Therefore, the amount of each of them must be 5% by weight or less. On the other hand, when the amount of addition is small, the temperature at which sintering can be performed increases, and sintering at 1000 ° C. or lower becomes difficult. Therefore, its addition needs to be 0.1% by weight or more. In particular, 0.5% by weight or more and 2% by weight
The following additions make it possible to set the sinterable temperature to around 900 ° C., which is preferable.

The addition of a Group 1A element oxide has a remarkable effect of lowering the softening point of glass, and is effective in lowering the firing temperature, but also greatly increases the dielectric loss. Therefore, the addition must be 3% by weight or less, and preferably 1% by weight or less.

When the glass having the above-mentioned composition is used as a composite with ceramic particles, the material strength can be enhanced and the dielectric constant, dielectric loss and thermal expansion coefficient can be changed by selecting the ceramic particles, which is useful. The ratio is desirably 50% by weight or less of the ceramic particles. If the ratio is higher than the above, firing at 1000 ° C. or lower becomes extremely difficult. Further, a blending ratio of 10% by weight or more and 30% by weight or less is preferable because it is effective for enhancing the material strength. The ceramic particles may be any of alumina, silica, mullite, cordierite, forsterite and the like, but those having a low dielectric constant and a low dielectric loss are preferable because they do not deteriorate the dielectric properties.

The glass having the above-mentioned composition is 800 to 100
In the firing process in a temperature range of 0 ° C., CaAl ₂ SiO
₆ , Ca ₃ Si ₂ O ₇ (Rankinite), CaSiO ₃ (W
ollastonite) or Al ₆ Si ₂ O ₁₃ (Mullite)
The crystals of are precipitated. The state of precipitation of these crystals differs depending on the glass composition and firing conditions, but it effectively acts to reduce dielectric loss and strengthen material strength.

When manufacturing a multilayer wiring board using the low-temperature fired glass ceramic of the present invention, a green sheet laminating method is effective. A glass powder of the above composition having an average particle diameter of about several microns to submicron and a plasticizer, a binder are added to a solvent serving as a dispersion medium, mixed to form a slurry, and this is formed into a green sheet by a slip casting film forming method or the like. I do. The particle size of the glass powder is related to the firing temperature, the shrinkage ratio before and after firing, the amount of various organic vehicles added during the above-mentioned slurry preparation, and the like.
About 3 μm is easy to handle. When the low-temperature fired glass ceramic of the present invention is used as a composite with ceramic particles, the ceramic particles to be added may have an average particle size of submicron to several microns, but like the above-mentioned glass powder, Particle size affects various factors. When the average particle size is about 0.5 to 2 μm, it is effective and preferable for the material strength. After forming via conductors, circuits, cavities, etc. on the green sheet, laminating these processed green sheets, performing heat pressing and integrating them,
By firing in a temperature range of 800 to 1000 ° C., a multilayer wiring board can be obtained. In the firing process, the glass having the above composition precipitates various crystals depending on firing conditions, glass composition, and the like. As a result, it is possible to further reduce the loss of the insulating layer and enhance the strength of the substrate, and it is possible to obtain a multilayer wiring board suitable for mounting a high-frequency circuit.

[0014]

EXAMPLES The present invention will be described in more detail below, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 A glass having a composition shown in Table 1 was produced, and wet pulverization was performed using alcohol as a dispersion medium. After filtering and drying the alcohol, the mixture was granulated to obtain glass powder A having an average particle size of 1 μm. Similarly, glass having the composition shown in Table 1 was produced and granulated, and glass powders B and C having an average particle diameter of 1 μm were produced.
I got After adding an organic binder, a plasticizer, and a solvent serving as a dispersion medium to these glass powders A, B, and C, respectively,
Knead well with ball mill, viscosity 3000 ~ 10000c
A ps slurry was made. As the organic vehicle such as an organic binder, a plasticizer, and a solvent, those commonly used are sufficient, and the components thereof are not particularly limited. Each of the obtained slurries was formed into a green sheet having a thickness of 100 μm by a slip casting method. Each of the produced green sheets is laminated and hot-pressed to form green sheet laminates A, B and C. The laminates A and B are fired at 900 ° C. and the laminate C is fired at 1000 ° C., and the fired bodies A, B and C was obtained. Here, the green sheet laminates A, B, and C and the fired bodies A, B, and C are glass powders A,
Corresponding to B and C. When the crystal phase of each fired body was identified by X-ray diffraction method, Rankinite, Wo
llastonite, CaAl ₂ SiO ₆ was identified. Similarly, Mullite and CaAl ₂ SiO ₆ are obtained from the fired body B,
From the fired body C, CaAl ₂ SiO ₆ was identified. The dielectric properties of each fired body were such that each fired body had a diameter of about 12 m.
The sample was processed into a cylindrical shape having a height of about 5 mm and a height of about 5 mm, and evaluated by measuring the dielectric constant and the dielectric loss tangent by a cavity resonator method. The dielectric constants of the fired bodies A, B, and C in the 10 GHz band were 6, 7, and 7, respectively, and the dielectric loss tangent was 0.001, respectively.

Example 2 A glass having the composition shown in Table 1 was produced, and a glass powder D having an average particle size of about 2 μm was obtained in the same process as in Example 1. Next, cordierite powder having an average particle diameter of 1 μm was weighed so that cordierite was 20% by weight and glass powder D was 80% by weight, and alcohol was used as a dispersion medium and mixed for 3 hours in a ball mill. The mixture was filtered and dried to obtain a homogeneous mixed powder D. Similarly, 80% by weight of glass powder E having the composition shown in Table 1 and an average particle size of 1 μm
To obtain a homogeneous mixed powder E composed of 20% by weight of an amorphous quartz powder. From these mixed powders D and E, green sheet laminates D and E were prepared in the same process as in Example 1, and baked at a firing temperature of 950 ° C., respectively.
I got When the dielectric properties were evaluated using the cavity resonator method, the dielectric constants of the fired bodies D and E in the 10 GHz band were 5.5 and 6, respectively, the dielectric loss tangent was 0.001, and the dielectric loss tangent was 0.001.
0.001, which was confirmed to be low dielectric constant and low dielectric loss.

Example 3 A glass having the composition shown in Table 1 was prepared, and a glass powder having an average particle size of about 1 μm was obtained in the same process as in Example 1. Next, the above-mentioned glass powder was weighed so that 70% by weight of alumina powder and 30% by weight of alumina powder having an average particle diameter of about 1 μm were mixed using ethanol as a dispersion medium in a ball mill for 3 hours, and then ethanol was filtered and dried. A homogeneous mixed powder was obtained. After adding an organic binder, a plasticizer, and a solvent serving as a dispersion medium to the obtained mixed powder, the mixture is sufficiently kneaded with a ball mill to obtain a slurry having a viscosity of about 5000 cps, and a green sheet having a thickness of about 100 μm is formed by a slip casting film forming method. did. After punching the produced green sheet into a predetermined shape, a via hole was formed at a predetermined position of each green sheet, and an Au paste was embedded in the via hole. Further, a wiring pattern was formed by printing an Au paste on each green sheet by a screen printing method. As the wiring conductor, in addition to the Au paste, a Cu paste, a CuO paste, an Ag paste, an Ag paste to which Pd or Pt is added as necessary, or the like is used. The green sheets thus produced were laminated and integrated by hot pressing to obtain a laminate. The laminate is placed in air at 900
It was fired at ℃ to obtain a multilayer wiring board. When the transmission characteristics were evaluated in the microstrip line portion of the obtained multilayer wiring board, the loss was 0.1 dB / mm at 30 GHz.
It was confirmed that a multilayer wiring board suitable for mounting a high-frequency analog circuit was obtained.

[0018]

[Table 1]

[0019]

As described above, according to the low-temperature fired glass ceramics of the present invention, firing can be performed at a temperature of 1000 ° C. or less, that is, interiorization by simultaneous firing of low-resistance conductors such as Au, Ag, and Cu is possible. It is possible to provide a multilayer wiring board suitable for mounting a high-frequency analog circuit having an insulating layer having a low dielectric constant and a low dielectric loss in a frequency band of microwave and millimeter wave regions.

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[Procedure amendment]

[Submission Date] August 7, 2000 (2000.8.7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 7

[Correction method] Change

[Correction contents]

Claims (10)

[Claims] 1. An oxide equivalent of 10 to 45% by weight of SiO ₂ , 20 to 50% by weight of CaO, and _{20 to} 45% of Al ₂ O ₃ .
Wt%, MgO0.1~5 wt%, SrO0.1~5 wt%, BaO0.1~5 _wt%, TiO 2 0.1 to 5 wt%, ZnO0.1~5 _wt%, ZrO 2 0.1 An SiO ₂ —CaO—Al ₂ O ₃ based glass having a composition of about 5 to 5% by weight and a group 1A element oxide of 0 to 3% by weight, which is densified in a firing process at a firing temperature of 800 to 1000 ° C. A low-temperature fired glass ceramic characterized by the following: _2. A composite comprising ceramic particles dispersed in a SiO ₂ —CaO—Al ₂ O ₃ system glass, wherein the glass is composed of 10 to 45% by weight of SiO _{2 in} terms of oxide, and
aO20~50 _{wt%, Al} 2 O 3 20 to 45 wt%,
MgO 0.1-5% by weight, SrO 0.1-5% by weight, B
aO 0.1 to 5% by weight, TiO ₂ 0.1 to 5% by weight, Z
nO0.1~5 _wt%, ZrO 2 0.1 to 5 wt%, and which has a composition consisting of Group 1A element oxide 0-3% by weight, densification in the firing process of firing temperature 800 to 1000 ° C. A low-temperature fired glass ceramic characterized by the following: 3. The oxide of a Group 1A element is Na ₂ O, K
_{2 O,} and 1 or more in the low-temperature firing glass-ceramic according to claim 1 or 2, characterized in that selected from Li 2 _O. 4. The low-temperature fired glass ceramic according to claim 2, wherein the ratio of the ceramic particles in the composite is 10 to 50% by weight in terms of weight ratio. 5. The method according to claim 1, wherein the ceramic particles are Al.₂O
₃(Alumina), SiO ₂(Silica), Mg₂Al₄S
i₅O₁₈(Cordierite), Mg₂SiO₄(Forsteri
te) and Al₆Si₂O₁₃(Mullite)
5. The method according to claim 2, wherein at least one kind is selected.
The low-temperature fired glass ceramic according to any one of the above. 6. The method according to claim 1, wherein the sintering process comprises CaAl.₂SiO
₆, Ca₃Si₂O ₇(Rankinite), CaSiO₃(W
ollastonite), and Al₆Si₂O₁₃(Mullite)
Among them, one or more types of crystals are precipitated
The method according to any one of claims 1, 2, 3, 4 to 5
Low temperature fired glass ceramics. 7. (A) SiO ₂ —CaO by weight percentage
A film-forming step of forming a green sheet from a mixed powder composed of 50 to 100% by weight of Al ₂ O ₃ -based glass powder and 0 to 50% by weight of ceramic powder; and (B) laminating the green sheets and hot pressing. (C) firing the laminated body obtained through the laminating step in a temperature range of 800 to 1000 ° C. to produce a sintered body. A method of manufacturing, wherein the glass is SiO 2 in terms of oxide.
₂ 10 to 45% by weight, CaO 20 to 50% by weight, Al ₂
O ₃ 20 to 45% by weight, MgO 0.1 to 5% by weight, Sr
O 0.1-5% by weight, BaO 0.1-5% by weight, TiO
₂ 0.1-5% by weight, ZnO 0.1-5% by weight, ZrO
_{2. A} method for producing a low-temperature fired glass ceramic, comprising a composition comprising 0.1 to 5% by weight and a group 1A element oxide of 0 to 3% by weight. 8. The method according to claim 1, wherein the group 1A element oxide is Na ₂ O, K
_{2 O,} and a manufacturing method of low-temperature firing glass-ceramic according to claim 7, characterized in that one or more selected from Li 2 _O. 9. The method according to claim 1, wherein the ceramic particles are Al.₂O
₃(Alumina), SiO ₂(Silica), Mg₂Al₄S
i₅O₁₈(Cordierite), Mg₂SiO₄(Forsteri
te), CaAl₂SiO₇, Ca₃Si₂O₇(Rankin
ite), CaSiO₃(Wollastonite) and Al₆S
i₂O₁₃(Mullite) One or more types selected from
The low-temperature fired glass according to claim 7 or 8, wherein
Manufacturing method of ceramics. 10. The method according to claim 1, wherein in the firing step, CaAl ₂ Si
O ₆ , Ca ₃ Si ₂ O ₇ (Rankinite), CaSiO ₃
(Wollastonite), and Al ₆ Si ₂ O ₁₃ (Mullit
The method for producing a low-temperature fired glass ceramic according to any one of claims 7, 8 and 9, wherein at least one kind of crystal is precipitated out of e).