JPH07242440A - Colored material fired at low temperature, production thereof and insulating colored electronic material using the same - Google Patents

Abstract

PURPOSE:To obtain a colored material burnt at a low temp. by uniformly dispersing and incorporating a metal oxide into the particles and grain boundaries of a material burnt at a low temp. such as cordierite-based crystallized glass or a glass-ceramic composite. CONSTITUTION:Cordierite-based crystallized glass is prepd. by blending SiO2, Al2O3 and MgO as principal components with a specific amt. of one or more among ZnO, CaO, Y2O3, B2O3, P2O5 and ZrO2 and converting them into frit. A glass-ceramic composite is prepd. by blending part of the crystallized glass with a specific amt. of ceramics such as mullite or Al2O3. Oxides or alkoxides of one or more kinds of metals such as Ti, V, Cr, Mn and Fe are added by about 0.1-10 pts.wt. to 100 pts.wt. of the cordierite-based crystallized glass or the glass-ceramics composite, they are mixed and the objective colored material contg. metal oxides uniformly dispersed in the particles and grain boundaries of the material is produced. A sintered compact is obtd. by laminating and firing compact sheets of the colored material at 900-1,000 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored low-temperature calcined material such as cordierite-based crystallized glass or a glass-ceramic composite having a light-shielding property, a method for producing the same, and a multilayer circuit to which the colored low-temperature calcined material is applied. The present invention relates to an insulating colored electronic material such as a substrate and a semiconductor (IC) package.

[0002]

2. Description of the Related Art Conventionally, alumina has been mainly used as an electrically insulating ceramic material suitable for a multilayer circuit board or a semiconductor (IC) package material. But,
As the processing speed increases and the wiring density increases,
Since alumina has a large dielectric constant and a large coefficient of thermal expansion, it causes a signal propagation delay and causes stress strain in a semiconductor chip. Further, since alumina ceramics has a high firing temperature, it is necessary to use a metal material having relatively high resistance such as tungsten (W) or molybdenum (Mo) having a high melting point as a signal conductor (wiring material) for internal wiring. There was a problem. Against this technical background, there is a demand that gold (Au), silver (Ag), copper (Cu), etc., can be used as a low resistance conductor in place of tungsten and molybdenum. Various low-temperature firing materials to replace the above have been developed and put to practical use. This low temperature firing material is roughly classified into a crystallized glass system and a glass-ceramic composite system.

In the crystallized glass system, there are cordierite type crystallized glass, Japanese Unexamined Patent Publication No. 59-92943, Japanese Unexamined Patent Publication No. 59-92957, and Japanese Unexamined Patent Publication No.
Various low-dielectric constants, low thermal expansion coefficients, and low-temperature fired crystallized glasses such as those found in Japanese Patent Publication No. 9-137341 have already been presented. Further, in the glass-ceramics composite system, Japanese Patent Publication No. 63-6503, JP-A-4-275.
Those disclosed in Japanese Patent No. 975, etc. are already known. Further, as a crystallized glass-glass composite, those disclosed in JP-A-5-186243 are also included.

Further, since the above-mentioned various low temperature firing materials are generally white to semi-transparent color, when a semiconductor (IC) element is mounted on a ceramic substrate made of these firing materials, the light passes through the ceramic substrate. There is a problem that a semiconductor (IC) element may malfunction.
Therefore, in order to solve this problem, it has been considered to add a colorant to the firing material. For example, Japanese Patent Laid-Open No. 2-4
Japanese Patent No. 4043 discloses a colored crystallized glass body obtained by fritizing cordierite-based crystallized glass with a powder of iron oxide (Fe ₂ O ₃ ), cobalt oxide (CoO) or the like, and a method for producing the same. Is disclosed.

[0005]

However, even if a coloring component is mixed with crystallized glass, such as the one disclosed in Japanese Patent Laid-Open No. 2-44043, the coloring component does not have crystal grains. It exists only between the grains and cannot enter into the crystallized glass, and since it is simply the one that is fired in a mixed state, the light is diffused through the crystallized glass portion and transmitted through the semiconductor ( There has been a concern that a malfunction occurs in the IC) element, that is, the light-shielding property of protecting the semiconductor (IC) element from light is slightly inferior.

Further, according to this publication, when the color component is mixed and fired in the frit glass, it is carried out in a powder state, so that the mixed dispersion state of the color powder is apt to become non-uniform, and the color component is agglomerated during firing, which causes There was also a concern that the adhesion of the wiring conductors such as Au and Ag may be hindered when the wiring conductors such as Au and Ag are later metallized on the substrate made of the colored firing material.

Furthermore, since the coloring component is mixed in a powder state in this publication, since the coloring component cannot enter the glass crystal grains, a relatively large amount of the coloring component is required to enhance the light-shielding property. As a result, the characteristics of the crystallized glass itself (dielectric constant, thermal expansion coefficient,
There is also a problem in that the strength is deteriorated, or the cost becomes considerably high especially when an expensive raw material such as cobalt is used.

The present invention has been made in order to solve such problems, and its object is to provide a uniform coloring as well as having an electric insulating property, a low dielectric constant and a low thermal expansion coefficient. An object of the present invention is to provide a colored low-temperature calcination material excellent in light-shielding property in a state. Another object of the present invention is to provide a method for producing a colored low-temperature fired material in such a homogeneous colored state. Furthermore, the present invention also provides an insulating electronic material to which such a colored low-temperature fired material in a homogeneous colored state is applied.

[0009]

In order to achieve this object, the colored low temperature firing material of the present invention is a crystal grain of a firing material having a relatively low firing temperature such as cordierite-based crystallized glass or glass-ceramic composite. Further, the gist is that the metal oxide is uniformly dispersed and contained in the grain boundary.

The term "low temperature calcination material" as used herein is a term used in comparison with a material such as alumina which is calcinated at a relatively high temperature of 1500 to 1600 ° C., and a temperature relatively lower than that, preferably 850 to 1000. A material that is fired at a firing temperature of about ° C. The "low temperature firing material" includes a crystallized glass-based material, a glass-ceramic composite material, and a crystallized glass-glass composite material.

The crystallized glass system includes various materials in addition to cordierite crystallized glass, and the "cordierite crystallized glass" is composed of a cordierite crystal phase and a glass phase. It means both a crystallized glass and a crystallized glass containing a small amount of β-quartz in addition to a cordierite crystal phase and a glass phase. Further, the glass-ceramic composite body also has various compositions as described above.

Particularly, as the "cordierite type crystallized glass", SiO ₂ , Al ₂ O ₃ and MgO are the main components (preferably 80% by weight or more), and ZnO and C
If necessary, one or more components selected from aO, Y ₂ O ₃ , B ₂ O ₃ , P ₂ O ₅ , and ZrO ₂ may be added.
It is preferable that the content in the range of 20% by weight or less is electric insulation, a low dielectric constant and a low coefficient of thermal expansion, and the "glass-ceramic composite" is SiO.
₂ , Al ₂ O ₃ and MgO as main components, and ZnO, C
_{aO, Y 2 O 3, B} 2 O 3, P 2 O 5 or a ceramic material of alumina or mullite glass material one or two or more components selected from among ZrO ₂ is contained as necessary, the It is preferable that a predetermined amount, preferably 20 to 80% by weight, is blended.

Further, as "colored metal oxide", T
In addition to i, V, Cu, Mn, Fe, Co, Ni, etc.
Group 6 such as Cr, Mo, W, Pr, Nd, Eu, T
Examples of the colorant include oxides of various metal elements such as rare earth group b, Ho, Er and the like, and it is preferable to use one kind or two or more kinds of materials appropriately selected from these materials. The metal oxide is added in an amount of 0.1 to 100 parts by weight of the above-mentioned low temperature firing material.
It is preferably contained in the range of 10 parts by weight.

If the amount of the metal oxide is less than 0.1 part by weight, the coloration may be low and sufficient light-shielding property may not be obtained, and if more than 10 parts by weight is added, it is meaningless in terms of the light-shielding property. Instead, weaken the firing material, and use the wiring conductors (Au, A
This is because the metallization property of (g, etc.) may be impaired. Further, the method for producing a colored low temperature fired material according to the present invention,
The gist of the present invention is to mix powder of a material which becomes a cordierite-based crystallized glass or a glass-ceramics composite after firing and a liquid substance which produces a metal oxide by firing and fire the mixture.

Here, the "liquid substance" is an alkoxide such as methoxide or ethoxide of the metal element of the colored metal oxide or a solution thereof, or an acid such as a nitrate or oxalate of the metal element of the metal oxide. A salt or a solution thereof is preferable. And as the "metal element of the metal oxide", Ti, V, Cr,
Mn, Fe, Co, Ni, Cu, Mo, W, Pr, N
Examples thereof include d, Eu, Tb, Ho, Er and the like. By mixing the liquid material having this coloring component with the powder of the low temperature firing material, the coloring component is uniformly dispersed throughout the powder, and the solid dispersion progresses uniformly during firing, and a coloring material having a high light-shielding property is obtained. It is a thing.

Finally, the electronic material of the present invention is an insulating electronic material suitable for use in multilayer circuit boards, IC packages and the like made of low temperature firing materials such as cordierite crystallized glass and glass-ceramic composites. hand,
The gist is that the metal oxide is uniformly dispersed and contained in the crystal grains and grain boundaries of the low-temperature calcination material.

[0017]

EXAMPLES Examples of the present invention will be described in detail below. First, the following Table 1 shows the material composition of the low-temperature fired material according to the present invention, which is used in various examples described below.

[0018]

[Table 1]

As shown in Table 1, Nos. 1 to 3 are
It is a cordierite-based crystallized glass, and its glass powder raw material contains SiO ₂ , Al ₂ O ₃ , and MgO as main components, and ZnO, CaO, Y ₂ O ₃ , B ₂ O ₃ , P ₂
A material fritified by appropriately mixing materials selected from O ₅ and ZrO ₂ is used. on the other hand,
Nos. 4 and 5 are glass-ceramic composites, and as the glass powder raw material, SiO ₂ ,
Al ₂ O ₃ and MgO are the main components, and CaO,
B ₂ O ₃ and ZrO ₂ were blended in appropriate proportions and used as a frit. Ceramic powder was added to this and a suitable amount of alumina or mullite was mixed.

The following Table 2 is a solution-like additive added as a coloring material to the above-mentioned cordierite-based crystallized glass (Nos. 1 to 3) and the glass-ceramics composite (Nos. 4 and 5). But alkoxide (ethoxide)
It shows the case of.

[0021]

[Table 2]

Further, the following Table 3 is a solution-like addition added as a coloring material to the above-mentioned cordierite type crystallized glass (Nos. 1 to 3) and the glass-ceramic type composite (Nos. 4 and 5). The case where the product is an acid salt (nitrate) is shown.

[0023]

[Table 3]

Then, the powder shown in Table 1 is blended with ethoxide which is the solution-like additive shown in Table 2, in such a proportion that the equivalent oxide amount shown in Table 4 is obtained. Mix in a resin pot to make mud, and add known molding aids to this mud to form a sheet.
Then, the obtained sheet-like material was punched with a die, laminated, cut into a predetermined size, and then resin was removed at 300 ° C., and then baked at a temperature of 900 to 1000 ° C. As test samples of the present invention, Nos. 18 to 25 are presented.
In addition, as a comparative example, those obtained by adding no alkoxide as a coloring material (Nos. 26 to 30) are shown in Table 4.
It is also shown inside.

[0025]

[Table 4]

On the other hand, in the case where the powder shown in Table 1 is blended with nitrate as a solution-like additive shown in Table 3,
The mixture is mixed in a resin pot at a ratio such that the oxide conversion amount shown in Table 5 below is obtained, and the obtained slurry is dried and then calcined at 600 ° C. Then, the calcined powder is dispersed in a solvent, and a known molding aid is further added to form a sheet. Then, the obtained sheet-like material was punched with a die, laminated, cut into a predetermined size, and then resin was removed at 300 ° C., and then baked at a temperature of 900 to 1000 ° C. As the test sample of the present invention, No. 31 to No. 3
Present 5.

[0027]

[Table 5]

Further, Japanese Patent Laid-Open No. 2-4 mentioned above as a prior art.
Table 4 below shows comparative data as a conventional example, which was prepared by blending cordierite-based crystallized glass with metal oxide powder and firing the mixture, as disclosed in Japanese Patent No. 4043.

[0029]

[Table 6]

Next, various test results will be described. Sintered body characteristics (appearance, bending strength, thermal expansion coefficient, relative dielectric constant) of the product of the present invention (No. 18 to 25, No. 31 to 35) and the comparative product (No. 26 to 30, No. 36 and 37) Comparative data of the ratio, the main crystal phase, etc.) are as shown in Tables 4 to 6 described above. In addition, scanning electron microscope (SEM)
The microstructure was observed and the elemental analysis was performed by energy dispersive X-ray spectroscopy (EDS) in the crystal grains and grain boundaries of the sintered body.

The sintered body obtained according to the present invention (No. 23
1) shows a structure photograph as a result of structure observation by a scanning electron microscope (SEM). The results of elemental analysis by energy dispersive X-ray spectroscopy (EDS) in the crystal grains and grain boundaries of the sintered body are shown in FIG. As comparative data for this, a structural photograph of the sintered body of the comparative product (No. 26) by a scanning electron microscope (SEM) is shown in FIG.
And the results of elemental analysis by energy dispersive X-ray spectroscopy (EDS) in the crystal grains and grain boundaries of the sintered body are shown in FIG.

From these results, it can be said that even if the product of the present invention initially contains a metal oxide with an alkoxide (No. 18 to 25), it contains a metal oxide with an acid salt ( No. 31-35),
First, it is that a colored fired material that is homogeneous can be obtained by visual observation. Further, in the observation results by the SEM scanning electron microscope of FIGS. 1 and 3, it seems that the shape of the crystal grains of the product of the present invention (No. 23) is relatively finer than that of the comparative product (No. 26). . It seems that the product of the present invention is affected by mixing the crystallized glass powder with the alkoxide and making the mixture into a sludge state and molding and firing.

Next, the results of the EDS elemental analysis in the crystal grains and in the grain boundaries in FIGS. 2 and 4 show that the product of the present invention (No. 23).
In the case of), a small amount of Ni element was observed at the grain boundaries, but most of the coloring materials were Cr ₂ O ₃ , MnO ₂ , CoO, N.
No localized presence of iO or the like was observed, and it was observed that they were uniformly dispersed and solid-dissolved in the crystal grains and in the grain boundaries. Therefore, although the light transmittance (light blocking rate) of these various materials is not particularly measured, a high light blocking effect is obtained as compared with the comparative product. When an IC chip is mounted on an IC package made of this material, it is expected that the risk of malfunction of the IC chip due to light transmission is reduced.

Further, considering the results of Tables 4 to 6, it was confirmed that the products of the present invention have a bending strength slightly higher than that of the comparative product in any case as a characteristic of the sintered body. This is the case of the product of the present invention (cordierite-based crystallized glass N
18 to 25, and glass-ceramic composite N
o.31 to 35)), the metal oxide is uniformly dispersed in the crystal grains of the fired material and in the grain boundaries to strengthen the bonded state in the crystal structure, and in the case of crystallized glass,
It is presumed that this is because the crystal grains became fine.

This point is also significant in comparison with the one disclosed in Japanese Patent Application Laid-Open No. 2-40443 disclosed in Table 6 as a conventional example, and it is recognized as a significant result.
This higher bending strength means that it is a multilayer substrate or IC.
When applied as a package, the strength of the material is increased, so it will not be damaged during handling in the manufacturing process of these products, and secondary effects such as thinning as a substrate material can be achieved. To be

The results of measurement of the thermal expansion coefficient and the relative permittivity show that the products of the present invention (Nos. 18 to 25, and No. 31).
~ 35) and comparative products (No. 26 to 30, and No. 36)
And 37), no significant difference was observed, and the results were neither excellent nor inferior to the product of the present invention. Although various embodiments have been described above, it is needless to say that the present invention is not limited to these embodiments and various modifications can be made without departing from the spirit of the present invention. .

For example, although the material composition of the cordierite-based crystallized glass and the glass-ceramic composite is shown in Table 1 in the above-mentioned examples, the composition is not limited to this, and various glass powder materials may be blended, or glass- In the ceramic composite, it is of course possible to mix various ceramic powders such as spinel, magnesia and forsterite other than alumina and mullite as the ceramic powder to be mixed.

In the case of alkoxide as a solution additive, only ethoxide was shown, and in the case of acid salt, only nitrate was shown. In the case of acid salt, it is of course possible to adopt other water-soluble salts such as oxalate. In addition to these, a chelate compound or the like combined with the above metal element may be used.

[0039]

As is apparent from the above description, according to the low temperature fired material of the present invention, the metal oxide is uniformly dispersed in the fired crystal grains and in the grain boundaries, and the insulating property and the high bending strength are obtained. Not only does it have a low coefficient of thermal expansion and low relative permittivity, but it also has excellent light-shielding properties, so it can be used in electronic materials such as multi-layer circuit boards and IC package materials to malfunction IC chips due to light transmission. These problems will be solved. Further, even in the manufacturing process of these electronic material parts, it is advantageous in securing the accuracy at the time of position detection using light, and the wiring conductors (Au, Ag
The adhesion of the metallization (1) and the like is improved, and problems such as poor conduction are eliminated. Furthermore, the homogenous dispersion of these metal oxides results in relatively high mechanical strength, which facilitates handling during the manufacturing process, reduces damage during the manufacturing process, improves product yield, and reduces the thickness of circuit boards. The economic effect of the achievement is also great. Therefore, the application of the colored low-temperature fired material of the present invention as these electronic material parts is extremely beneficial industrially.

[Brief description of drawings]

FIG. 1 is a diagram showing a result of observing a texture of a colored low-temperature fired material according to an example of the present invention with a scanning electron microscope (SEM).

FIG. 2 is a diagram showing a result of performing elemental analysis of the material shown in FIG. 1 by energy dispersive X-ray spectroscopy (EDS). (A) is an elemental analysis result of grain boundaries, (b) is an enlarged view thereof, (c) is an elemental analysis result of grains,
(D) is an enlarged view of it.

FIG. 3 is a diagram showing a result of observing the structure of a low temperature fired material as a comparative example with a scanning electron microscope (SEM).

FIG. 4 is a diagram showing a result of carrying out elemental analysis of the material shown in FIG. 3 by energy dispersive X-ray spectroscopy (EDS).

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[Procedure amendment]

[Submission date] August 2, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a colored low temperature firing ceramic according to an embodiment of the present invention.
It is a micrograph which observed the structure of the black material by a scanning electron microscope (SEM).

FIG. 2 is a diagram showing a result of performing elemental analysis of the material shown in FIG. 1 by energy dispersive X-ray spectroscopy (EDS). (A) is an elemental analysis result of grain boundaries, (b) is an enlarged view thereof, (c) is an elemental analysis result of grains,
(D) is an enlarged view of it.

[Figure 3] micrograph observed by tissue a scanning electron microscope of the low-temperature fired ceramic material as a comparative example (SEM)
Is true .

FIG. 4 is a diagram showing a result of carrying out elemental analysis of the material shown in FIG. 3 by energy dispersive X-ray spectroscopy (EDS).

Claims (9)

[Claims] 1. A colored color characterized in that a metal oxide is uniformly dispersed and contained in crystal grains and grain boundaries of a low temperature fired material such as cordierite-based crystallized glass or glass-ceramic composite. Low temperature firing material. 2. The cordierite-based crystallized glass is made of Si.
O ₂ , Al ₂ O ₃ and MgO are the main components, and ZnO,
_{CaO, Y 2 O 3, B} 2 O 3, P 2 O 5 or claims, characterized in that the selected one or two or more components out of the ZrO ₂ is intended to be included as needed, 1. The colored low temperature firing material according to 1. 3. The glass-ceramic composite is made of SiO.
₂ , Al ₂ O ₃ and MgO as main components, and ZnO and C
_{aO, Y 2 O 3, B} 2 O 3, P 2 O 5 or a ceramic material of alumina or mullite glass material one or two or more components selected from among ZrO ₂ is contained as necessary, the The colored low-temperature fired material according to claim 1, wherein the colored low-temperature fired material is blended. 4. The metal oxide comprises Ti, V, Cr, Mn,
Fe, Co, Ni, Cu, Mo, W, Pr, Nd, E
The colored low-temperature calcined material according to claim 1, which is an oxide of one or more metal elements selected from u, Tb, Ho, and Er. 5. The colored low temperature fired material according to claim 1, wherein the metal oxide is contained in the range of 0.1 to 10 weight parts with respect to 100 weight parts of the low temperature fired material. 6. A powder obtained by mixing a powder of a material which becomes a cordierite-based crystallized glass or a glass-ceramics composite after firing and a liquid substance which produces a metal oxide by firing and firing the mixture. A method for producing a colored low temperature fired material. 7. The method for producing a colored low-temperature fired material according to claim 6, wherein the liquid substance is an alkoxide such as methoxide or ethoxide of a metal element of the metal oxide, or a solution thereof. 8. The method for producing a colored low-temperature fired material according to claim 6, wherein the liquid substance is an acid salt of a metal element such as a nitrate or oxalate of the metal oxide, or a solution thereof. 9. An insulating electronic material used for a multi-layer circuit board, an IC package, etc. made of a low-temperature fired material such as cordierite-based crystallized glass or a glass-ceramics composite, wherein the inside of the crystal grains of the low-temperature fired material and An insulating colored electronic material characterized in that a metal oxide is uniformly dispersed and contained in grain boundaries.