JPH0597470A - Sealing composition having low melting point - Google Patents

Sealing composition having low melting point

Info

Publication number
JPH0597470A
JPH0597470A JP28357691A JP28357691A JPH0597470A JP H0597470 A JPH0597470 A JP H0597470A JP 28357691 A JP28357691 A JP 28357691A JP 28357691 A JP28357691 A JP 28357691A JP H0597470 A JPH0597470 A JP H0597470A
Authority
JP
Japan
Prior art keywords
sealing
powder
pbo
glass
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP28357691A
Other languages
Japanese (ja)
Inventor
Hajime Hikata
元 日方
Hisami Tanaka
久美 田中
Kazuyoshi Shindo
和義 新藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP28357691A priority Critical patent/JPH0597470A/en
Publication of JPH0597470A publication Critical patent/JPH0597470A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C03C8/245Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders containing more than 50% lead oxide, by weight

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

PURPOSE:To obtain a sealing compsn. having a low m.p., not contg. a poisonous substance such as T1, capable of sealing at a low temp. of <=400 deg.C without applying load and fit to seal an IC package, a quartz oscillator package CONSTITUTION:This sealing compsn. consists of 45-80 vol.% glass powder having a low m.p. and 20-55 vol.% powder of a low expansion or high expansion refractory filler. The glass powder has a compsn. consisting of, by weight, 70.3-92.0% PbO, 1.0-10.0% B2O3 (B2O3/PbO<=0.11), 5.2-20.0% Bi2O3, 0.01-8.0% F2, 0-15.0% ZnO, 0-5.0% V2O5, 0-2.0% SiO2, 0-2.0% Al2O3, 0-2.0% SnO2 and 0-4.0% BaO.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は低融点封着用組成に関
し、より詳しくはICパッケージや水晶振動子パッケー
ジ等の電子部品を封着するのに好適な低融点封着用組成
物に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low melting point sealing composition, and more particularly to a low melting point sealing composition suitable for sealing electronic parts such as IC packages and crystal oscillator packages.

【0002】[0002]

【従来の技術】ICパッケージや水晶振動子パッケージ
の封着に使用される封着用組成物には、ICや水晶振動
子に悪影響を及ぼさないように低温で封着できること
や、熱膨張係数がパッケージの材料に適合していること
が要求される。また特にICパッケージ用の封着材料に
は、これらの条件の他に機械的強度が高いこと、信号電
流がリークしないように絶縁特性が良好であること、I
C素子にα線が照射されるとソフトエラーが発生するた
め、α線を放出する物質を極力含まないこと等の条件を
満たす必要がある。
2. Description of the Related Art A sealing composition used for sealing an IC package or a crystal oscillator package can be sealed at a low temperature so as not to adversely affect the IC or the crystal oscillator, and has a thermal expansion coefficient of the package. It is required to be compatible with the material. In addition to these conditions, the sealing material for the IC package has high mechanical strength and good insulation characteristics so that signal current does not leak.
When the C element is irradiated with α rays, a soft error occurs. Therefore, it is necessary to satisfy the condition that the substance that emits α rays is not included as much as possible.

【0003】従来より、上記諸条件を満たすものとし
て、PbO−B23 系、PbO−B23 −ZnO
系、PbO−B23 −Bi23 系等の低融点ガラス
粉末や、これらのガラス粉末に耐火性フィラー粉末を添
加してなる各種の封着用組成物が知られている。しかし
ながらこれら従来の封着用組成物は、400℃以下の温
度で封着することが困難であり、熱に非常に敏感な素
子、例えば集積度の高いICや特殊な水晶振動子等を搭
載したパッケージの封着には使用することができない。
Conventionally, as the various condition is satisfied, PbO-B 2 O 3 system, PbO-B 2 O 3 -ZnO
System, and the low melting point glass powder, such as PbO-B 2 O 3 -Bi 2 O 3 system, various sealing compositions obtained by adding a refractory filler powder to these glass powders are known. However, these conventional sealing compositions are difficult to seal at a temperature of 400 ° C. or lower, and are extremely sensitive to heat, for example, a package equipped with a highly integrated IC or a special crystal oscillator. Can not be used for sealing.

【0004】このような事情から、400℃以下の温度
で封着できる封着用組成物の開発が進められている。例
えばPbO−B23 −Tl2 O系ガラス粉末や、これ
に低膨張耐火フィラー粉末を混合して低膨張化した封着
用組成物が特公昭63−8060号において提案され、
また米国特許第4743302号にはPbO−V25
−TeO2 系ガラス粉末や、これに低膨張耐火フィラー
粉末を混合してなる封着用組成物が開示されている。
Under these circumstances, the development of a sealing composition which can be sealed at a temperature of 400 ° C. or lower is underway. For example, PbO-B 2 O 3 -Tl 2 O -based glass powder, a mixture of low-expansion refractory filler powder sealing composition low expansion of is proposed in Japanese Patent Publication No. 63-8060 to,
Also U.S. Pat. No. 4743302 PbO-V 2 O 5
A TeO 2 -based glass powder and a sealing composition prepared by mixing it with a low expansion refractory filler powder are disclosed.

【0005】[0005]

【発明が解決しようとする課題】しかしながら、上記特
公昭63−8060号に開示の封着用組成物は、有毒物
質であるTlを多量に含むため、製造時や封着作業時に
粉塵の飛散を防ぐための特別な設備を必要とする。また
米国特許第4743302号に開示の封着用組成物は、
結晶化傾向が強いために流動性が悪く、それゆえ封着時
に強い荷重をかけなければならないといった問題を有し
ている。
However, since the sealing composition disclosed in Japanese Patent Publication No. 63-8060 contains a large amount of Tl which is a toxic substance, dust scattering is prevented during manufacturing or sealing work. Need special equipment for. The sealing composition disclosed in U.S. Pat. No. 4,743,302 is
Since it has a strong tendency to crystallize, it has poor fluidity, and therefore has a problem that a strong load must be applied during sealing.

【0006】本発明の目的は、Tl等の有毒物質を含ま
ず、また荷重をかけることなく400℃以下の低温で封
着することができ、ICパッケージや水晶振動子パッケ
ージ等の封着に好適な低融点封着用組成物を提供するこ
とである。
An object of the present invention is that it does not contain toxic substances such as Tl and can be sealed at a low temperature of 400 ° C. or lower without applying a load, and is suitable for sealing IC packages, crystal oscillator packages, etc. A low melting point sealing composition is provided.

【0007】[0007]

【課題を解決するための手段】本発明者等は種々の研究
を行った結果、PbO−B23 −Bi23 系ガラス
において、重量比でB23 /PbOを0.11以下に
調整し、且つ、Bi23 を5.2%以上、及びF2
0.01%以上含有させることにより、上記目的が達成
できることを見いだし、本発明として提案するものであ
る。
The present inventors have SUMMARY OF THE INVENTION The result of various studies, the PbO-B 2 O 3 -Bi 2 O 3 based glass, a B 2 O 3 / PbO in a weight ratio 0.11 It has been found that the above object can be achieved by adjusting below and containing Bi 2 O 3 of 5.2% or more and F 2 of 0.01% or more, and it is proposed as the present invention.

【0008】即ち、本発明の低融点封着用組成物は、重
量百分率で、PbO 70.3〜92.0%、B23
1.0〜10.0%、Bi23 5.2〜20.0%、
20.01〜8.0%、ZnO 0〜15.0%、V2
5 0〜5.0%、SiO2 0〜2.0%、Al23
0〜2.0%、SnO2 0〜2.0%、BaO 0〜
4.0%の組成を有し、且つ、B23 /PbO比が
0.11以下のガラス粉末からなることを特徴とする。
That is, the low melting point sealing composition of the present invention has a weight percentage of PbO 70.3 to 92.0% and B 2 O 3
1.0~10.0%, Bi 2 O 3 5.2~20.0 %,
F 2 0.01~8.0%, ZnO 0~15.0% , V 2
O 5 0~5.0%, SiO 2 0~2.0 %, Al 2 O 3
0-2.0%, SnO 2 0-2.0%, BaO 0-
It is characterized in that it is composed of glass powder having a composition of 4.0% and a B 2 O 3 / PbO ratio of 0.11 or less.

【0009】また本発明の低融点封着用組成物は、重量
百分率で、PbO 70.3〜92.0%、B23
1.0〜10.0%、Bi23 5.2〜20.0%、
2 0.01〜8.0%、ZnO 0〜15.0%、V
25 0〜5.0%、SiO20〜2.0%、Al23
0〜2.0%、SnO2 0〜2.0%、BaO 0〜
4.0%の組成を有し、且つ、B23 /PbO比が
0.11以下であるガラス粉末45〜80体積%と、耐
火性フィラー粉末20〜55体積%からなることを特徴
とする。
The low melting point sealing composition of the present invention has a weight percentage of PbO 70.3 to 92.0% and B 2 O 3
1.0~10.0%, Bi 2 O 3 5.2~20.0 %,
F 2 0.01 to 8.0%, ZnO 0 to 15.0%, V
2 O 5 0-5.0%, SiO 2 0-2.0%, Al 2 O 3
0-2.0%, SnO 2 0-2.0%, BaO 0-
45% to 80% by volume of a glass powder having a composition of 4.0% and a B 2 O 3 / PbO ratio of 0.11 or less, and 20 to 55% by volume of a refractory filler powder. To do.

【0010】[0010]

【作用】本発明の低融点封着用組成物において、ガラス
粉末の組成範囲を上記のように限定した理由を以下に述
べる。
The reason why the composition range of the glass powder in the low melting point sealing composition of the present invention is limited as described above will be described below.

【0011】PbOの含有量は70.3〜92.0%、
好ましくは70.5〜83.0%である。PbOが7
0.3%より少ないとガラスの粘度が高くなって、ガラ
スが十分に流動せず、92.0%より多いと封着時に結
晶化を起こして流動しなくなる。
The PbO content is 70.3-92.0%,
It is preferably from 70.5 to 83.0%. PbO is 7
If it is less than 0.3%, the viscosity of the glass becomes high and the glass does not flow sufficiently, and if it is more than 92.0%, crystallization occurs at the time of sealing and it does not flow.

【0012】B23 の含有量は1.0〜10.0%、
好ましくは2.0〜9.5%である。B23 が1.0
%より少ないと封着時に結晶化を起こして流動せず、1
0.0%より多いと400℃以下の温度では流動し難く
なる。
The content of B 2 O 3 is 1.0 to 10.0%,
It is preferably 2.0 to 9.5%. B 2 O 3 is 1.0
If it is less than%, it will not crystallize due to crystallization during sealing, and 1
If it exceeds 0.0%, it becomes difficult to flow at a temperature of 400 ° C. or lower.

【0013】Bi23 はガラスの粘性を上げずに安定
化させる効果があり、その含有量は5.2〜20.0
%、好ましくは5.2〜19.0%である。Bi23
が5.2%より少ないと上記した効果がなく、20.0
%より多いとガラスの粘性が高くなって400℃以下の
温度で十分に流動しなくなる。
Bi 2 O 3 has the effect of stabilizing the glass without increasing its viscosity, and its content is 5.2 to 20.0.
%, Preferably 5.2 to 19.0%. Bi 2 O 3
Is less than 5.2%, the above effect does not occur and 20.0
If it is more than%, the viscosity of the glass becomes high and the glass does not flow sufficiently at a temperature of 400 ° C. or lower.

【0014】F2 はBi23 が多量に含まれるガラス
組成系において、ガラスの転移点を下げて失透を防止す
る効果があり、その含有量は0.01〜8.0%、好ま
しくは0.1〜7.0%である。F2 が0.01%より
少ないと上記した効果が得られず、封着時に失透が著し
くなって流動しなくなる。また8.0%より多くなると
ガラスの安定性が崩れ、結晶化が著しくなって流動しな
くなる。
In a glass composition system containing a large amount of Bi 2 O 3, F 2 has the effect of lowering the glass transition point and preventing devitrification, and the content thereof is 0.01 to 8.0%, preferably. Is 0.1 to 7.0%. If F 2 is less than 0.01%, the above-mentioned effect cannot be obtained, and devitrification becomes remarkable at the time of sealing, so that it does not flow. On the other hand, if it exceeds 8.0%, the stability of the glass will be impaired, and crystallization will be remarkable, resulting in no flow.

【0015】ZnOの含有量は0〜15.0%、好まし
くは0〜13.0%である。ZnOはガラスを安定化さ
せ、且つ、耐水性を向上させる効果があるが、その含有
量が15.0%より多いとガラスが結晶化して十分に流
動しなくなる。
The content of ZnO is 0 to 15.0%, preferably 0 to 13.0%. ZnO has the effect of stabilizing the glass and improving the water resistance, but if its content exceeds 15.0%, the glass crystallizes and does not flow sufficiently.

【0016】V25 の含有量は0〜5.0%、好まし
くは0〜3.0%である。V25はガラスの表面張力
を下げる効果があり、流動性を向上させるものである
が、その含有量が5.0%より多いと結晶化傾向が著し
くなって流動しなくなる。
The content of V 2 O 5 is 0 to 5.0%, preferably 0 to 3.0%. V 2 O 5 has the effect of lowering the surface tension of glass and improves the fluidity, but if its content is more than 5.0%, the tendency to crystallize becomes remarkable and it does not flow.

【0017】SiO2 の含有量は0〜2.0%、好まし
くは0〜1.0%である。SiO2は結晶化を防止する
効果があるが、その含有量が2.0%より多いとガラス
の粘度が高くなって400℃以下の温度で十分流動しな
くなる。
The content of SiO 2 is 0 to 2.0%, preferably 0 to 1.0%. SiO 2 has the effect of preventing crystallization, but if its content is more than 2.0%, the viscosity of the glass increases and it does not flow sufficiently at a temperature of 400 ° C. or lower.

【0018】Al23 の含有量は0〜2.0%、好ま
しくは0〜1.0%である。Al23 はガラスを安定
化させる効果があるが、その含有量が2.0%より多い
とガラスの粘度が高くなって400℃以下の温度で十分
流動しなくなる。
The content of Al 2 O 3 is 0 to 2.0%, preferably 0 to 1.0%. Al 2 O 3 has the effect of stabilizing the glass, but if its content is more than 2.0%, the viscosity of the glass becomes high and it does not flow sufficiently at a temperature of 400 ° C. or lower.

【0019】SnO2 の含有量は0〜2.0%、好まし
くは0〜1.5%である。SnO2はガラスの結晶化を
防止する効果があるが、その含有量が2.0%より多い
とガラスの粘度が高くなって400℃以下の温度で十分
流動しなくなる。
The content of SnO 2 is 0 to 2.0%, preferably 0 to 1.5%. SnO 2 has the effect of preventing crystallization of glass, but if its content is more than 2.0%, the viscosity of the glass becomes high and it does not flow sufficiently at a temperature of 400 ° C. or lower.

【0020】BaOの含有量は0〜4.0%、好ましく
は0〜3.0%である。BaOはガラスの結晶化を防止
する効果があるが、その含有量が4.0%より多いとガ
ラスの粘度が高くなって400℃以下の温度で十分流動
しなくなる。
The content of BaO is 0 to 4.0%, preferably 0 to 3.0%. BaO has an effect of preventing crystallization of glass, but if its content is more than 4.0%, the viscosity of glass becomes high and the glass does not flow sufficiently at a temperature of 400 ° C. or lower.

【0021】また本発明の低融点封着用組成物は、重量
比でB23 /PbOが0.11以下である。B23
/PbO比が0.11より大きくなるとガラス転移点や
封着温度が高くなって、400℃以下の温度での封着が
困難になる。
The low melting point sealing composition of the present invention has a weight ratio of B 2 O 3 / PbO of 0.11 or less. B 2 O 3
When the / PbO ratio is larger than 0.11, the glass transition point and the sealing temperature become high, and sealing at a temperature of 400 ° C. or lower becomes difficult.

【0022】なお、本発明の低融点封着用組成物は、上
記成分以外にも5.0%以下のAgO、SrO、P2
5 、Co23 、3.0%以下のMo23 、Rb2
O、Cs2 O、Nb25 、Ta23 、ZrO2 、N
iO、Cr23やLa23、CeO2 等の希土類酸化
物を他成分として含有することができる。
The low melting point sealing composition of the present invention contains, in addition to the above components, 5.0% or less of AgO, SrO and P 2 O.
5 , Co 2 O 3 , 3.0% or less of Mo 2 O 3 , Rb 2
O, Cs 2 O, Nb 2 O 5 , Ta 2 O 3 , ZrO 2 , N
Rare earth oxides such as iO, Cr 2 O 3 , La 2 O 3 and CeO 2 can be contained as other components.

【0023】以上の組成を有するガラス粉末は非晶質で
あり、封着時に結晶を析出する傾向がないため流動性が
良く、またガラス転移点が約240〜300℃以下と低
く、ガラスの粘性も低いために、低温での封着に適した
封着用組成物である。しかし熱膨張係数が110〜14
0×10-7/℃であり、アルミナ(熱膨張係数70×1
-7/℃)や窒化アルミニウム(同45×10-7/℃)
に比べて高いため、これらの材料からなるセラミックパ
ッケージや水晶振動子パッケージの封着を行うには熱膨
張係数を低下させる必要がある。一方、Al−Si合金
(熱膨張係数160×10-7/℃)等の材料からなる金
属製パッケージの封着を行うには熱膨張係数を高くする
必要がある。
The glass powder having the above composition is amorphous, has a good fluidity because it does not tend to precipitate crystals during sealing, and has a low glass transition point of about 240 to 300 ° C. or less and a glass viscosity. Since it is also low, it is a sealing composition suitable for sealing at low temperatures. However, the coefficient of thermal expansion is 110-14
A 0 × 10 -7 / ℃, alumina (thermal expansion coefficient of 70 × 1
0 -7 / ° C) and aluminum nitride (45 × 10 -7 / ° C)
Therefore, it is necessary to lower the coefficient of thermal expansion in order to seal the ceramic package and the crystal unit package made of these materials. On the other hand, in order to seal a metal package made of a material such as Al-Si alloy (coefficient of thermal expansion 160 × 10 −7 / ° C.), it is necessary to increase the coefficient of thermal expansion.

【0024】本発明の低融点封着用組成物は、先記した
範囲で1種以上の低膨張あるいは高膨張の耐火性フィラ
ーを使用することにより、所望の熱膨張係数に調整する
ことが可能である。
The low melting point sealing composition of the present invention can be adjusted to a desired coefficient of thermal expansion by using at least one low expansion or high expansion refractory filler within the above-mentioned range. is there.

【0025】低膨張の耐火性フィラーとしては、ウイレ
マイト系、酸化錫系、ジルコン系、チタン酸鉛系、及び
ムライト系のセラミック粉末や、β−ユークリプタイト
粉末、コーディエライト粉末を使用することが好まし
く、またこれらのフィラーの他に石英ガラス粉末、五酸
化ニオブ粉末等を使用することができる。
As the low-expansion refractory filler, willemite-based, tin oxide-based, zircon-based, lead titanate-based, and mullite-based ceramic powders, β-eucryptite powders, and cordierite powders should be used. In addition to these fillers, quartz glass powder, niobium pentoxide powder and the like can be used.

【0026】高膨張の耐火性フィラーとしては、錫酸亜
鉛粉末、クリストバライト粉末、立方晶ジルコニア粉末
等を使用することが好ましい。
As the high-expansion refractory filler, it is preferable to use zinc stannate powder, cristobalite powder, cubic zirconia powder, or the like.

【0027】次に、本発明においてガラス粉末と耐火性
フィラー粉末の混合割合を先記のように限定した理由を
以下に述べる。
Next, the reason for limiting the mixing ratio of the glass powder and the refractory filler powder in the present invention as described above will be described below.

【0028】ガラス粉末が45%より少ない場合、即ち
耐火性フィラー粉末が55%より多い場合は流動性が悪
くなり、400℃以下の温度での封着が困難になる。一
方、ガラス粉末が80%より多い場合、即ち耐火性フィ
ラー粉末が20%より少ない場合は上記した効果が得ら
れなくなる。
When the glass powder content is less than 45%, that is, when the refractory filler powder content is more than 55%, the fluidity is deteriorated and sealing at a temperature of 400 ° C. or less becomes difficult. On the other hand, when the glass powder content is more than 80%, that is, when the refractory filler powder content is less than 20%, the above effect cannot be obtained.

【0029】[0029]

【実施例】以下、実施例に基づいて本発明の低融点封着
用組成物を説明する。
EXAMPLES The low melting point sealing composition of the present invention will be described below based on examples.

【0030】(実施例1)(Example 1)

【0031】表1は、PbO−B23 −Bi23
ガラスにおいて、B23 /PbO比、及びBi2
3 、F2 の効果を説明するものである。試料No.aは
一般的なPbO−B23 −Bi23 系ガラス、試料
No.bは試料No.aの組成からB23 の含有量を
11.0%少なくしてB23 /PbO比を0.05に
したPbO−B23 −Bi23 系ガラスである。ま
た試料No.cは試料No.aの組成からB23 の含
有量を11.0%少なくしてB23 /PbO比を0.
05にするとともに、Bi23 の含有量を11.3%
に増加し、しかもF2 を2.0%添加した本発明の低融
点封着用組成物を示すものである。
[0031] Table 1, in the PbO-B 2 O 3 -Bi 2 O 3 based glass, B 2 O 3 / PbO ratio, and Bi 2 O
3 , to explain the effect of F 2 . Sample No. a typical PbO-B 2 O 3 -Bi 2 O 3 based glass, Sample No. b is sample No. and 11.0% less content of B 2 O 3 of a composition of a an B 2 O 3 / PbO ratio is PbO-B 2 O 3 -Bi 2 O 3 based glass was 0.05. In addition, sample No. c is sample No. From the composition of a, the B 2 O 3 content was reduced by 11.0%, and the B 2 O 3 / PbO ratio was reduced to 0.
And the Bi 2 O 3 content was 11.3%
The present invention shows a low melting point sealing composition of the present invention in which F 2 is added to 2.0% and F 2 is added at 2.0%.

【0032】[0032]

【表1】 [Table 1]

【0033】表1の各試料は次のようにして調製した。Each sample in Table 1 was prepared as follows.

【0034】表中の組成になるように原料粉末を調合、
混合し、白金坩堝に入れて900℃で1時間溶融し、薄
板状に成形した後、粉砕し、350メッシュのステンレ
ス製篩を通過させて平均粒径が4μmの試料を得た。
The raw material powders are blended so as to have the composition shown in the table,
The mixture was mixed, put in a platinum crucible, melted at 900 ° C. for 1 hour, molded into a thin plate, pulverized, and passed through a 350 mesh stainless sieve to obtain a sample having an average particle diameter of 4 μm.

【0035】表1から明らかなように、B23 の含有
量を少なくし、B23 /PbO比を0.11以下にし
た試料No.bはガラス転移点が285℃であり、試料
No.aに比べて25℃低下したものの、流動性及び安
定性が悪かった。一方、B23 /PbO比が0.11
以下であり、且つ、Bi23 を5.2%以上、またF
2 を0.01%以上含有した試料No.cは、ガラス転
移点が274℃であり、試料No. bよりさらに11℃
も低い値を示し、しかも流動性が試料No.aより優れ
ており、また安定性が良好であった。
As is clear from Table 1, the sample No. 1 having the B 2 O 3 content reduced and the B 2 O 3 / PbO ratio set to 0.11 or less. The glass transition point of sample b is 285 ° C. Although it was 25 ° C lower than that of a, the fluidity and stability were poor. On the other hand, the B 2 O 3 / PbO ratio is 0.11
And less than 5.2% of Bi 2 O 3 and F
No. 2 containing 0.01% or more of No. 2 C has a glass transition point of 274 ° C, which is 11 ° C higher than that of sample No. b.
Also shows a low value, and the fluidity of sample No. It was superior to a and had good stability.

【0036】これらの事実は、PbO−B23 −Bi
23 系ガラスにおいて、B23/PbO比を0.1
1以下に調整するとともに、Bi23 及びF2 を所定
量含有することによって、低融点で、しかも良好な流動
性及び安定性を有する封着用組成物が得られることを示
している。
These facts indicate that PbO-B 2 O 3 -Bi
In the 2 O 3 system glass, the B 2 O 3 / PbO ratio is 0.1
It is shown that a sealing composition having a low melting point and having good fluidity and stability can be obtained by adjusting the amount to 1 or less and containing Bi 2 O 3 and F 2 in predetermined amounts.

【0037】なお、ガラス転移点は示差熱分析計(DT
A)により求めた。また流動性は、1cm3 に相当する
重量の試料を外径17mm、高さ5mmのボタンに成形
した後、380℃、10分の条件で加熱し、このときの
ボタンの直径が23mmを超えるものを良、20〜23
mmのものを可、20mm未満のものを不可とした。安
定性は、流動性試験後の試料表面を目視で観察し、結晶
が全く認められなかったものを良、認められたものを不
可とした。
The glass transition point is measured by a differential thermal analyzer (DT
Determined according to A). The fluidity is such that a sample having a weight equivalent to 1 cm 3 is molded into a button having an outer diameter of 17 mm and a height of 5 mm and then heated at 380 ° C. for 10 minutes, and the diameter of the button at this time exceeds 23 mm. Good, 20-23
mm was acceptable, and those less than 20 mm were not acceptable. Regarding the stability, the surface of the sample after the fluidity test was visually observed, and the case where no crystals were observed was good, and the case where it was observed was not good.

【0038】(実施例2)(Example 2)

【0039】表2はガラス粉末からなる本発明の実施例
を示すものである。
Table 2 shows examples of the present invention made of glass powder.

【0040】[0040]

【表2】 [Table 2]

【0041】表2から明らかなように、試料No.A〜
Eは、ガラス転移点が249〜293℃、熱膨張係数が
120〜135×10-7/℃であり、すべて良好な流動
性を示した。
As is clear from Table 2, the sample No. A ~
E had a glass transition point of 249 to 293 ° C. and a thermal expansion coefficient of 120 to 135 × 10 −7 / ° C., and all showed good fluidity.

【0042】なお、表2の各試料は、実施例1と同様に
して調製した。
Each sample in Table 2 was prepared in the same manner as in Example 1.

【0043】表3乃至表5は、表2の各試料に耐火性フ
ィラー粉末を混合して作製した本発明の実施例を示すも
のであり、試料No.1〜5はアルミナパッケージ封着
用、試料No.6〜9は窒化アルミニウムパッケージ封
着用、試料No.10〜12はAl−Si合金製パッケ
ージ封着用である。
Tables 3 to 5 show Examples of the present invention prepared by mixing the refractory filler powder with each of the samples of Table 2. Sample Nos. 1 to 5 are used for sealing alumina packages. Sample Nos. 6 to 9 are for aluminum nitride package sealing. 10 to 12 are Al-Si alloy package seals.

【0044】[0044]

【表3】 [Table 3]

【0045】[0045]

【表4】 [Table 4]

【0046】[0046]

【表5】 [Table 5]

【0047】表3乃至表5から明らかなように、試料N
o.1〜12は、抗折強度が590〜640kg/cm
2 、絶縁抵抗が13.2〜14.5Ω・cm、α線放出
量が0.11〜0.19count/cm2 ・hrと良
好な値を示した。また熱膨張係数は、試料No.1〜5
が63〜70×10-7/℃、試料No.6〜9が51〜
53×10-7/℃、試料No.10〜12が155〜1
66×10-7/℃であり、それぞれアルミナ(70×1
-7/℃)、窒化アルミニウム(45×10-7/℃)、
Al−Si合金(160×10-7/℃)に近似した値を
示した。
As is clear from Tables 3 to 5, sample N
o. 1-12 has a bending strength of 590-640 kg / cm
2 , the insulation resistance was 13.2 to 14.5 Ω · cm, and the α ray emission amount was 0.11 to 0.19 count / cm 2 · hr, which were favorable values. The thermal expansion coefficient is the same as that of Sample No. 1-5
Of 63 to 70 × 10 −7 / ° C., sample No. 6-9 is 51-
53 × 10 −7 / ° C., sample No. 10-12 is 155-1
66 × 10 −7 / ° C., and alumina (70 × 1
0 -7 / ° C), aluminum nitride (45 x 10 -7 / ° C),
The value approximated to that of Al-Si alloy (160 × 10 −7 / ° C.) was shown.

【0048】また各試料を通常行われているようにビー
クルを添加してペースト状にし、試料No.1〜5をア
ルミナに、試料No.6〜9を窒化アルミニウムに、試
料No.10〜12をAl−Si合金にそれぞれ印刷し
て封着温度を測定したところ、アルミナパッケージ封着
用の試料が360〜390℃で、窒化アルミニウムパッ
ケージ封着用の試料が370〜400℃で、Al−Si
合金製パッケージ用の試料が380〜400℃で荷重を
かけることなく封着できた。
In addition, each sample was added with a vehicle to form a paste as in a conventional method. Sample Nos. 1 to 5 in alumina. Sample Nos. 6 to 9 in aluminum nitride. When 10 to 12 were printed on Al-Si alloys and the sealing temperature was measured, the sample for alumina package sealing was 360 to 390 ° C, the sample for aluminum nitride package sealing was 370 to 400 ° C, and Al- Si
The sample for the alloy package could be sealed at 380-400 ° C without any load.

【0049】これらの事実は本発明の低融点封着用組成
物が、ICパッケージの封着用組成物に求められる諸条
件を満足し、特に荷重をかけることなく400℃以下の
温度で封着できること、また適当な耐火性フィラー粉末
を混合することにより、所望の熱膨張係数に調整できる
ことを示している。なお本実施例ではICパッケージの
封着用組成物について述べたが、熱膨張係数を適当な値
に調節することによって、他の電子部品、例えば水晶振
動子パッケージの封着にも使用することが可能である。
These facts indicate that the low melting point sealing composition of the present invention satisfies the various conditions required for the IC package sealing composition, and can be sealed at a temperature of 400 ° C. or less without applying a load. It also shows that the desired coefficient of thermal expansion can be adjusted by mixing a suitable refractory filler powder. Although the composition for sealing the IC package has been described in this embodiment, it can be used for sealing other electronic components such as a crystal oscillator package by adjusting the thermal expansion coefficient to an appropriate value. Is.

【0050】なお、各表中の熱膨張係数は、押棒式熱膨
張測定装置を用いて測定した。また抗折強度は試料を焼
結した後、10×10×50mmの角柱に成形し、3点
荷重測定法によって求めた。絶縁抵抗はメガオームメー
ターを用いて150℃における値を測定し、α線放出量
はZnSシンチレーションカウンターを用いて測定し
た。
The coefficient of thermal expansion in each table was measured using a push rod type thermal expansion measuring device. The bending strength was obtained by sintering the sample, molding it into a prism of 10 × 10 × 50 mm, and measuring it with a three-point load. The insulation resistance was measured at 150 ° C. using a mega ohm meter, and the α-ray emission was measured using a ZnS scintillation counter.

【0051】また表3乃至表5に示した耐火性フィラー
粉末は次のようにして作製した。
The refractory filler powders shown in Tables 3 to 5 were prepared as follows.

【0052】ウイレマイト系セラミック粉末は、重量%
でZnO 70%、SiO2 25%、Al23 5%の
組成になるように原料粉末を調合し、混合後、1440
℃で15時間焼成し、次いでこの焼成物を粉砕し、25
0メッシュのステンレス製篩を通過したものを使用し
た。
The willemite-based ceramic powder is the weight%
Then, the raw material powder was prepared so that the composition of ZnO was 70%, SiO 2 was 25%, and Al 2 O 3 was 5%.
Bake at 15 ° C. for 15 hours, then crush this baked product to 25
The one that passed through a 0 mesh stainless steel sieve was used.

【0053】酸化錫系セラミック粉末は、重量%でSn
2 93%、TiO2 2%、MnO2 5%の組成になる
ように原料粉末を調合し、混合後、1400℃で16時
間焼成し、次いでこの焼成物を粉砕し、250メッシュ
のステンレス篩を通過したものを使用した。
The tin oxide ceramic powder is Sn in weight%.
Raw material powders were blended so as to have a composition of O 2 93%, TiO 2 2%, and MnO 2 5%, and after mixing, calcination was performed at 1400 ° C. for 16 hours, and then the calcination product was crushed and 250 mesh stainless sieve. The one that passed through was used.

【0054】ジルコン系セラミック粉末は次のようにし
て作製した。まず、天然ジルコンサンドを一旦ソーダ分
解し、塩酸に溶解した後、濃縮結晶化を繰り返すことに
よって、α線放出物質であるU、Thの極めて少ないオ
キシ塩化ジルコニウムにし、アルカリ中和後、加熱して
精製ZrO2 を得た。さらにこの精製ZrO2 に高純度
珪石粉、酸化第二鉄を重量%でZrO2 66%、SiO
2 32%、Fe232%の組成になるように調合し、
混合後、1400℃で16時間焼成し、次いでこの焼成
物を粉砕し、250メッシュのステンレス製篩を通過し
たものを使用した。
The zircon ceramic powder was produced as follows. First, natural zircon sand is once decomposed with soda, dissolved in hydrochloric acid, and concentrated crystallization is repeated to obtain zirconium oxychloride having extremely small amounts of U and Th that are α-ray emitting substances. Purified ZrO 2 was obtained. Furthermore, high-purity silica stone powder and ferric oxide were added to the purified ZrO 2 in a weight percentage of ZrO 2 66%, SiO 2
Formulated to have a composition of 2 32% and Fe 2 O 3 2%,
After mixing, the mixture was fired at 1400 ° C. for 16 hours, and then the fired product was crushed and passed through a 250-mesh stainless sieve.

【0055】チタン酸鉛系セラミック粉末は、重量%で
PbO 70%、TiO2 20%、CaO 10%の組
成になるように原料粉末を調合し、混合後、1100℃
で5時間焼成し、次いでこの焼成物を粉砕し、350メ
ッシュのステンレス製篩を通過したものを使用した。
The lead titanate-based ceramic powder was prepared by mixing the raw material powders so that the composition of PbO was 70%, TiO 2 was 20%, and CaO was 10% by weight.
Then, the product was pulverized and passed through a 350-mesh stainless sieve, which was then used.

【0056】ムライト粉末は、3Al23 ・2SiO
2 の組成になるように原料粉末を調合し、混合後、16
00℃で10時間焼成し、次いでこの焼成物を粉砕し、
250メッシュのステンレス製篩を通過したものを使用
した。
Mullite powder is 3Al 2 O 3 .2SiO
Mix the raw material powder so that it has the composition of 2 , and after mixing,
Bake at 00 ° C. for 10 hours, then crush this fired product,
It was passed through a 250-mesh stainless sieve.

【0057】β−ユークリプタイト粉末は、Li2 O・
Al23 ・2SiO2 の組成になるように原料粉末を
調合し、混合後、1250℃で5時間焼成し、次いでこ
の焼成物を粉砕し、250メッシュのステンレス製篩を
通過したものを使用した。
The β-eucryptite powder is Li 2 O.
Raw material powders are blended so as to have a composition of Al 2 O 3 .2SiO 2 , and after mixing, they are fired at 1250 ° C. for 5 hours, and then the fired product is crushed and passed through a 250-mesh stainless sieve. did.

【0058】コーディエライト粉末は、2MgO・2A
23 ・5SiO2 の割合になるように原料粉末を調
合し、混合後、1400℃で10時間焼成し、次いでこ
の焼成物を粉砕し、250メッシュのステンレス製篩を
通過したものを使用した。
Cordierite powder is 2MgO.2A
The raw material powders were blended so as to have a ratio of 1 2 O 3 .5SiO 2 , and after mixing, they were fired at 1400 ° C. for 10 hours, and then the fired product was crushed and passed through a 250 mesh stainless sieve. did.

【0059】錫酸亜鉛粉末は、2ZnO・SnO2 の組
成になるように原料粉末を調合し、乾式混合後、145
0℃で16時間焼成し、次いでこの焼成物を粉砕し、2
50メッシュのステンレス製篩を通過したものを用い
た。
[0059] zinc stannate powder to prepare a raw material powder so that the composition of 2ZnO · SnO 2, after dry mixing, 145
Bake at 0 ° C. for 16 hours, then crush this fired product to 2
The one that passed through a 50-mesh stainless sieve was used.

【0060】クリストバライト粉末は、まず球形化され
た平均粒径10μmの石英ガラス粉末を1480℃で1
6時間焼成してクリストバライト化した。なおクリスト
バライト粉末は流動性を改善するために、さらに平均粒
径0.1μmのZnO微粒子を5体積%添加して乾式混
合後、1000℃で1時間処理し、表面にZnO被膜を
形成した。
Cristobalite powder was prepared by first spheroidizing silica glass powder having an average particle size of 10 μm at 1480 ° C.
It was calcined for 6 hours to form cristobalite. In order to improve the fluidity of the cristobalite powder, 5% by volume of ZnO fine particles having an average particle diameter of 0.1 μm was further added and dry-mixed, followed by treatment at 1000 ° C. for 1 hour to form a ZnO coating film on the surface.

【0061】立方晶ジルコニア粉末は、まず低α線タイ
プのジルコニア原料及び炭酸カルシウムをZrO2 80
mol%、CaO 20mol%の割合になるように調
合し、混合後、1550℃で16時間焼成し、次いでこ
の焼成物を粉砕し、350メッシュのステンレス製篩を
通過したものを用いた。
The cubic zirconia powder was prepared by first adding a low α-ray type zirconia raw material and calcium carbonate to ZrO 2 80
A mixture was prepared such that the ratio of mol% and CaO was 20 mol%, and after mixing, the mixture was fired at 1550 ° C. for 16 hours, and then the fired product was crushed and passed through a 350-mesh stainless sieve.

【0062】[0062]

【発明の効果】以上説明したように、本発明の低融点封
着用組成物は、有害物質を含まず、また荷重をかけるこ
となく400℃以下の低い温度で封着が可能である。し
かも耐火性フィラーを使用することによって所望の熱膨
張係数が得られるため、ICパッケージや水晶振動子パ
ッケージ等の電子部品の封着に好適である。
As described above, the low melting point sealing composition of the present invention does not contain harmful substances and can be sealed at a low temperature of 400 ° C. or lower without applying a load. Moreover, since a desired coefficient of thermal expansion can be obtained by using the refractory filler, it is suitable for sealing electronic components such as IC packages and crystal oscillator packages.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C03C 8/10 6971−4G 8/14 6971−4G ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C03C 8/10 6971-4G 8/14 6971-4G

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 重量百分率で、PbO 70.3〜9
2.0%、B23 1.0〜10.0%、Bi23
5.2〜20.0%、F2 0.01〜8.0%、ZnO
0〜15.0%、V25 0〜5.0%、SiO2
〜2.0%、Al23 0〜2.0%、SnO2 0〜
2.0%、BaO 0〜4.0%の組成を有し、且つ、
23 /PbO比が0.11以下のガラス粉末からな
ることを特徴とする低融点封着用組成物。
1. PbO 70.3-9 in percentage by weight.
2.0%, B 2 O 3 1.0~10.0 %, Bi 2 O 3
5.2~20.0%, F 2 0.01~8.0%, ZnO
0 to 15.0%, V 2 O 5 0 to 5.0%, SiO 2 0
~2.0%, Al 2 O 3 0~2.0 %, SnO 2 0~
2.0%, BaO 0-4.0% composition, and
A low melting point sealing composition comprising a glass powder having a B 2 O 3 / PbO ratio of 0.11 or less.
【請求項2】 重量百分率で、PbO 70.3〜9
2.0%、B23 1.0〜10.0%、Bi23
5.2〜20.0%、F2 0.01〜8.0%、ZnO
0〜15.0%、V25 0〜5.0%、SiO2
〜2.0%、Al23 0〜2.0%、SnO2 0〜
2.0%、BaO 0〜4.0%の組成を有し、且つ、
23 /PbO比が0.11以下であるガラス粉末4
5〜80体積%と、耐火性フィラー粉末20〜55体積
%からなることを特徴とする低融点封着用組成物。
2. PbO 70.3-9 in percentage by weight.
2.0%, B 2 O 3 1.0~10.0 %, Bi 2 O 3
5.2~20.0%, F 2 0.01~8.0%, ZnO
0 to 15.0%, V 2 O 5 0 to 5.0%, SiO 2 0
~2.0%, Al 2 O 3 0~2.0 %, SnO 2 0~
2.0%, BaO 0-4.0% composition, and
Glass powder 4 having a B 2 O 3 / PbO ratio of 0.11 or less
A low melting point sealing composition comprising 5 to 80% by volume and a refractory filler powder of 20 to 55% by volume.
JP28357691A 1991-10-02 1991-10-02 Sealing composition having low melting point Pending JPH0597470A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28357691A JPH0597470A (en) 1991-10-02 1991-10-02 Sealing composition having low melting point

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28357691A JPH0597470A (en) 1991-10-02 1991-10-02 Sealing composition having low melting point

Publications (1)

Publication Number Publication Date
JPH0597470A true JPH0597470A (en) 1993-04-20

Family

ID=17667316

Family Applications (1)

Application Number Title Priority Date Filing Date
JP28357691A Pending JPH0597470A (en) 1991-10-02 1991-10-02 Sealing composition having low melting point

Country Status (1)

Country Link
JP (1) JPH0597470A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752292A1 (en) * 1995-07-07 1997-01-08 Sintokogio, Ltd. Low pressure casting apparatus with two holding furnaces
US6163106A (en) * 1997-09-09 2000-12-19 Asahi Glass Company Ltd. Color cathode ray tube and water resistant glass frit
JP4819999B2 (en) * 1998-03-17 2011-11-24 日本板硝子株式会社 Double glazing
EP4129942A1 (en) 2021-08-03 2023-02-08 Corning Incorporated Borate and silicoborate optical glasses with high refractive index and low liquidus temperature

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752292A1 (en) * 1995-07-07 1997-01-08 Sintokogio, Ltd. Low pressure casting apparatus with two holding furnaces
US6163106A (en) * 1997-09-09 2000-12-19 Asahi Glass Company Ltd. Color cathode ray tube and water resistant glass frit
JP4819999B2 (en) * 1998-03-17 2011-11-24 日本板硝子株式会社 Double glazing
EP4129942A1 (en) 2021-08-03 2023-02-08 Corning Incorporated Borate and silicoborate optical glasses with high refractive index and low liquidus temperature

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