WO2020071093A1 - Verre pour revêtement d'élément à semi-conducteurs, et matériau pour revêtement de semi-conducteur mettant en œuvre celui-ci - Google Patents

Verre pour revêtement d'élément à semi-conducteurs, et matériau pour revêtement de semi-conducteur mettant en œuvre celui-ci

Info

Publication number
WO2020071093A1
WO2020071093A1 PCT/JP2019/036160 JP2019036160W WO2020071093A1 WO 2020071093 A1 WO2020071093 A1 WO 2020071093A1 JP 2019036160 W JP2019036160 W JP 2019036160W WO 2020071093 A1 WO2020071093 A1 WO 2020071093A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
semiconductor element
coating
semiconductor
content
Prior art date
Application number
PCT/JP2019/036160
Other languages
English (en)
Japanese (ja)
Inventor
将行 廣瀬
Original Assignee
日本電気硝子株式会社
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 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to CN201980051203.4A priority Critical patent/CN112512982B/zh
Publication of WO2020071093A1 publication Critical patent/WO2020071093A1/fr

Links

Classifications

    • 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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a glass for coating a semiconductor element and a material for coating a semiconductor using the glass.
  • a semiconductor element such as a silicon diode or a transistor has a surface including a PN junction of the semiconductor element covered with glass. This makes it possible to stabilize the surface of the semiconductor element and suppress deterioration of characteristics over time.
  • the characteristics required of the glass for covering a semiconductor element are as follows: (1) The coefficient of thermal expansion conforms to the coefficient of thermal expansion of the semiconductor element so that cracks and the like due to the difference in thermal expansion coefficient from the semiconductor element do not occur; In order to prevent the deterioration of the characteristics of the semiconductor element, it can be coated at a low temperature (for example, 900 ° C. or lower), and (3) it does not contain impurities such as alkali components which adversely affect the surface of the semiconductor element.
  • zinc-based glass such as ZnO—B 2 O 3 —SiO 2 , PbO—SiO 2 —Al 2 O 3 -based glass, and PbO—SiO 2 —Al 2 O 3 —B 2
  • Lead-based glass such as O 3 -based glass
  • PbO—SiO 2 —Al 2 O 3 -based glass and PbO—SiO 2 —Al 2 O 3 —B 2 O lead-based glass such as 3 based glass has become the mainstream (for example, see Patent documents 1-4).
  • JP-A-48-43275 JP-A-50-129181 Japanese Patent Publication No. 1-49653 JP 2008-162881 A
  • the lead component of lead-based glass is a harmful component to the environment. Since the above zinc-based glass contains a small amount of a lead component and a bismuth component, it cannot be said that it is completely harmless to the environment.
  • zinc-based glass is inferior in chemical durability to lead-based glass and has a problem that it is easily eroded in an acid treatment step after forming a coating layer. For this reason, it was necessary to further form a protective film on the surface of the coating layer and perform an acid treatment.
  • the present invention has been made in view of the above circumstances, and a technical problem thereof is to provide a glass for coating a semiconductor element, which has a small environmental load, is excellent in acid resistance, and has a low surface charge density.
  • the present inventors have found that the above technical problem can be solved by using a SiO 2 —B 2 O 3 —Al 2 O 3 —ZnO-based glass having a specific glass composition. It is proposed as an invention. That is, the glass for coating a semiconductor element of the present invention has, as a glass composition, 18 to 43% of SiO 2 , 5 to 21% of B 2 O 3, 8 to 21% of Al 2 O 3 , and 10 to 25% of ZnO in mol%. , MgO + CaO in an amount of 10 to 25%, and substantially no lead component.
  • MgO + CaO indicates the total amount of MgO and CaO.
  • substantially does not contain means that the corresponding component is not intentionally added as a glass component, and does not mean that impurities that are unavoidably mixed are completely excluded. Specifically, it means that the content of the relevant component including impurities is less than 0.1% by mass.
  • the glass for coating a semiconductor element of the present invention regulates the content range of each component, whereby the environmental load is small, the acid resistance is improved, and the surface charge density is reduced. As a result, it can be suitably used for coating a semiconductor element for low withstand voltage.
  • the material for coating a semiconductor element of the present invention preferably contains 75 to 100% by mass of a glass powder composed of the glass for coating a semiconductor element described above and 0 to 25% of a ceramic powder.
  • the coefficient of thermal expansion in a temperature range of 30 to 300 ° C. is preferably 20 ⁇ 10 ⁇ 7 / ° C. or more and 55 ⁇ 10 ⁇ 7 / ° C. or less.
  • “the coefficient of thermal expansion in the temperature range of 30 to 300 ° C.” indicates a value measured by a push-rod type thermal expansion coefficient measuring device.
  • the glass for semiconductor element coating of the present invention has a glass composition of 18 to 43% of SiO 2 , 5 to 21% of B 2 O 3, 8 to 21% of Al 2 O 3 , 10 to 25% of ZnO, and MgO + CaO in terms of mol%. It is characterized by containing from 10 to 25% and containing substantially no lead component. The reason for limiting the content of each component will be described below. In the following description of the content of each component, the unit of% means mol% unless otherwise specified.
  • SiO 2 is a glass network-forming component and a component that enhances acid resistance.
  • the content of SiO 2 is 18-43%, preferably 20-40%, especially 22-36%. If the content of SiO 2 is too small, the acid resistance tends to decrease. On the other hand, if the content of SiO 2 is too large, the devitrification at the time of melting becomes strong, and it becomes difficult to obtain a homogeneous glass.
  • B 2 O 3 is a glass network-forming component and a component that enhances softening fluidity.
  • the content of B 2 O 3 is 5 to 21%, preferably 5 to 18%, particularly 7 to 15%. If the content of B 2 O 3 is too small, the crystallinity becomes strong, so that the softening fluidity is impaired during coating, making it difficult to uniformly coat the surface of the semiconductor element. On the other hand, if the content of B 2 O 3 is too large, the coefficient of thermal expansion tends to be unduly high and the acid resistance tends to decrease.
  • Al 2 O 3 is a component that stabilizes the glass and adjusts the surface charge density.
  • the content of Al 2 O 3 is 8 to 21%, preferably 5 to 20%, particularly 8 to 18%. If the content of Al 2 O 3 is too small, the glass tends to be devitrified. On the other hand, if the content of Al 2 O 3 is too large, the surface charge density may be too large.
  • ZnO is a component that stabilizes glass.
  • the content of ZnO is 10 to 25%, preferably 12 to 22%. If the content of ZnO is too small, the devitrification at the time of melting becomes strong, and it becomes difficult to obtain a homogeneous glass. On the other hand, when the content of ZnO is too large, the acid resistance tends to decrease.
  • MgO and CaO are components that lower the viscosity of glass.
  • the total amount of MgO and CaO is 10 to 25%, preferably 12 to 20%. If the combined amount of MgO and CaO is too small, the firing temperature of the glass tends to increase. On the other hand, when the total amount of MgO and CaO is too large, there is a possibility that the thermal expansion coefficient becomes too high, the acid resistance is reduced, and the insulation property is reduced.
  • the content of MgO is preferably 0 to 20%, particularly 0 to 5%.
  • the content of CaO is preferably 1 to 25%, particularly 10 to 20%.
  • the composition does not substantially contain a lead component (for example, PbO or the like) and does not substantially contain Bi 2 O 3 , F, or Cl. Further, it is preferable that alkali components (Li 2 O, Na 2 O, and K 2 O) that adversely affect the surface of the semiconductor element are not substantially contained.
  • a lead component for example, PbO or the like
  • Bi 2 O 3 for example, F, or Cl.
  • alkali components Li 2 O, Na 2 O, and K 2 O
  • the glass for coating a semiconductor element of the present invention is preferably in the form of powder, that is, glass powder. If processed into glass powder, the surface of the semiconductor element can be easily coated using, for example, a paste method, an electrophoretic coating method, or the like.
  • the average of the glass powder the particle diameter D 50 is preferably 25 ⁇ m or less, particularly 15 ⁇ m or less.
  • the lower limit of the average particle diameter D 50 of the glass powder is not particularly limited, in practice it is 0.1 ⁇ m or more.
  • the “average particle diameter D 50 ” is a value measured on a volume basis, and indicates a value measured by a laser diffraction method.
  • the glass for coating a semiconductor element of the present invention is prepared, for example, by mixing the raw material powders of the respective oxide components into a batch, fusing at about 1500 ° C. for about 1 hour, vitrifying, and then forming (then, if necessary, pulverizing) , Classification).
  • the material for coating a semiconductor element of the present invention includes a glass powder made of the glass for coating a semiconductor element, but may be mixed with a ceramic powder to form a composite powder, if necessary.
  • the addition of ceramic powder makes it easier to adjust the coefficient of thermal expansion.
  • the amount of the ceramic powder is preferably less than 25%, particularly less than 20% with respect to 100 parts by mass of the glass powder. If the content of the ceramic powder is too large, the softening fluidity of the glass is impaired, and it becomes difficult to coat the surface of the semiconductor element.
  • the average particle diameter D 50 of the ceramic powder is preferably 30 ⁇ m or less, particularly 20 ⁇ m or less. When the average particle diameter D 50 of the ceramic powder is too large, the surface smoothness of the coating layer is liable to lower.
  • the lower limit of the average particle diameter D 50 of the ceramic powder is not particularly limited, but realistically is 0.1 ⁇ m or more.
  • the coefficient of thermal expansion in the temperature range of 30 to 300 ° C. is preferably 20 ⁇ 10 ⁇ 7 / ° C. or more and 55 ⁇ 10 ⁇ 7 / ° C. or less, particularly 30 ⁇ 10 ⁇ 7 / ° C. It is not less than 50 ° C. and not more than 50 ⁇ 10 ⁇ 7 / ° C.
  • the coefficient of thermal expansion is out of the above range, cracks, warpage, and the like due to a difference in coefficient of thermal expansion with the semiconductor element are likely to occur.
  • the surface charge density is preferably 6 ⁇ 10 11 / cm 2 or less, particularly 5 ⁇ 10 11 / cm 2 or less when the surface of the semiconductor element having a voltage of 1000 V or less is coated, for example. If the surface charge density is too high, the breakdown voltage increases, but at the same time, the leakage current tends to increase.
  • the “surface charge density” refers to a value measured by a method described in the section of Examples described later.
  • Table 1 shows Examples (Samples Nos. 1 to 4) of the present invention and Comparative Examples (Samples Nos. 5 and 6).
  • Each sample was produced as follows. First, raw material powders were prepared into a batch so as to have the glass composition shown in the table, melted at 1500 ° C. for 1 hour, and vitrified. Subsequently, after forming the molten glass into a film and then pulverized by a ball mill, and classified with a 350 mesh sieve to obtain a glass powder having an average particle diameter D 50 is 12 [mu] m. The sample No. In No. 4, a cordierite powder (average particle diameter D 50 : 12 ⁇ m) was added to the obtained glass powder in an amount of 15% by mass to obtain a composite powder.
  • the thermal expansion coefficient is a value measured in a temperature range of 30 to 300 ° C. using a push-rod type thermal expansion coefficient measuring apparatus.
  • the surface charge density was measured as follows. First, each sample was dispersed in an organic solvent, attached to a silicon substrate surface by electrophoresis so as to have a constant thickness, and then baked to form a coating layer. Next, after an aluminum electrode was formed on the surface of the coating layer, the change in electric capacity in the coating layer was measured using a CV meter, and the surface charge density was calculated.
  • the acid resistance was evaluated as follows. Each sample was press-molded to a size of about 20 mm in diameter and about 4 mm in thickness, and then fired to produce a pellet-shaped sample. This sample was immersed in 30% nitric acid at 25 ° C. for 1 minute to reduce the unit area from the mass loss. Per mass change was calculated and used as an index of acid resistance. Note that " ⁇ " mass change is less than 1.0 mg / cm 2 per unit area was 1.0 mg / cm 2 or more as " ⁇ ".
  • the sample No. In Nos. 1 to 4 the surface charge density was 6 ⁇ 10 11 / cm 2 or less, and the evaluation of acid resistance was also good. Therefore, the sample No. Nos. 1 to 4 are considered to be suitable as a semiconductor element coating material used for coating a low breakdown voltage semiconductor element.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

Le verre pour revêtement d'élément à semi-conducteurs de l'invention est caractéristique en ce qu'il comprend, en tant que composition de verre, en % en moles, 18 à 43% de ＳｉＯ２, 5 à 21% de Ｂ２Ｏ３, 8 à 21% de Ａｌ２Ｏ３, 10 à 25% de ZnO ainsi que 10 à 25% de ＭｇＯ＋ＣａＯ, et ne comprend substantiellement pas de composant plomb.
PCT/JP2019/036160 2018-10-04 2019-09-13 Verre pour revêtement d'élément à semi-conducteurs, et matériau pour revêtement de semi-conducteur mettant en œuvre celui-ci WO2020071093A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980051203.4A CN112512982B (zh) 2018-10-04 2019-09-13 半导体元件被覆用玻璃以及使用其的半导体被覆用材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-189156 2018-10-04
JP2018189156A JP7185181B2 (ja) 2018-10-04 2018-10-04 半導体素子被覆用ガラス及びこれを用いた半導体被覆用材料

Publications (1)

Publication Number Publication Date
WO2020071093A1 true WO2020071093A1 (fr) 2020-04-09

Family

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Family Applications (1)

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PCT/JP2019/036160 WO2020071093A1 (fr) 2018-10-04 2019-09-13 Verre pour revêtement d'élément à semi-conducteurs, et matériau pour revêtement de semi-conducteur mettant en œuvre celui-ci

Country Status (4)

Country Link
JP (1) JP7185181B2 (fr)
CN (1) CN112512982B (fr)
TW (1) TWI819109B (fr)
WO (1) WO2020071093A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060001A1 (fr) * 2019-09-24 2021-04-01 日本電気硝子株式会社 Verre pour revêtement d'élément semi-conducteur et matériau pour revêtement semi-conducteur l'utilisant

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55113641A (en) * 1979-02-22 1980-09-02 Asahi Glass Co Ltd Insulating glass composition
US4319215A (en) * 1979-07-13 1982-03-09 Hitachi, Ltd. Non-linear resistor and process for producing same
US5216207A (en) * 1991-02-27 1993-06-01 David Sarnoff Research Center, Inc. Low temperature co-fired multilayer ceramic circuit boards with silver conductors
JPH08188446A (ja) * 1995-01-11 1996-07-23 Sumitomo Metal Mining Co Ltd ガラスセラミック基板
JP2004039355A (ja) * 2002-07-02 2004-02-05 Sumitomo Metal Mining Co Ltd 導電性組成物
WO2012160704A1 (fr) * 2011-05-26 2012-11-29 新電元工業株式会社 Composition de verre pour protection de jonction de semi-conducteurs, procédé de production pour dispositif à semi-conducteur et dispositif à semi-conducteur
JP2013060353A (ja) * 2011-08-25 2013-04-04 Nippon Electric Glass Co Ltd 半導体素子被覆用ガラス
WO2013168236A1 (fr) * 2012-05-08 2013-11-14 新電元工業株式会社 Dispositif semi-conducteur scellé à la résine, et procédé de production de dispositif semi-conducteur scellé à la résine

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009119433A1 (ja) * 2008-03-25 2011-07-21 日本山村硝子株式会社 無鉛ガラス及び無鉛ガラスセラミックス用組成物
WO2011013776A1 (fr) * 2009-07-31 2011-02-03 旭硝子株式会社 Verre d’étanchéité, matériau d’étanchéité et pâte pour matériau d’étanchéité pour dispositifs semi-conducteurs, et dispositif semi-conducteur et procédé de production associé
WO2013114562A1 (fr) * 2012-01-31 2013-08-08 新電元工業株式会社 Composition de verre pour la protection de jonctions de semi-conducteurs, procédé de fabrication de dispositif à semi-conducteurs, et dispositif à semi-conducteurs

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55113641A (en) * 1979-02-22 1980-09-02 Asahi Glass Co Ltd Insulating glass composition
US4319215A (en) * 1979-07-13 1982-03-09 Hitachi, Ltd. Non-linear resistor and process for producing same
US5216207A (en) * 1991-02-27 1993-06-01 David Sarnoff Research Center, Inc. Low temperature co-fired multilayer ceramic circuit boards with silver conductors
JPH08188446A (ja) * 1995-01-11 1996-07-23 Sumitomo Metal Mining Co Ltd ガラスセラミック基板
JP2004039355A (ja) * 2002-07-02 2004-02-05 Sumitomo Metal Mining Co Ltd 導電性組成物
WO2012160704A1 (fr) * 2011-05-26 2012-11-29 新電元工業株式会社 Composition de verre pour protection de jonction de semi-conducteurs, procédé de production pour dispositif à semi-conducteur et dispositif à semi-conducteur
JP2013060353A (ja) * 2011-08-25 2013-04-04 Nippon Electric Glass Co Ltd 半導体素子被覆用ガラス
WO2013168236A1 (fr) * 2012-05-08 2013-11-14 新電元工業株式会社 Dispositif semi-conducteur scellé à la résine, et procédé de production de dispositif semi-conducteur scellé à la résine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060001A1 (fr) * 2019-09-24 2021-04-01 日本電気硝子株式会社 Verre pour revêtement d'élément semi-conducteur et matériau pour revêtement semi-conducteur l'utilisant

Also Published As

Publication number Publication date
JP7185181B2 (ja) 2022-12-07
CN112512982B (zh) 2023-02-24
TW202028143A (zh) 2020-08-01
CN112512982A (zh) 2021-03-16
JP2020055724A (ja) 2020-04-09
TWI819109B (zh) 2023-10-21

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