JP3149929B2 - Low melting point sealing composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low melting point sealing composition, and more specifically to a low melting point sealing composition suitable for sealing electronic components such as ceramic packages for ICs , display devices , and magnetic heads. It is about things.

[0002]

2. Description of the Related Art IC packages , display devices and magnetic devices
Materials used for sealing electronic components such as a pad include
It is required that sealing can be performed at a low temperature so as not to adversely affect C, a quartz oscillator, or the like, and that the coefficient of thermal expansion conforms to that of the object to be sealed . Particularly, in addition to these conditions, a sealing material for an IC package has a high mechanical strength, a good insulating property so that a signal current does not leak, and an IC element is irradiated with α rays. Therefore, it is necessary to satisfy such a condition that a substance emitting α-rays is not contained as much as possible.

Conventionally, those satisfying the above conditions are as follows:
PbO-B ₂ O ₃ -based, and low-melting glass such as PbO-B ₂ O ₃ -ZnO system, the sealing material made by adding a refractory filler to these glasses have been proposed. For example, in Japanese Patent Laid-Open No. 2-229738 comprising the invention of the present inventors, the PbO-B ₂ O ₃ -based glass, the sealing material is disclosed comprising the addition of lead titanate-based ceramic powder and a low-expansion ceramic powder ing.

[0004]

Generally, PbO-B ₂
In O ₃ glass and PbO—B ₂ O ₃ —ZnO glass, the lower the content of B ₂ O ₃ , the lower the transition point,
It is known that the sealing temperature can be lowered. However, since B ₂ O ₃ needs to be contained in a certain amount or more for stabilizing the glass, there is a limit to the lowering of the melting point in the sealing material using these glasses, and the sealing temperature is set at 400 ° C.
It is difficult to keep the temperature below ° C. Therefore, these sealing materials are very sensitive to heat, such as highly integrated ICs.
It cannot be used for sealing a package or a device mounted with a special crystal resonator.

[0005] The present invention has been made in view of the above circumstances,
Electronic parts such as IC packages , display devices , and magnetic heads
Satisfies the characteristics required for the sealing material of the product.
An object of the present invention is to provide a sealing composition that can be sealed at a temperature of not more than ° C.

[0006]

As a result of various studies, the present inventors have found that PbO--B ₂ O ₃ based
It has been found that e ₂ O ₃ is very effective in stabilizing the glass, and that the content of B ₂ O ₃ can be reduced by adding Fe ₂ O ₃ , and this is proposed as the present invention.

That is, the low melting point sealing composition of the present invention comprises 65.0 to 85.0% of PbO and B ₂ O _{3 by} weight percentage.
_{1.0~11.0%, Fe 2 O 3 0.2~10.0} %,
_{Bi 2 O 3 1.0~15.0%, ZnO} 0~10.0
_{%, CuO 0~5.0%, Bi 2} O 3 + ZnO + Cu
O 1.0 to 15.0%, SiO ₂ + Al ₂ O ₃ 0
_{5.0%, V 2 O 5 0~5.0} %, F 2 0~6.0%,
It is characterized by being made of glass having a composition of SnO _{2 0 to} 5.0%.

[0008] Low-melting sealing composition of the present invention, PbO from 65.0 to 85.0% by weight percentage, B ₂ O ₃ 1.
_{0~11.0%, Fe 2 O 3 0.2~10.0} %, Bi
₂ O ₃ 1.0-15.0%, ZnO 0-10.0%,
_{CuO 0~5.0%, Bi 2 O 3} + ZnO + CuO
1.0-15.0%, SiO ₂ + Al ₂ O ₃ 0-5.0
_{%, V 2 O 5 0~5.0%} , F 2 0~6.0%, SnO
₂ glass having a 0 to 5.0% of the composition 45-80% by volume
And 20 to 55% by volume of the refractory filler.

[0009]

[Action] low melting point sealing composition of the present invention, PbO-B ₂
Some of the B ₂ O ₃ of O ₃ based glass was replaced by Fe ₂ O _3,
The content of B ₂ O ₃ was reduced.

The reasons for limiting the glass composition in the low melting point sealing composition of the present invention as described above will be described below.

[0011] The content of PbO is 65.0 to 85.0%,
Preferably it is 70.0 to 83.0%. PbO is 6
If it is less than 5.0%, the viscosity of the glass increases,
The glass does not flow sufficiently at a temperature of not more than ℃, and if it is more than 85.0%, crystallization becomes remarkable at the time of sealing and the glass does not flow.

The content of B ₂ O ₃ is 1.0 to 11.0%,
Preferably it is 2.0 to 10.0%. B ₂ O ₃ is 1.
If the amount is less than 0%, the glass becomes unstable, and crystallization becomes remarkable at the time of sealing, and the glass does not flow.

Fe ₂ O ₃ has a function of stabilizing glass, and its content is 0.2 to 10.0%, preferably 0.5 to 8.5%. If the content of Fe ₂ O ₃ is less than 0.2%, the above-mentioned effects are not obtained, and the crystallization becomes remarkable at the time of sealing, the fluid does not flow. Will not flow sufficiently.

Bi ₂ O ₃ , ZnO and CuO are components that stabilize the glass without increasing the viscosity of the glass.
It is contained in a total amount of 1.0 to 15.0%. Bi ₂ O ₃ , Zn
If the total amount of O and CuO is less than 1.0%, crystallization is remarkable, the fluidity is reduced, and sealing cannot be performed at a temperature of 400 ° C. or less. Also, when it is more than 15.0%, precipitation of crystals becomes remarkable at the time of sealing, and the fluidity decreases. Note in these components, in particular Bi ₂ O ₃ is above effects is large, you containing from 1.0 to 15.0%. ZnO and Cu
O content is 0 to 10.0% and 0 to 5.0%, respectively.
It is .

SiO ₂ and Al ₂ O ₃ have an effect of preventing devitrification, and their content is 0 to 5.0% in total, preferably 0 to 3.0%. If the total amount of SiO ₂ and Al ₂ O ₃ is more than 5%, the viscosity of the glass increases and the fluidity deteriorates.

V ₂ O ₅ is a component that lowers the surface tension of glass to improve the flowability, and its content is 0 to 5.0.
%, Preferably 0 to 3.0%. V ₂ O ₅ is 5.0
%, The crystallization of the glass becomes remarkable and the glass does not flow.

F ₂ has the function of lowering the sealing temperature of glass, and its content is 0 to 6.0%, preferably 0 to 4.0%.
%. If the content of F ₂ is more than 6.0%, crystallization becomes remarkable at the time of sealing, making it difficult to flow.

SnO ₂ is used in order to stabilize the glass.
It contains 5.0%, preferably 0 to 2.0%. SnO ₂
Is more than 5.0%, the viscosity of the glass becomes high and the glass becomes difficult to flow.

In addition to the above components, 5% or less of Ag _{2
O, SrO, BaO, P 2} O 5, Co 2 O 3 and 3% or less of _{Mo 2 O 3, Rb 2 O} , Cs 2 O, Nb 2 O 5, T
a ₂ O ₃ , ZrO ₂ , CeO ₂ , NiO, Cr ₂ O ₃ ,
Rare earth oxides such as Sb ₂ O ₃ and La ₂ O ₃ can be contained as other components.

Glass having the above composition has a low glass transition point of 240 to 300 ° C., is stable as glass, and has good fluidity, so that it can be sealed at a low temperature. It is a wearing composition. However, 30-2
The thermal expansion coefficient at 50 ° C. is 110 to 140 × 10 ⁻⁷ , alumina (70 × 10 ⁻⁷ / ° C.), aluminum nitride (4
5 × 10 ⁻⁷ / ° C.) and higher than window glass (85 × 10 ⁻⁷ / ° C.), so the thermal expansion coefficient is adjusted to seal IC packages and display devices using these materials. There is a need to.

The low melting point sealing composition of the present invention can obtain a thermal expansion coefficient suitable for sealing an IC package or a display device by containing a refractory filler in the above-mentioned range. Examples of the refractory filler include powders of lead titanate-based ceramic, willemite-based ceramic, β-eucryptite, cordierite, zircon-based ceramic, tin oxide-based ceramic, mullite-based ceramic, quartz glass, alumina, and titanium oxide. It is preferable to use them alone or in combination.

In the present invention, the reason why the mixing ratio of the glass and the refractory filler is limited as described above will be described below.

When the glass content is less than 45%, that is, when the content of the refractory filler is more than 55%, the fluidity deteriorates and the sealing cannot be performed at a temperature of 400 ° C. or less. On the other hand, when the glass content is more than 80%, that is, when the refractory filler content is less than 20%, the above effects cannot be obtained.

Next, a method for producing the low melting point sealing composition of the present invention will be described. First, each raw material is prepared so as to have a desired composition, melted at 700 to 1000 ° C. for 1 to 2 hours, and then formed into a plate. Next, the plate-like material is pulverized by a ball mill or the like, and then classified to a predetermined particle size to obtain a powdery glass. If necessary, the glass powder thus obtained and the refractory filler are mixed at a predetermined ratio.

[0025]

EXAMPLES The low melting point sealing composition of the present invention will be described below based on examples.

Example 1 Table 1 shows Fe ₂ O ₃ in PbO—B ₂ O ₃ glass.
The effect of the sample No. a is a sample No. a is a general PbO—B ₂ O ₃ glass, and the sample No. b is a sample No. b.
Pb in which the content of B ₂ O ₃ is reduced by 4% from the composition of a
OB ₂ O ₃ -based glass, sample No. c shows the low melting point sealing composition of the present invention in which 2% of Fe ₂ O ₃ was added to sample No. b.

[0027]

[Table 1]

The samples in Table 1 were prepared as follows.

The raw material powder was prepared so as to have the composition shown in the table,
The mixture was put into a platinum crucible, melted at 900 ° C. for 1 hour, formed into a thin plate, crushed, and passed through a 250-mesh stainless steel sieve to obtain a sample having an average particle size of 4 μm.

As is clear from Table 1, the glass transition point of Sample No. b having a reduced B ₂ O ₃ content was 285 ° C.
Although the temperature was lowered by 20 ° C. as compared with Sample No. a,
The fluidity and stability were poor. On the other hand, Sample No. c to which Fe ₂ O ₃ was added had a glass transition point of 287 ° C., exhibited a low value equivalent to that of Sample No. b, and had better fluidity than Sample No. a. The stability was good.

These facts indicate that even if the content of B ₂ O ₃ is reduced to lower the glass transition point, good fluidity and stability can be obtained by adding Fe ₂ O ₃ , 2 shows that a sealing composition that can be sealed by the above method is obtained.

The glass transition point is determined by a differential thermal analyzer (DT).
A). The fluidity is 20 m outside diameter from the sample.
m, a button with a height of 5 mm, and then
Minutes, the diameter of the button at this time is 23mm
Over 20 mm, 20 to 23 mm, 20 m
Those less than m were rejected. The stability was evaluated by visually observing the surface of the sample after the fluidity test. If no crystal was observed, the sample was evaluated as good.

Example 2 Table 2 shows Examples of the low melting point sealing composition comprising glass in the present invention.

[0034]

[Table 2]

As is clear from Table 2, Sample Nos.
F has a glass transition point of 246 to 295 ° C. and a thermal expansion coefficient of 1
15 to 132 × 10 ⁻⁷ / ° C., all showing good fluidity.

Each sample in Table 2 was prepared in the same manner as in Example 1.

Tables 3 and 4 show Examples (Sample Nos. 1 to 9) of low melting point sealing compositions for IC packages prepared by mixing each sample of Table 2 with a refractory filler. is there.

[0038]

[Table 3]

[0039]

[Table 4]

As apparent from Tables 3 and 4, the sample N
o. 1 to 9, the sealing temperature was 360 to 400 ° C., the bending strength was 590 to 680 kg / cm ² , and the insulation resistance was 13.2 to 13.
14.8Ω · cm, α-ray emission 0.11-0.25c
out / cm ² · hr, which was a good value. The thermal expansion coefficient of Sample Nos. 1 to 6 was 60 to 73 × 10 ⁻⁷ /
° C, Sample Nos. 7 to 9 have a value of 51 to 55 × 10 ^-7 / ° C, which are values approximate to alumina (70 × 10 ^-7 / ° C) and aluminum nitride (45 × 10 ^-7 / ° C), respectively. Was.

Table 5 shows examples (sample Nos. 10 to 12) of low melting point sealing compositions for display devices prepared by mixing a refractory filler with the samples of Table 2.

[0042]

[Table 5]

As is clear from Table 5, Sample No. 10
No. 12 has a low sealing temperature of 380 to 390 ° C. and a coefficient of thermal expansion of 73 to 78 × 10 ⁻⁷ / ° C., which is a value close to that of the window glass (85 × 10 ⁻⁷ / ° C.). Was.

These facts indicate that the low melting point sealing composition of the present invention satisfies various conditions required for sealing materials for IC packages and display devices, and that the composition can be sealed particularly at a low temperature of 400 ° C. or less. It shows that the thermal expansion coefficient can be adjusted to be compatible with alumina, aluminum nitride, window glass, etc., by containing an appropriate amount of the conductive filler powder.

The coefficient of thermal expansion was measured using a push rod type thermal expansion measuring device. In addition, an outer diameter of 20
A button having a height of 5 mm and a height of 5 mm was heated and caused to flow, and the temperature when the outer diameter became 21 mm or more was defined as the sealing temperature.
The transverse rupture strength was determined by sintering the sample into a 10 × 10 × 50 mm prism and measuring it by a three-point load measurement method. The insulation resistance was measured at 150 ° C. using a megohmmeter, and the α-ray emission was measured using a ZnS scintillation counter.

The refractory fillers shown in Tables 3 to 5 were produced as follows.

The lead titanate-based ceramic contains 65% by weight of PbO by weight of litharge, titanium oxide and calcium carbonate.
The mixture was prepared so as to have a composition of TiO ₂ 30% and CaO 5%. After mixing, the mixture was fired at 1100 ° C. for 5 hours. Then, the fired product was pulverized with alumina balls and passed through a 350 mesh stainless steel sieve. A powder having an average particle size of 5 μm was obtained.

The willemite-based ceramic is composed of zinc oxide, optical stone powder, and aluminum oxide in a weight percentage of 70% ZnO,
It is prepared so as to have a composition of 25% of SiO _{2 and} 5% of Al ₂ O _3. After mixing, the mixture is baked at 1440 ° C. for 15 hours, and then the baked product is pulverized and passed through a 250-mesh stainless steel sieve. used.

Β-eucryptite is lithium carbonate,
Alumina, optical stone powder Li ₂ O.Al ₂ O ₃ .2SiO
Formulated such that the _second composition, after mixing, 5 at 1250 ° C.
After firing for a time, the fired product was pulverized and used after passing through a 250-mesh stainless steel sieve.

The zircon-based ceramic was produced as follows. First, the natural zircon sand is once decomposed with soda, dissolved in hydrochloric acid, and then concentrated and crystallized repeatedly, thereby obtaining zirconium oxychloride having a very small amount of U and Th, which are α-ray emitting substances, neutralizing with alkali, and heating. Purified ZrO ₂ was obtained. Moreover high purity silica powder in this purification ZrO _2, ZrO ₂ 66% ferric oxide by weight%, SiO
₂ 32%, formulated to be Fe ₂ O ₃ 2% of the composition, after mixing, was calcined for 16 hours at 1400 ° C., then grinding the calcined product, used after passing through a stainless steel sieve of 250 mesh did.

The tin oxide ceramic is SnO ₂ in weight%.
93%, TiO _{2 2%,} formulated to be MnO ₂ 5% of the composition, after mixing, was calcined for 16 hours at 1400 ° C., then grinding the calcined product, those having passed through the 250-mesh stainless sieve used.

The mullite ceramic is prepared by mixing aluminum oxide and optical stone powder so as to have a composition of 3Al ₂ O ₃ .2SiO ₂ , and after mixing, firing at 1600 ° C. for 10 hours.
Next, the fired product was pulverized and used after passing through a 250 mesh stainless sieve.

Cordierite is magnesium oxide,
Aluminum oxide, optical stone powder 2MgO.2Al ₂ O ₃
・ Mix to a ratio of 5SiO ₂ , and after mixing, 14
Calcined at 00 ° C. for 10 hours, then pulverized the calcined product,
What passed through a 250 mesh stainless sieve was used.

[0054]

As described above, the low melting point sealing composition of the present invention can be used for an IC package , a display device , and a magnetic head.
It satisfies various characteristics required for a sealing material for electronic parts such as a pad and can be sealed at a low temperature of 400 ° C. or less.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 8/10 C03C 3/072 C03C 3/074 C03C 8/24

Claims (2)

(57) [Claims] 1. PbO 65.0 to 85.
0%, B ₂ O ₃ 1.0 to 11.0%, Fe ₂ O ₃ 0.2
_{~10.0%, Bi 2 O 3 1.0~15.0} %, ZnO
0~10.0%, CuO 0~5.0%, Bi 2 O 3 +
ZnO + CuO 1.0-15.0%, SiO ₂ + Al
_{2 O 3 0~5.0%, V 2} O 5 0~5.0%, F 2 0~
A low melting point sealing composition comprising glass having a composition of 6.0% and SnO _{2 of 0 to} 5.0%. 2. PbO 65.0 to 85.5% by weight.
0%, B ₂ O ₃ 1.0 to 11.0%, Fe ₂ O ₃ 0.2
_{~10.0%, Bi 2 O 3 1.0~15.0} %, ZnO
0~10.0%, CuO 0~5.0%, Bi 2 O 3 +
ZnO + CuO 1.0-15.0%, SiO ₂ + Al
_{2 O 3 0~5.0%, V 2} O 5 0~5.0%, F 2 0~
45-80% by volume of glass having a composition of 6.0% and SnO ₂ 0-5.0%, and 20-55% by volume of a refractory filler.
A low melting point sealing composition, comprising: