KR950009987B1 - Glass composition for sealing - Google Patents

Glass composition for sealing Download PDF

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KR950009987B1
KR950009987B1 KR1019880007564A KR880007564A KR950009987B1 KR 950009987 B1 KR950009987 B1 KR 950009987B1 KR 1019880007564 A KR1019880007564 A KR 1019880007564A KR 880007564 A KR880007564 A KR 880007564A KR 950009987 B1 KR950009987 B1 KR 950009987B1
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glass
oxide
composition
glass powder
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KR900000305A (en
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이헌식
전표용
홍유식
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삼성코닝주식회사
한형수
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion 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
    • C03C8/245—Fusion 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

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  • 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

The glass, which has low thermal expansion coefficient and high shear strength, for sealing is composed of 45.0-86.0 wt% glass powder having low melting point and 13.0-55.0 wt% refractory filler. The glass powder consists of 75.0-86.0 wt% lead oxide, 6.0-16.0 wt% boron oxide, 0.7-6 wt% zinc oxide, 0.5-3.5 wt% silica, less than 3.0 wt% alumina, less than 5.0 wt% magnesia and less than 1.0 wt% RO(calcium oxide, barium oxide, strontium oxide). The refractory filler comprises 2.0-40.0 wt% antimony-titanium solid solution, below 30 wt% kyanite and cordierite, respectively.

Description

기밀 접착용 저융점 유리 조성물Low melting glass composition for hermetic bonding

본 발명은 저온의 열처리를 통하여 비실투상태의 기밀 접착에 사용되며, 저융점 유리와 열팽창율이 작은 내화물 충진재(filler)로 구성된 것으로, 특히 알루미나 패키지의 베이스와 캡의 기밀접착에 뛰어난 효과가 있는 분말상의 기밀 접착용 저융점 유리 조성물에 관한 것이다.The present invention is used for non-devitrified hermetic adhesion through low temperature heat treatment, and consists of a low melting point glass and a refractory filler having a low thermal expansion rate. In particular, the present invention has an excellent effect on the hermetic adhesion between the base and the cap of an alumina package. A low melting glass composition for hermetic sealing.

종래의 IC용 알루미나 패키지의 접착에는 PbO-B2O3계의 저융점유리(Frit)가 사용되었으나, 이는 접착후 알루미나 패키지와 같은 열팽창계수를 갖는 접착부를 형성하는 반면, 열처리시 약 470℃의 고온이 요구될 뿐만 아니라 결정화를 위해 요구되는 열처리의 조건(온도, 시간)을 조절하기에 까다로운 단점이 있었다. 또한, 저팽창성 내화물 충진재를 첨가하여 복합제 접착물을 제조할 경우, 접착에 필요한 온도는 감소되나 기밀 접착후의 전단강도 등이 강하지 못할 뿐만 아니라, 반도체의 오동작 원인이 되는 많은 양의 α선이 접착용 유리구성원소의 방사선 붕괴에 의해 발생되기 때문에 α선 방출량의 제어에 문제점이 있어 256K바이트(byte) 이상의 고집적회로를 위한 접착물의 조성물로서는 적당치 못한 단점이 있었다.Conventional IC alumina package was used to bond PbO-B 2 O 3 based low melting point glass (Frit), but after bonding, it forms an adhesive part with the same thermal expansion coefficient as alumina package, Not only high temperature is required but also difficult to control the conditions (temperature, time) of heat treatment required for crystallization. In addition, when a composite adhesive is prepared by adding a low-expandable refractory filler, the temperature required for adhesion is reduced, but the shear strength after airtight adhesion is not strong, and a large amount of α-ray, which causes malfunction of the semiconductor, is used for adhesion. Since it is caused by the radiation decay of the glass component, there is a problem in the control of the amount of α-ray emission, there was an unsuitable disadvantage as a composition of the adhesive for a high-integrated circuit of 256K bytes or more.

따라서 본 발명은 충분한 유동성으로 알루미나 패키지와 완전한 기밀접착을 이루고, IC회로의 오동작을 유발시키는 α선의 방출량을 최대한으로 억제하며, 내열성, 절연성 및 낮은 유전율 등의 조건을 충분히 만족시키고, 특히 IC 패키지의 리드ㆍ플레임의 주석도금시 충분한 내산성을 유지할 수 있는 접착용 유리조성물을 제공하는데 그 목적이 있다.Therefore, the present invention achieves a complete hermetic adhesion with the alumina package with sufficient fluidity, suppresses the amount of α-rays causing malfunction of the IC circuit to the maximum, satisfies conditions such as heat resistance, insulation and low dielectric constant, and particularly, An object of the present invention is to provide an adhesive glass composition that can maintain sufficient acid resistance during tin plating of lead and flame.

본 발명은 PbO-B2O3-ZnO계의 특정한 범위의 저융점 유리분말과 충진재로서 저열팽창성 분말을 사용하여 상술한 목적을 달성할 수 있었다.The present invention was able to achieve the above object by using a low thermal expansion powder as a filler and a low melting point glass powder of a specific range of PbO-B 2 O 3 -ZnO system.

구체적으로 본 발명의 조성물은 중량비로서 저융점 유리분말 45.0%~86.0%에 저열팽창성 내화물 분말 14.0%~55.0%, 즉 Sn-Ti 고용체 2.0~40.0%, 카이어나이트(Kyanite) 30.0% 이하, 코디어라이트(Cordierite) 30.0% 이하를 혼합하여 제조한 접착용 유리 조성물로서 저융점 유리분말은 PbO 75.0~86.0%, B2O36.0~16.0%, ZnO 0.7~6%, SiO20.5~3.5%, Al2O33.0% 이하, MgO 5.0% 이하, RO(CaO, BaO, SrO) 1.0% 이하로 구성된 것이다.Specifically, the composition of the present invention has a low melting point glass powder of 45.0% to 86.0% by weight ratio, 14.0% to 55.0% of low thermal expansion refractory powder, that is, 2.0 to 40.0% of Sn-Ti solid solution, 30.0% or less of Kyneite, and Cody Adhesion glass composition prepared by mixing 30.0% or less of aluminite. Low melting glass powder contains PbO 75.0 ~ 86.0%, B 2 O 3 6.0 ~ 16.0%, ZnO 0.7 ~ 6%, SiO 2 0.5 ~ 3.5% , Al 2 O 3 3.0% or less, MgO 5.0% or less, RO (CaO, BaO, SrO) 1.0% or less.

본 발명에 사용된 저융점 유리의 조성물에서 성분함량이 한정된 범위를 갖는 이유는 다음과 같다 ; PbO의 함량이 75% 이하이면 연화점이 높아져 저온에서 접착하기에 적당치 않으며, 86% 이상이면 유리의 열팽창 계수가 커지게 되는 문제점이 있고, B2O3의 함량이 6% 이하이면 유리의 접착중에 실투가 발생되기 쉽고, 16% 이상이면 유리의 연화점이 높아져 저온접착의 어려움은 물론, ZnO의 함량이 0.7% 이하이면 유리의 비실투성은 좋아지나, 연화점이 높아져 저온접착이 어려워지고, 6% 이상이면 유리의 결정화 속도가 빨라져 접착중에 실투되기 쉬운 경향이 있었다.The reason why the component content in the composition of the low melting glass used in the present invention has a limited range is as follows; If the PbO content is 75% or less, the softening point is high, and thus it is not suitable for adhesion at low temperatures. If the PbO content is more than 86%, the thermal expansion coefficient of the glass is increased. If the B 2 O 3 content is 6% or less, the glass is bonded. It is easy to cause devitrification in the glass, and if it is more than 16%, the softening point of the glass becomes high, so that the low temperature adhesion is difficult, and if the ZnO content is 0.7% or less, the non-permeability of the glass is good, but the softening point becomes high, making the low temperature adhesion difficult, 6% If it was the above, the crystallization rate of the glass would increase and tend to be devitrified during adhesion.

또한 SiO2의 함량이 0.5% 이하이면 유리의 결정화 경향이 강해지고, 3.5% 이상이면 유리의 연화점이 높아져 저온접착이 적합하지 않았다.Further, when the content of SiO 2 is 0.5% or less, the crystallization tendency of the glass becomes stronger, and when it is 3.5% or more, the softening point of the glass is increased, so that low temperature bonding is not suitable.

또한, 3.0% 이하의 Al2O3, 5.0% 이하의 MgO 및 1% 이하의 RO를 첨가하는 것은 유리의 결정화 경향을 조정하기 위한 것이다.In addition, the addition of 3.0% or less of Al 2 O 3 , 5.0% or less of MgO and 1% or less of RO is to adjust the crystallization tendency of the glass.

본 발명은 접착후에 알루미나와 같은 열팽창계수, 즉 약 65~70×10℃(25~400℃)의 열팽창 계수값을 갖고 IC회로에 오동작을 일으키는 α선의 방출이 없는 조성물을 만들기 위해서, 종래의 내화물 충진재로 많이 사용해 오던 지르코니아(ZrO2ㆍSiO2) 대신에 카이어나이트(Al2O3ㆍSiO2) 30% 이하, SnO2와 TiO2의 고용체 2.0~40% 및 코디어라이트 30% 이하를 첨가하여 열팽창계수를 맞추어 주며, 접착물의 전단강도는 물론 화학적 성질을 향상시킬 수 있었다.The present invention provides a conventional refractory material for making a composition having a thermal expansion coefficient such as alumina after adhesion, that is, a thermal expansion coefficient value of about 65 to 70 × 10 ° C. (25 to 400 ° C.) and no emission of α rays causing malfunction in the IC circuit. Instead of zirconia (ZrO 2 ㆍ SiO 2 ), which has been widely used as a filler, 30% or less of chineite (Al 2 O 3 ㆍ SiO 2 ), 2.0-40% of solid solution of SnO 2 and TiO 2 , and 30% or less of cordierite The thermal expansion coefficient was added to improve the shear strength of the adhesive as well as the chemical properties.

이들 각각의 내화물 충진재의 특성과 함량을 제한한 이유는 다음과 같다 ; SnO2와 TiO2의 고용체는 유리조성물의 접합후 전단강도를 높여주기 위해 사용하였지만, 함량이 40%가 넘으면 조성물에 충분한 유동성을 부여할 수 없고, 카이어나이트(Al2O3ㆍSiO2)는 IC 패키지 리드ㆍ플레임의 주석도금 공정시 유리조성물의 내산성을 증가시키기 위해 사용하였지만, 함량이 30%가 넘으면 유동성이 저하되어 IC 패키지와의 접합에 문제가 발생된다.The reasons for limiting the properties and content of each of these refractory fillers are as follows; A solid solution of SnO 2 and TiO 2 was used to increase the shear strength after bonding the glass composition. However, if the content is more than 40%, it cannot give sufficient fluidity to the composition, and it may be made of chineite (Al 2 O 3 ㆍ SiO 2 ). Was used to increase the acid resistance of the glass composition during the tin plating process of the IC package lead / flame. However, if the content exceeds 30%, the fluidity decreases, causing problems in bonding to the IC package.

또한, 코디어라이트는 열팽창계수 및 조성물의 내구성, 내화학성을 개선하기 위해 사용하였으나, 그 함량이 30% 이상이면 유동성이 저하되어 충분한 기밀의 접착이 불가능하게 된다.In addition, cordierite was used to improve the coefficient of thermal expansion and durability and chemical resistance of the composition, but if the content is 30% or more, the fluidity is lowered and sufficient airtight adhesion is impossible.

Sn-Ti의 고용체는 SnO2분말과 TiO2분말의 혼합물을 약 1200~1400℃에서 고상반응시켜 합성한 다음, 생성된 소결체를 분쇄하여 얻고, 카이어나이트는 Al2O3분말과 SiO2분말의 혼합물을 1100~1300℃의 고온에서 소성, 고상반응시켜 합성하고 분쇄하여 얻었다.Solid solution of Sn-Ti is synthesized by solid-phase reaction of SnO 2 powder and TiO 2 powder at about 1200 ~ 1400 ° C, and then the resulting sintered compact is pulverized, and chineite is Al 2 O 3 powder and SiO 2 powder Was obtained by calcining and solidifying the mixture at a high temperature of 1100 to 1300 ° C. to obtain a mixture.

다음의 실시예에서 본 발명을 좀더 구체적으로 설명한다.The present invention is explained in more detail in the following examples.

[실시예 1-4]Example 1-4

유리의 각 성분 원료를 표 1에 기재된 비율로 혼합한 후, 백금도가니를 사용하여 전기로중에서 약 800~1000℃로 30~60분 동안 가열 용융한 다음, 용융유리를 판상의 형태로 성형하여 볼-밀에서 입경이 1-10~ 정도가 되도록 분쇄하였다. 이렇게 제조한 유리분말과 충진재를 표 1에 기재된 비율로 트윈-블렌더(Twin-Blender)에서 균일하게 혼합하여 본 발명의 기밀 접착용 유리조성물을 제조하였으며, 이들의 특성치는 표 2에 기재하였다.After mixing each component raw material of glass in the ratio of Table 1, using a platinum crucible, it heat-melts at about 800-1000 degreeC for 30 to 60 minutes in an electric furnace, and shape | molds a molten glass in plate shape, and the ball- The mill was pulverized to a particle size of about 1-10 ~. The glass powder and the filler thus prepared were uniformly mixed in a twin blender at the ratio shown in Table 1 to prepare an airtight adhesive glass composition of the present invention, and their characteristics are shown in Table 2.

플로우 버튼경의 측정은 접착조성물의 유동성 정도를 실현하기 위한 것으로, 비중 g만큼의 양을 금형에 넣어 약 20kg/㎠의 압력으로 프레싱함으로써, 직경 12.5mm, 높이 약 20mm의 원통형의 버튼을 만들어 면이 편편한 판유리위에 올려놓고 온도 분포를 일정하게 하고 430℃까지 가열하여 10분 동안 유지시킨 다음 냉각하여 외경을 측정한다.The flow button diameter is measured to realize the fluidity of the adhesive composition. The specific gravity g is placed in the mold and pressed at a pressure of about 20 kg / cm 2 to form a cylindrical button having a diameter of 12.5 mm and a height of about 20 mm. Place on flat glass, make the temperature distribution constant, heat to 430 ℃, hold for 10 minutes, cool and measure outer diameter.

내산성 측정은 접착조성물의 산에 대한 용해 정도를 측정하기 위해 실시하며, 25℃에서 1N HCl 용액에 10분 동안 넣어 그 중량 감소분을 측정하였다.Acid resistance measurement was carried out to determine the degree of dissolution of the adhesive composition in the acid, it was put in 1N HCl solution at 25 ℃ for 10 minutes to measure the weight loss.

열팽창계수는 제조된 저융점 유리 봉착제와 피봉착제의 접합특성을 결정하는 주요항목으로 TMA를 사용하여 측정하였다.The coefficient of thermal expansion was measured using TMA as a main item to determine the bonding properties of the prepared low melting point glass encapsulation agent and the encapsulation agent.

또한 반도체소자의 봉착제는 반도체의 열화를 방지하기 위하여 가능한한 저온에서 봉착할 수 있어야 하므로 봉착온도를 결정하는 전이점과 연화점을 DTA를 사용하여 측정하였다.In addition, since the sealing agent of the semiconductor device should be able to seal at low temperature as possible to prevent deterioration of the semiconductor, the transition point and softening point for determining the sealing temperature were measured using DTA.

반도체의 패키지는 반도체를 국한적인 사용환경에서도 보호하기 위하여 열충격에 강해야 하므로, 봉착제도 열충격에 강해야 한다. 본 발명에 의해 제조된 봉착재료를 납유리(Paste)로 만든 다음 반도체 소자와 봉착한 후 MIL STD-883c-1011에 의해 실험한 결과, 실시예 1 내지 6의 어느 것에서도 크랙(crack)을 발견할 수 없었다.Since the package of the semiconductor must be resistant to thermal shock in order to protect the semiconductor even in a limited use environment, the sealing agent must also be resistant to thermal shock. The sealing material prepared by the present invention was made of lead glass and then sealed with a semiconductor device, and then tested by MIL STD-883c-1011. As a result, cracks were not found in any of Examples 1 to 6. Could not.

접착강도의 측정은 알루미나 패키지(28 LEAD MSI)를 사용하여 MIL STD-883c-2024의 방법으로 강도실험을 실시하였으며 유전율은 1MHz, 25℃에서 LCR Mater를 사용하여 측정하였다.Adhesion strength was measured using alumina package (28 LEAD MSI) using the MIL STD-883c-2024 method, and the dielectric constant was measured using LCR Mater at 1MHz and 25 ℃.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

[표 2]TABLE 2

Figure kpo00002
Figure kpo00002

상술한 표 1 및 표 2의 기재로부터 알 수 있듯이 본 발명의 유리조성물은 410℃~430℃의 온도에서 10분 이내의 열처리로 기밀 접착이 가능하며 열팽창 계수가 낮고, 유동성뿐만 아니라 전단 강도 및 열충격성이 좋으며, 또한 α선의 방출량이 적은 장점이 있어 특히 IC 패키지용 기밀 접착에 유용한 것이다.As can be seen from the description of Table 1 and Table 2, the glass composition of the present invention can be hermetically bonded by heat treatment within 10 minutes at a temperature of 410 ° C. to 430 ° C., and has a low coefficient of thermal expansion, as well as shear strength and thermal shock. It has good properties and has a low amount of α-ray emission, which is particularly useful for hermetic bonding for IC packages.

Claims (3)

중량비로서 저융점 유리분말 45.0%~86.0%와 내화물 충진재 14.0%~55.0%를 함유함을 특징으로 하는 기밀 접착용 저융점 유리 조성물.A low melting glass composition for hermetic bonding, characterized by containing 45.0% to 86.0% of low melting point glass powder and 14.0% to 55.0% of a refractory filler as a weight ratio. 제1항에 있어서, 저융점 유리분말은 중량비로서 PbO 75.0~86.0%, B2O36.0~16.0%, ZnO 0.7~6%, SiO20.5~3.5%, Al2O33.0% 이하, MgO 5.0% 이하, RO(CaO, BaO, SrO) 1.0% 이하로 구성된 것임을 특징으로 하는 조성물.The low-melting-point glass powder according to claim 1, wherein the low melting point glass powder is PbO 75.0-86.0%, B 2 O 3 6.0-16.0%, ZnO 0.7-6%, SiO 2 0.5-3.5%, Al 2 O 3 3.0% or less, MgO 5.0% or less, RO (CaO, BaO, SrO) The composition, characterized in that composed of 1.0% or less. 제1항에 있어서, 내화물 충진재는 중량비로서 Sn-Ti 고용체 2.0~40.0%, 카이어나이트 30.0% 이하, 코디어라이트 30.0% 이하의 비율로 혼합하여 유리분말에 첨가함을 특징으로 하는 조성물.The composition according to claim 1, wherein the refractory filler is added to the glass powder by mixing at a ratio of 2.0 to 40.0% of Sn-Ti solid solution, 30.0% or less of Cainite, and 30.0% or less of cordierite as a weight ratio.
KR1019880007564A 1988-06-22 1988-06-22 Glass composition for sealing KR950009987B1 (en)

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