JPS61261233A - Sealing low-melting glass composition - Google Patents

Abstract

PURPOSE:A sealing low-melting glass composition, obtained by mixing low- melting glass powder prepared by combining two kinds of amorphous glass groups having different transition temperatures with a low-expansion filler and capable of sealing alumina packages for IC at a relatively low temperature. CONSTITUTION:A sealing low-melting glass composition obtained by combining (A) an amorphous glass group having <=260 deg.C transition temperature with (B) an amorphous glass group having 260-290 deg.C transition temperature to prepare low-melting glass powder and mixing the resultant low-melting glass powder with a low-expansion filler, e.g. cordierite or zircon. Preferably, th component (A) is a composition consisting of 40-50wt% PbO, 10-12wt% B2O3, 2-3wt% SiO2, 1-3wt% Bi2O3, 5-10wt% PbF2 and 15-35wt% Tl2O, and the component (B) is composition consisting of 80-85wt% PbO, 5-7wt% B2O3, 1-3wt% SiO2, 2-5wt% Bi2O3, 0-7wt% PbF2, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a low melting point glass composition for sealing comprising a low melting point glass powder and a low expansion filler.

In particular, the present invention relates to a low-melting, α-terrace composition for sealing that can seal alumina packages for ICs at temperatures below 400°C.

[Prior Art] Conventional sealing compositions for sealing alumina packages for ICs are usually produced by adding a low expansion filler to one type of low melting point glass.

Furthermore, many patent applications have been filed regarding sealing compositions for bonding Alumina Pack-7 for ICs.

Particularly recent ones include pbo, B201.5iOz, ZnO,^12 as disclosed in Japanese Patent Publication No. 59-45620, Japanese Patent Publication No. 59-45619, etc.
0. and Pb)'.

A glass composition having a sealing temperature of 440 to 450°C, or a glass composition containing pbo, B2O3,2 as essential components as disclosed in JP-A-58-161943.
Contains nO1SiO□, v206, CuO, ^1zo
s, P2O2, 5n02, Litu, Na, 0, etc., with a transition temperature of 288-310℃,
A glass composition having a sealing temperature of 390 to 430°C, and further, PbO2B205, ZnO1SiOz, ^120. and a glass composition having a sealing temperature of 480° C. or lower, which is made of GeO□. The components of the glass compositions described in these publications are mainly PbO-B, O, and i, but various other components can be added to create a sealing composition for sealing an alumina package. It was developed as a glass composition.

In addition, the low expansion filler is used, for example, in order to match the thermal expansion coefficient of the low melting point glass composition for sealing with that of the alumina package and to increase the thermal shock resistance strength of the low melting point glass composition for sealing. , β-eucryptite, lead titanate, willemite, etc.
It is used by adding it to low melting point glass.

[Problem to be solved by the invention 1 The transition temperature of the low melting point glass constituting the sealing composition currently used is often in the range of 300 to 320°C;
Therefore, the sealing temperature of the alumina package is 420~4
Although it is carried out within a range of 80℃, the most related to the sealing temperature of the alumina puff cake is the transition temperature of the low melting point glass, and the lower the sealing temperature of the alumina package, the more it will be mounted on the alumina package. Since the reliability of IC elements is increased, it is desired to develop a low melting point glass composition that can be sealed at a lower temperature.

In general, the transition temperature of low melting point glass is 260°C, although it varies depending on the components that make up the low melting point glass.
In order to obtain a glass with a low melting point below .degree. C., it may be necessary to use relatively expensive raw materials such as thallium oxide, and even if the sealing temperature is low, it may not be practical.

On the other hand, a low melting point glass with a transition temperature of over 260°C and below 290°C can be obtained using relatively inexpensive raw materials, but the sealing temperature of a sealing composition using this low melting point glass is 40°C.
The temperature is around 0°C, and there is almost no difference from the conventional one.

An object of the present invention is to provide a low-melting glass composition for sealing that can seal an alumina package at a lower temperature than conventional sealing compositions.

Means for Solving Problem E] The present invention provides low melting point glass powder and low The present invention relates to a low melting point glass composition for sealing characterized by comprising an expanded filler. More specifically, a low melting point glass powder that is a combination of an amorphous glass group with a transition temperature of 260°C or lower and an amorphous glass group with a transition temperature of over 260°C and 290°C or lower,
By adding a conventionally known low expansion filler, the sealing temperature can be increased to 40
Alumina packages can be sealed at temperatures below 0℃! Regarding wear low melting point glass compositions.

[Example] In the present invention, a low-melting-point molten glass is produced from an amorphous glass group with a transition temperature of 260°C or lower and an amorphous glass group with a transition temperature above 260°C and 290°C or lower.

In order to obtain a low melting point glass whose transition temperature (the temperature at which the viscosity of /7 bus becomes 1011-voids) is 260°C or less, PbO40-50% by weight, BIo, 10-121i
fi%, 51021-3% by weight, Bi2O, 1-31!
Amount %, PbFz5~101ij1%, Tl2O15~3
Preferably, the composition comprises 5% by weight.

As mentioned above, PbO is the main component of the low melting point glass and is a necessary component to lower the transition temperature, but if the proportion in the low melting point glass exceeds 50% by weight, it tends to crystallize.
If it is less than % by weight, the transition temperature will exceed 260°C, and crystallization will tend to occur.

B20. is a component that makes glass easily soluble and prevents crystallization; however, if the proportion of low-melting J:t in the glass exceeds 12% by weight, the transition temperature will exceed 280°C, and if it is less than 10% by weight, it will not crystallize. It tends to become easier.

SiO□ is a component that improves the water resistance of glass and makes it ink-soluble.
The transition temperature exceeds 260°C when it exceeds 1aX% by weight.
If it is less than that, the water resistance of the glass will deteriorate.

BizO3 is one of the two components that lowers the transition temperature, but if its proportion in the low melting point glass exceeds 3% by weight, the glass tends to crystallize, and if it is less than i'% by weight, the effect of adding it is small and the transition temperature decreases. Temperatures tend to exceed 260°C.

PbF is a component that makes glass easily soluble and lowers the transition temperature, and its proportion in the above low melting point glass is 10% by weight.
If the content is less than 5% by weight, the transition temperature of the glass tends to exceed 260°C.

Tl2O is the component that lowers the transition temperature of glass the most, and if its proportion in the low melting point glass exceeds 35% by weight, the water resistance of the glass will deteriorate, and if it is less than 15% by weight, the transition temperature of the glass will drop to 260°C. There is a tendency to increase.

As a raw material for obtaining the above-mentioned low melting point glass, use analogy 5.
Red lead, boric acid, silica powder, bismuth oxide manufactured by Tsu Pharmaceutical Co., Ltd.
Use lead fluoride, thallium oxide, etc. These raw materials are mixed to have a predetermined composition, placed in a platinum crucible, for example, and melted at approximately 800 to 1000°C for 30 to 60 minutes, cooled, and ground to 10 μl or less using, for example, an alumina ball mill. .

Next, this glass powder is analyzed using a thermal analyzer manufactured by Rigakusha Type A Co., Ltd.
Ken Hamano wai! ! The transition temperature and heat distortion temperature of this glass powder are measured according to the method described in 644, published by Asakura Shoten in 1980.

In addition, in order to obtain a low melting point glass with a transition temperature exceeding 260°C and below 290°C, pbo so ~ 85% by weight, B
tos 5~7m! Amount% 25ift 1-3% by weight, B
i, 0°3-5% by weight, PbF, 0-7% by weight 25b
Js, 0-4 weight 1%, AlF30-2! lj1%, T1
．． Preferably, the composition consists of 0 to 3% by weight of O.

The above PbO is the main component of the amorphous low melting point glass and is a necessary component to lower the transition temperature, but if the proportion in the above low melting α glass exceeds 85% by weight, it tends to crystallize, If the temperature is less than 290°C, the transition temperature tends to exceed 290°C, and therefore the sealing temperature becomes 400°C or higher, which is almost the same as conventional low melting point glass.

B. Islands are components that make glass easily soluble and prevent crystallization, but if the proportion in the low melting point glass exceeds 71!1%, the transition temperature will exceed 290 ° C., and if it is less than 25% by weight, it will not crystallize. It tends to become easier.

5in2 is a component that improves the water resistance of glass and makes it easily soluble, but the proportion in the above low melting point glass is 3m
When it exceeds 11%, the transition temperature exceeds 290'C, and when it is less than 1% by weight, the water resistance of the glass tends to deteriorate.

BizO is a component that lowers the transition temperature of glass, but if its proportion in the low melting point glass exceeds 5% by weight, the glass tends to crystallize easily, and if it is less than 3% by weight, it lowers the transition temperature. It has no effect.

PbF2 is a component that lowers the transition temperature of glass,
If the proportion in the low melting point glass exceeds 7% by weight, the glass tends to crystallize easily, which is not preferable.

sb, o, are components that lower the transition temperature of glass, and if their proportion in the low melting point glass exceeds 4% by weight, the glass tends to crystallize, which is not preferred.

AffiF is a component that lowers the transition temperature of glass, and if its proportion in the low melting point glass exceeds 2% by weight, the glass tends to crystallize, which is not preferred.

Tffi,0 is a component that lowers the transition temperature of glass, and even if its proportion in the low melting point glass exceeds 3% by weight, it can be replaced with an amorphous glass with a low transition temperature, but this is not preferred because it increases the cost.

The raw material for obtaining the above-mentioned low melting point glass has a transition temperature of 2.
In addition to the raw materials for obtaining a low melting point glass of 60° C. or lower, antimony dioxide and aluminum fluoride manufactured by Gotsu Pharmaceutical Co., Ltd., for example, are used.

The preparation method for obtaining the above-mentioned low melting point glass and the method for measuring the transition temperature and heat distortion temperature are as follows:
It is carried out according to the method for obtaining low melting point glass below.

Next, low melting point glass with a transition temperature of 260°C or less (hereinafter referred to as
A low melting point glass composition can be obtained by blending a low melting point glass (hereinafter referred to as group 1) with a transition temperature of over 260°C and below 290°C (hereinafter referred to as group Ⅰ) in a predetermined ratio. The ratio of group 1 to group 2 is 20 to 50% by weight for group 1 and 50 to 80% by weight for group 2. The ratio of group 1 in the low melting point glass composition is 201! amount%
When the glass is less than 80% (the amount of the ■ group exceeds 80!!), the effect of the low melting point glass of the ■ group is large, and when it is used as a sealing composition, the sealing temperature is lower than when the ■ group is used as it is. In the low melting point glass composition with no change, the proportion of the 1st group exceeds 50% by weight (the ■ group is less than 50% by weight)
In this case, the sealing temperature of the sealing composition becomes low and the influence of the first group increases, but the cost increases and is not very practical.

Next, by adding a low expansion filler to the low melting point composition obtained above, a low melting point glass composition for M wear can be obtained. I filler is 15 to 20% by weight based on the low melting point glass composition in order to match the thermal expansion of the obtained low melting point glass composition with the alumina paracake and to increase the impact strength of the low melting point glass composition. Use the ratio of

The low expansion filler is added to the glass powder with a diameter of 10 μm or less.
A low expansion filler of about 10 #m is mixed in a ball mill or the like. Examples of low-expansion fillers commonly used include copillite, zircon, β-eucryptite, lead titanate, and willemite.

Production Examples 1 to 4 As raw materials for obtaining the first group of low melting point glasses, red lead, boric acid, silica powder, bismuth oxide, lead fluoride, manufactured by Gotsu Pharmaceutical Co., Ltd.
Ilffi example 1 in Table 1 using thallium oxide etc.
Adjust the composition so that it has a composition of ~4, put it in a platinum crucible, and add
After melting at 00 to 1000°C for 30 to 60 minutes, the mixture was poured onto a metal plate and cooled to obtain a thin plate of glass. This thin glass plate was ground to 10 μm or less using an alumina ball mill or the like.

Next, this glass powder Loomg was heated to r7 using a thermal analyzer manufactured by Rigaku Denki Co., Ltd. at a heating rate of 10°C/win.
According to the method described in ``Yin Ceramic Handbook'', Kenya Hamano Collection, published by Asakura Shoten in 1981, 644, the transition temperature of this glass powder and thermal production examples 5 to 10 ■ Group low melting point glasses were obtained. In addition to the raw materials for obtaining a low-melting glass having a transition temperature of 260° C. or lower, antimony dioxide and aluminum fluoride manufactured by Ishizu Pharmaceutical Co., Ltd. were used as raw materials for this purpose.

Preparation method for obtaining the above-mentioned low melting point glass The measuring method of the transition temperature and heat distortion temperature was carried out according to the method explained in Production Examples 1 to 4, and the results were summarized as Example 1 Group 1 of low melting point glass. As for the glass powder with a transition temperature of 258.5°C described in Production Example 2 in Table 1, 40% by weight, the transition temperature described in Production Example 9 in Table 2 as the low melting point glass of Group ■ is 286% by weight. .5℃ glass powder 60wt 1%
A low melting point glass composition prepared at a ratio of 1 to 1 was prepared, and the transition temperature was measured according to the method described in Production Examples 1 to 4.

The transition temperature of this low melting point glass composition was 281.0° C., which was between the transition temperatures of Group 1 and Group II, and showed a combined effect of Group 1 and Group II. The reason for this is not as clear as it is now, but it is due to the effect that glass with a low transition temperature melts first, which promotes the melting of glass with a high transition temperature, shifting the transition temperature to the lower temperature side. it is conceivable that.

Next, a sealing composition was prepared by adding 15'ml of hoopillite powder with a particle size of 8 μl as a low expansion filler to 85% by weight of the powder of this low melting point glass composition.

I got it next! Measuring the B deposition temperature of the t'Jt composition;
, the results are shown in Table 3.

The sealing temperature was determined by measuring the 70-button diameter. That is, sealing composition 10. Take a diameter of 20
Samples were pressure-molded into cylindrical shapes of 11 waterfalls and heated at each temperature for 10 minutes. Then measure the 70-button diameter,
The lowest temperature at which the diameter became 25.6 mm or more was defined as the sealing temperature.

(When sealing an alumina package, it is said that the 70-button diameter of the sealing tube composition needs to be 25.6 g in diameter + waterfall after heating.) Additional Example 2~
6 A low melting point glass composition was prepared by blending the low melting point glass of Group 1 in Table 1 and the m.f. melting point glass of Group ■ in Table #Ik2 to have the composition shown in Table 3, and manufacturing examples 1 to 6. The transition temperature was measured according to the method described in 4.

Next, the copillite powder used in Example 1 as a low-expansion filler was added to this low-melting point glass composition so as to have the composition shown in 3R to obtain a sealed @acid.

The sealing temperature of the obtained sealing composition was measured in the same manner as in Example 1.

The results are also listed in Table 3.

Comparative Example 1 A sealing composition was obtained by adding the low melting point glass prepared in 91 Preparation Example 2 and the copillite powder used in Example 1 so as to have the composition shown in Table 3.

The sealing temperature of the original ITS composition was measured in the same manner as in Example 1. The results are also listed in Table 3.

Comparative Example 2 A powder composition was obtained by adding the low melting point glass with a particle size of 10 μl obtained in Production Example 9 and the copillite powder used in Example 1 so as to achieve the ffi values shown in Table 3.

The obtained IT clothing composition! The tM temperature was measured in the same manner as in Example 1. The results are also listed in Table 3.

[Effects of 5 & Bright] As explained above, the present invention has a first group of low melting point glasses and
By utilizing the advantages of both low melting point glasses in the group, the sealing temperature of the alumina package can be lowered to 400°C or less, thereby providing a low melting point glass with an economically superior composition for ITl. It is urume.

Further, the low melting point glass of the present invention is particularly suitable for sealing IC packages, but can also be used for sealing panel glass and 77-nel glass when manufacturing cathode ray tubes.

Claims (3)

[Claims] (1) It is characterized by consisting of a low melting point glass powder and a low expansion filler, which are a combination of an amorphous glass group with a transition temperature of 260°C or lower and an amorphous glass group with a transition temperature of over 260°C and 290°C or lower. A low melting point glass composition for sealing. (2) The composition of the amorphous glass group having a transition temperature of 260°C or less is PbO40 to 50% by weight, B_2O_310 to
12% by weight, SiO_21-3% by weight, Bi_2O_3
1-3% by weight, PbF_25-10% by weight, Tl_2O
The low melting point glass composition for sealing according to claim (1), wherein the content is 15 to 35% by weight. (3) The composition of the amorphous glass group whose transition temperature exceeds 260°C and is below 290°C is PbO80 to 85% by weight, B
_2O_35-7% by weight, SiO_21-3% by weight, B
i_2O_33-5% by weight, PbF_20-7% by weight,
Sb_2O_30-4% by weight, AlF_30-2% by weight
, Tl_2O0 to 3% by weight
) The low melting point glass composition for sealing as described in item 1.