JP2504351B2 - Multi-layer glass ceramic substrate and manufacturing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer glass ceramic substrate for mounting an LSI element, and more particularly to a multi-layer glass ceramic substrate which can be sintered at a low temperature and a manufacturing method thereof.

[0002]

2. Description of the Related Art With the development of semiconductor technology, there is an increasing demand for miniaturization and higher speed of electronic devices and systems. Semiconductor elements are highly integrated and highly integrated with VLSI and ULSI, and a mounting technique for assembling these elements requires extremely high density and fineness. In particular, a mounting board for mounting a semiconductor element is required to have fine wiring due to an increase in wiring density, a reduction in wiring resistance, a low dielectric constant of a substrate material corresponding to high speed, and a high density wiring. . Alumina multilayer substrates have been conventionally used as a substrate material. As a method of manufacturing this substrate,
There are thick film printing multi-layer method and green sheet lamination method,
The green sheet lamination method is advantageous for the demand for high density. Since the green sheet lamination method is obtained by printing and forming wiring on each layer of thin ceramic green sheets and laminating them integrally, the number of wiring layers can be arbitrarily increased.
As a result, the wiring density can be higher than that of the thick film printing multilayer. However, alumina ceramic has a sintering temperature of 1
It is difficult to miniaturize the wiring because it is necessary to use Mo or W metal having a relatively high electric resistance for the wiring conductor as high as 500 ° C. or higher.

On the other hand, recently, low resistance conductors such as Au and Ag-P have been used.
Low temperature sintering type ceramic materials using d, Ag, Cu, etc. have been developed. For example, in the case of a composite material of alumina and lead borosilicate glass, it is possible to sinter at a low temperature of 1000 ° C. or lower, and a multilayer substrate using Au, Ag—Pd, or Ag as a wiring conductor has been developed. However, since this material contains lead, it is difficult to use Cu, which is a base metal, for the wiring, and the dielectric constant can be reduced only to 7.5 or more. In addition, low dielectric constant and 10
Glass-ceramic materials using borosilicate glass aimed at firing in a reducing atmosphere at 00 ° C. or lower have also been developed.
This has a low dielectric constant of about 5.5, and multilayering with Cu wiring has been realized by the simultaneous sintering method of the glass ceramic and conductor, but crystallization does not occur during sintering, and However, there was a drawback that the dynamic strength was significantly reduced.

[0004]

The conventional alumina multi-layer substrate can be sintered only at a high temperature and therefore has a high electric resistance.
Since only o and W can be used for the conductor, the wiring resistance was high and fine wiring was impossible. Further, the dielectric constant of alumina is as high as about 10, which is disadvantageous for speeding up signals.
The composite material of alumina and lead borosilicate glass can be sintered at a low temperature, and a low resistance conductor can be used for wiring, but it was difficult to perform firing in a reducing atmosphere or to realize base metal conductor wiring. Further, in a glass ceramic substrate using borosilicate glass, C
Although u multilayer wiring and a low dielectric constant are possible, the mechanical strength is significantly reduced. The mechanical strength of the board is an extremely important characteristic.In particular, in a multi-chip mounting board in which many semiconductor elements are mounted on the board, the board size becomes large and many input / output terminals or pins are connected. As a result, not only the assembly process but also the product state may cause problems such as substrate damage and defective joining with metal. The object of the present invention is to solve the above problems of the conventional mounting substrate, so that it can be fired at a low temperature of 1000 ° C. or less and in a neutral or reducing atmosphere as well as in an oxidizing property, and has a low dielectric constant and mechanical properties. The object is to provide a multilayer glass ceramic substrate having excellent strength.

[0005]

The present invention provides an inorganic composition in which a glass-ceramic layer is composed of alumina, α-quartz, borosilicate glass and anorthite crystals, wherein the alumina is 12 to 59.6% by weight, α -Quartz 10 to 30% by weight, borosilicate glass 18 to 69.6% by weight, and anorthite crystal 1 to 50% by weight in a composition range so that the total amount is 100%, and a plurality of conductor layers are formed in the glass ceramic. It is a multilayer glass-ceramic substrate characterized by being laminated via layers. Further, the first of the manufacturing methods thereof is that the raw material powder is 10 to 50% by weight of alumina powder, 10 to 50% by weight of α-quartz powder, and 40 to 70% by weight of calcium borosilicate glass powder so that the total amount is 100%. It is characterized in that a mixed powder is used. In this method, it is preferable that the calcium composition contained in the calcium borosilicate-based glass is 5% by weight or more of calcium oxide with respect to the glass composition, according to the oxide conversion notation. The second manufacturing method is to use alumina powder, α-quartz powder, borosilicate glass powder and anorthite powder as raw material powders, and the average particle size of each is 0.5 to 3 μm of alumina powder and α-quartz powder. 0.5-10μ
m, borosilicate glass powder 1 to 5 μm, and anorthite powder 1 to 10 μm, and a step of mixing these powders, a step of making the mixed powders into a slurry state and then forming a green sheet, and the green Forming a via hole on the sheet, printing and filling the conductor, and laminating and thermo-compressing the printed sheets, 1000 ℃
And a step of firing at the following temperature.

The glass ceramic substrate of the present invention is 100
Since it becomes possible to sinter at a temperature of 0 ° C. or less, it is possible to easily form a multilayer by the desired green sheet lamination method, and not only the elements such as Au, Ag, Pd and Pt but also the neutral or Multi-layer glass ceramics that have a high mounting density and excellent mechanical strength can now be used without anxiety, including the use of one type or alloys containing two or more types of base metals such as Cu and Ni that are fired in a reducing atmosphere. The substrate can be put to practical use. Here, the mechanical strength of the substrate according to the present invention has a bending strength of 2000 kg / cm ² or more, which is sufficient strength.

Next, the reasons for limiting each constituent of the present invention will be described. If the alumina content is less than 12% by weight, the bending strength is 20.
It becomes less than 00 kg / cm ^2, which is insufficient. Also 59.
If it exceeds 6% by weight, sintering becomes insufficient at a temperature of 1000 ° C. or less, resulting in a decrease in insulation resistance and a bending strength of less than 2000 kg / cm ² . Furthermore, since the dielectric constant exceeds 7, it is disadvantageous for speeding up, and a practical multilayer glass ceramic substrate cannot be obtained. When the content of α-quartz is less than 10% by weight, the dielectric constant exceeds 7. Also, if it exceeds 30% by weight, sintering becomes insufficient, the insulation resistance is lowered, and the bending strength is 2000 kg /
It drops to less than cm ² . When the content of the borosilicate glass is less than 18% by weight, it becomes impossible to obtain a glass phase sufficient to occupy the voids between the alumina particles, so that the strength decreases and the reliability cannot be obtained. If it exceeds 69.6% by weight, the original strength of glass becomes dominant and the bending strength is 2000 kg / cm.
It will be less than ² .

When the anorthite crystal is less than 1% by weight, the effect of strengthening strength by the anorthite crystal is lost,
A bending strength of 2000 kg / cm ² or more cannot be obtained. 50
If it exceeds 5% by weight, the shrinkability of the multi-layer glass ceramic substrate becomes non-uniform and the reliability decreases. If the amount of the alumina powder used as the raw material powder is less than 10% by weight, the chemical reactivity with the glass with respect to the anorthite crystal formation at the time of sintering is lowered and the crystal formation becomes insufficient.
Alternatively, crystals will be nonuniformly produced, resulting in a bending strength of less than 2000 kg / cm ² . If it exceeds 50% by weight, sintering will be insufficient at a temperature of 1000 ° C. or less, and the insulation resistance will decrease and the bending strength will also decrease. Also, the dielectric constant exceeds 7. When the amount of the calcium borosilicate glass powder used as the raw material powder is less than 40% by weight, the reactivity with alumina is lowered, the formation of anorthite crystals is largely inhibited, and the nonuniform crystal formation occurs, so that the strength is lowered. If the amount exceeds 70% by weight, the glass softening reaction proceeds during firing, so that the dimensional stability of the fired substrate deteriorates and a practical substrate cannot be obtained.

When the calcium composition of the calcium borosilicate glass used as the raw material powder is less than 5% by weight of calcium oxide according to the oxide conversion notation, anorthite crystals are hardly generated during firing. When the alumina powder used as the raw material powder is less than 0.5 μm or more than 3 μm, the α-quartz powder is 0.5 μm.
If the borosilicate glass powder is less than 1 μm or more than 5 μm, and if the anorthite powder is less than 1 μm or more than 10 μm, the sinterability of the mixture is poor and the properties of the multilayer glass ceramic substrate are A practical multilayer glass-ceramic substrate cannot be obtained because the above reliability is significantly reduced.

[0010]

The composition of the multilayer glass ceramic substrate of the present invention is
The reason why sintering can be performed at a temperature of 1000 ° C. or lower is as follows. Calcium borosilicate glass or borosilicate glass starts softening at about 700 ° C. or higher during firing.
The liquefied glass fills the voids between the ceramic powders of alumina and α-quartz or alumina and α-quartz and anorthite, and the densification progresses. Thus 8
A sufficiently dense glass ceramic body is formed in the temperature range of 00 to 1000 ° C., and the sintering is completed. Next, the reason why the composition can be sintered in a reducing atmosphere is that the present composition uses an element which is suppressed from being reduced from an oxide state to a metal element under this condition. For example, in the case of a composition containing lead oxide, it changes into metallic lead in a reducing atmosphere, and the insulating properties of the glass ceramic body deteriorate significantly. Mechanical strength is one of the important properties in a multilayer glass ceramic substrate, and the present invention is particularly effective for this property. The reason why the strength can be achieved at 2000 kg / cm ² or more is due to the structure of the glass ceramic body after sintering. That is, the alumina and the liquid-phased glass can generate anorthite crystals along with a chemical reaction during sintering. In this way, alumina particles, α-quartz particles and vitreous parts and anorthite crystals are three-dimensionally and densely formed in the sintered glass-ceramic body, and the ceramic and glass are firmly bonded, As a result, a substrate having sufficient bending strength can be obtained.

[0011]

EXAMPLES Examples of the present invention will be described in detail below. Example 1 Alumina powder, α-quartz powder and calcium borosilicate glass powder were mixed as shown in Table 1 (alumina powder + α-
Quartz powder): Calcium borosilicate glass = 30% by weight: 70% by weight to 60% by weight: 40% by weight, mixed sufficiently and molded into a sheet by the green sheet laminating method. At this time, the alumina powder was contained at least 10% by weight or more, and the calcium borosilicate glass powder used here contained 5% by weight of calcium oxide in terms of oxide conversion. As a method for forming a green sheet, a mixed powder is dispersed in a solvent together with an organic binder such as polyvinyl butyral, polyvinyl alcohol, or a polyacrylic resin to make a sludge, and then the slip casting method is used. The thickness of the green sheet can be uniformly and freely controlled within the range of 10 to 400 μm.

Next, a via hole for connecting the upper and lower conductors is formed on the green sheet by a punching device. Embedding of a conductor paste for electrically connecting to the via hole and wiring pattern printing are performed. The conductors used here are Au, Ag, Ag-Pd, Cu, Ni,
It is a conductor paste containing Ag-Pt as a main component and is printed at a predetermined position by a screen printing method. The green sheet with the conductor pattern printed and via-filled is laminated to have a predetermined number of layers and thermocompression bonded. 400-700 ℃ the organic binder and solvent added during molding
After removing by the binder removal process at the temperature of 800-1
Firing was performed in the temperature range of 000 ° C. to obtain a multilayer glass ceramic substrate. During the main calcination, the glass is softened and the voids between the alumina particles are occupied by the glass, and the densification progresses.
Furthermore, anorthite crystals are generated by a chemical reaction with alumina. The composition ratio of the obtained glass ceramic layer is shown in Table 2.
Shown in The sample numbers 1 to 6 in Table 2 correspond to the raw material numbers 1 to 6 in Table 1.

Example 2 Next, another method for producing a glass ceramic body will be described. The alumina powder is pulverized and controlled so that the average particle diameter becomes 0.5 to 3 μm. Similarly, α-quartz powder is ground to an average particle size of 0.5 to 10 μm. In addition, borosilicate glass is used, for example, with an alumina ball mill to obtain an average particle size of 1 to 5 μ
The powder is pulverized to a fine powder. Further, the anorthite powder is similarly pulverized to have a particle size of 1 to 10 μm. These powders are weighed so as to have a target composition and uniformly mixed by an alumina ball mill or the like. The mixed powder is dispersed in a solvent together with an organic binder such as polyacrylic resin, polyvinyl butyral and polyvinyl alcohol to prepare a slurry. The sludge is formed into a green sheet in a film thickness suitable for forming an insulating layer by a slip casting method such as a doctor blade method or a roll method, for example, in the range of 10 to 400 μm. Next, a via hole for obtaining vertical conduction is formed on the green sheet with a die and a punch. A conductor paste is embedded in the sheet in which the via holes are formed, and a wiring pattern is printed. A plurality of sheets in which printing and paste are embedded are laminated and thermocompression-bonded at a temperature of 100 to 120 ° C and a pressure of 100 to 300 kg / cm ² , to obtain a laminate. Decomposes organic binder at 400-600 ℃
After the removal, the sintering is completed within the range of 800 to 1000 ° C. The conductor paste used here is Au, Ag, Ag-P.
A paste containing d, Cu or the like as a main component was used. The composition ratio of the obtained glass-ceramic body is shown as sample number 7 in Tables 2 to 3.
~ 40.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

Tables 4 to 7 show firing conditions, wiring specifications and characteristics when the multilayer glass ceramic substrates were produced in Examples 1 and 2. The sample numbers in Tables 2 and 3 and the sample numbers in Tables 4 to 7 showing the composition of the glass ceramic layer in the substrate after sintering correspond to each other.

[0018]

[Table 4]

[0019]

[Table 5]

[0020]

[Table 6]

[0021]

[Table 7]

As is clear from Tables 4 to 7, by using the composition of the present invention, not only a high-density and fine wiring can be easily formed, but also the characteristics are excellent and the composition is practically used. It is possible to obtain a multi-layer glass ceramic substrate that also sufficiently satisfies the mechanical strength required for being provided.

[0023]

As described above, according to the present invention, 1
It is possible to obtain a substrate that can be sintered at a low temperature of 000 ° C. or lower, can be fired in a neutral or reducing atmosphere, and can have a sufficiently low dielectric constant, and that has a large bending strength as mechanical strength.

Claims (4)

(57) [Claims] 1. A glass-ceramic layer is an inorganic composition comprising alumina, α-quartz, borosilicate glass and anorthite crystals, wherein 12-59.6% by weight of alumina and 10-30% by weight of α-quartz, Borosilicate glass 1
8-69.6% by weight, anorthite crystals 1-50% by weight
A multilayer glass ceramic substrate, wherein the total amount is 100% in the composition range, and a plurality of conductor layers are laminated via the glass ceramic layer. 2. The method for manufacturing a multilayer glass ceramic substrate according to claim 1, wherein the raw material powder is alumina powder 1
A multi-layer glass ceramic substrate comprising 0 to 50% by weight, α-quartz powder of 10 to 50% by weight, and calcium borosilicate glass powder of 40 to 70% by weight so that a total amount of 100% is mixed. Manufacturing method. 3. The multilayer glass ceramic substrate according to claim 2, wherein when the calcium composition contained in the calcium borosilicate glass is in oxide conversion notation, calcium oxide is 5% by weight or more based on the glass composition. Production method. 4. The method for producing a multi-layer glass ceramic substrate according to claim 1, wherein alumina powder, α-quartz powder, borosilicate glass powder and anorthite powder are used as raw material powders, and the respective average particles are used. Alumina powder 0.5 to 3 μm, α-quartz powder 0.5 to 10 μm,
The borosilicate glass powder is in the range of 1 to 5 μm and the anorthite powder is in the range of 1 to 10 μm, and a step of mixing these powders, a step of making the mixed powders into a slurry state and then forming a green sheet, and a via sheet on the green sheet A method for producing a multilayer glass ceramic substrate, comprising: forming holes, printing and filling conductors; and stacking and thermocompressing printed sheets and firing at a temperature of 1000 ° C. or less. .