WO2024253096A1 - Verre pour revêtir un élément semi-conducteur et corps fritté pour revêtir un élément semi-conducteur - Google Patents

Verre pour revêtir un élément semi-conducteur et corps fritté pour revêtir un élément semi-conducteur Download PDF

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Publication number
WO2024253096A1
WO2024253096A1 PCT/JP2024/020388 JP2024020388W WO2024253096A1 WO 2024253096 A1 WO2024253096 A1 WO 2024253096A1 JP 2024020388 W JP2024020388 W JP 2024020388W WO 2024253096 A1 WO2024253096 A1 WO 2024253096A1
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WO
WIPO (PCT)
Prior art keywords
glass
zno
semiconductor element
sio
semiconductor elements
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
PCT/JP2024/020388
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English (en)
Japanese (ja)
Inventor
将行 廣瀬
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 JP2025526116A priority Critical patent/JPWO2024253096A1/ja
Priority to CN202480037730.0A priority patent/CN121335867A/zh
Publication of WO2024253096A1 publication Critical patent/WO2024253096A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

  • the present invention relates to glass for covering semiconductor elements and sintered bodies for covering semiconductor elements.
  • Semiconductor elements such as silicon diodes and transistors generally have their surfaces, including the P-N junctions, covered with glass. This stabilizes the surface of the semiconductor element and prevents deterioration of characteristics over time.
  • the properties required for glass used to cover semiconductor elements include (1) a thermal expansion coefficient that matches that of the semiconductor element to prevent cracks due to differences in thermal expansion coefficients with the semiconductor element, (2) the ability to cover the semiconductor element at low temperatures (e.g., 900°C or lower) to prevent deterioration of the characteristics of the semiconductor element, and (3) the absence of impurities such as alkaline components that adversely affect the surface of the semiconductor element.
  • zinc-based glasses such as ZnO-B 2 O 3 -SiO 2- based glasses and lead-based glasses such as PbO-SiO 2 -Al 2 O 3 -based glasses and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 -based glasses have been known as glasses for covering semiconductor elements.
  • lead-based glasses such as PbO-SiO 2 -Al 2 O 3- based glasses and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 -based glasses are becoming mainstream (for example, see Patent Documents 1 to 4).
  • the lead component in lead-based glass is harmful to the environment.
  • the zinc-based glass mentioned above contains small amounts of lead and bismuth, so it cannot be said to be completely harmless to the environment.
  • Another problem is that zinc-based glass is more susceptible to devitrification during the melting process than lead-based glass.
  • the present invention was developed in consideration of the above circumstances, and its technical objective is to provide a glass for covering semiconductor elements that has a small environmental impact and is less susceptible to devitrification during the melting process.
  • the devitrified material generated in the glass melting process is gahnite (ZnAl 2 O 4 ), and that by regulating the ratio of the content of Al 2 O 3 to the total content of SiO 2 and ZnO in SiO 2 -ZnO-Al 2 O 3 based glass, gahnite is less likely to be generated in the glass melting process, and propose this invention.
  • the glass for covering semiconductor elements of the present invention contains, in mole percent, SiO 2 +ZnO 40-75%, B 2 O 3 0-20%, Al 2 O 3 5-15%, and MgO + CaO 8-22%, and is characterized in that, in mole ratio, Al 2 O 3 /(SiO 2 +ZnO) is 0.2 or less, and is substantially free of lead components.
  • SiO 2 +ZnO refers to the total content of SiO 2 and ZnO.
  • MgO+CaO is the total content of MgO and CaO.
  • Al 2 O 3 /(SiO 2 +ZnO) is the value obtained by dividing the content of Al 2 O 3 by the total content of SiO 2 and ZnO.
  • Substantially free of means that the component is not intentionally added as a glass component, and does not mean that even unavoidable impurities are completely excluded. Specifically, it means that the content of the component, including impurities, is less than 0.1 mass%.
  • the glass for covering semiconductor elements of the present invention preferably has a thermal expansion coefficient of 20 to 55 ⁇ 10 -7 /° C. in the temperature range of 30 to 300° C.
  • the "thermal expansion coefficient in the temperature range of 30 to 300° C.” refers to a value measured using a push rod type thermal expansion coefficient measuring device.
  • the present invention makes it possible to provide glass for covering semiconductor elements that has a small environmental impact and is less susceptible to devitrification during the melting process.
  • the glass for covering semiconductor elements of the present invention is characterized in that it contains, in mole percent, SiO 2 +ZnO 40-75%, B 2 O 3 0-20%, Al 2 O 3 5-15%, and MgO + CaO 8-22% as a glass composition, and that the molar ratio Al 2 O 3 /(SiO 2 +ZnO) is 0.2 or less, and it is substantially free of lead components.
  • % means mol % unless otherwise specified.
  • the numerical range indicated by "to” means a range including the numerical values before and after "to” as the minimum and maximum values, respectively.
  • SiO2 and ZnO are components that stabilize glass.
  • SiO2 + ZnO is 40 to 75%, preferably 45 to 70%, 50 to 68%, 53 to 65%, and particularly preferably 55 to 64%. If the amount of SiO2 + ZnO is too small, gahnite is likely to precipitate in the melting process. On the other hand, if the amount of SiO2 + ZnO is too large, the softening point of the glass is likely to increase significantly.
  • the SiO2 content is preferably 25 to 40%, 22 to 38%, 24 to 36%, particularly preferably 26 to 34%.
  • the ZnO content is preferably 15-40%, 22-38%, 24-36%, and particularly preferably 26-34%.
  • B 2 O 3 is a component for forming a glass network and for increasing the softening fluidity.
  • the content of B 2 O 3 is 0 to 20%, preferably 0 to 18%, and particularly preferably 0 to 16%. If the content of B 2 O 3 is too high, the thermal expansion coefficient tends to be unduly high and the acid resistance tends to be reduced.
  • Al 2 O 3 is a component that stabilizes glass.
  • the content of Al 2 O 3 is 5 to 15%, and preferably 6 to 14%, 7 to 13%, 8 to 12%, 8 to 11%, and particularly preferably 9 to 10%. If the content of Al 2 O 3 is too low, vitrification becomes difficult. On the other hand, if the content of Al 2 O 3 is too high, gahnite is likely to precipitate in the melting process. In addition, the softening point of the glass is likely to increase significantly.
  • Al2O3 /( SiO2 +ZnO) is 0.2 or less, preferably 0.19 or less, and particularly preferably 0.18 or less. If Al2O3 /( SiO2 +ZnO) is too large, gahnite tends to precipitate in the melting process. There is no particular lower limit for Al2O3 /( SiO2 + ZnO), but it is practically 0.07 or more.
  • MgO and CaO are components that lower the viscosity of glass.
  • the MgO + CaO content is 8-22%, and preferably 10-20%. If the MgO + CaO content is too low, the softening temperature of the glass tends to increase. On the other hand, if the MgO + CaO content is too high, the thermal expansion coefficient may become too high, acid resistance may decrease, and insulation properties may decrease.
  • the MgO content is preferably 2-20%, 3-15%, and especially 4-13%.
  • the CaO content is preferably 2-20%, 3-15%, and particularly preferably 4-13%.
  • other components e.g., SrO, BaO, MnO2 , Ta2O5 , Nb2O5 , CeO2 , Sb2O3 , etc.
  • other components e.g., SrO, BaO, MnO2 , Ta2O5 , Nb2O5 , CeO2 , Sb2O3 , etc.
  • the material contains substantially no lead components (e.g., PbO, etc.) and substantially no Bi 2 O 3 , F, or Cl. It is also preferable that the material contains substantially no alkaline components (Li 2 O, Na 2 O, and K 2 O) that adversely affect the surface of semiconductor elements.
  • lead components e.g., PbO, etc.
  • Bi 2 O 3 e.g., F, or Cl.
  • alkaline components Li 2 O, Na 2 O, and K 2 O
  • the glass for covering a semiconductor element of the present invention preferably has a thermal expansion coefficient of 20 to 55 ⁇ 10 ⁇ 7 /° C., particularly 30 to 50 ⁇ 10 ⁇ 7 /° C., in the temperature range of 30 to 300° C. If the thermal expansion coefficient is outside the above range, cracks, warping, etc. are likely to occur due to the difference in thermal expansion coefficient with the semiconductor element.
  • the glass for coating semiconductor elements of the present invention is preferably in powder form. If it is processed into powder form, it can be easily used to coat the surface of a semiconductor element using, for example, a paste method or an electrophoretic coating method.
  • the average particle diameter D50 of the glass powder is preferably 25 ⁇ m or less, particularly 15 ⁇ m or less. If the average particle diameter D50 of the glass powder is too large, it becomes difficult to make a paste. In addition, it becomes difficult to apply the paste by electrophoresis.
  • the lower limit of the average particle diameter D50 of the glass powder is not particularly limited, but in reality, it is 0.1 ⁇ m or more.
  • the "average particle diameter D50" is a value measured on a volume basis, and refers to a value measured by a laser diffraction method.
  • the glass for covering semiconductor elements of the present invention may be mixed with ceramic powder to form a composite powder, if necessary. Adding ceramic powder makes it easier to adjust the thermal expansion coefficient.
  • the amount of ceramic powder is less than 25 parts by mass, and especially less than 20 parts by mass, per 100 parts by mass of glass powder. If the ceramic powder content is too high, the softening fluidity of the glass is impaired, making it difficult to coat the surface of the semiconductor element.
  • the average particle diameter D50 of the ceramic powder is preferably 30 ⁇ m or less, particularly 20 ⁇ m or less. If the average particle diameter D50 of the ceramic powder is too large, the surface smoothness of the coating layer is likely to decrease.
  • the lower limit of the average particle diameter D50 of the ceramic powder is not particularly limited, but is practically 0.1 ⁇ m or more.
  • raw material powders mixed to obtain the desired glass composition are melted at 1300-1550°C for 1-2 hours until a homogeneous glass is obtained.
  • the resulting molten glass is then formed into a film or other shape, which is then crushed and classified to produce powdered glass for coating semiconductor elements.
  • the surface of the semiconductor element is coated with powdered glass for covering semiconductor elements, for example, by using a paste method, electrophoretic coating method, or the like.
  • the glass for covering semiconductor elements that has covered the surface of the semiconductor element becomes a sintered body for covering semiconductor elements in which no crystals are precipitated.
  • the sintered body for covering semiconductor elements has the same composition range as the glass composition of the glass for covering semiconductor elements.
  • Table 1 shows examples of the present invention (samples No. 1-4, 9, 10) and comparative examples (samples No. 5-8).
  • Each sample was prepared as follows: First, raw material powders were mixed to obtain the glass composition shown in the table, and the mixture was melted at 1500° C. for 1 hour to vitrify the glass. The molten glass was then formed into a film, which was then pulverized in a ball mill and classified using a 350 mesh sieve to obtain a glass powder with an average particle size D50 of 12 ⁇ m.
  • the thermal expansion coefficient was measured using a push rod type thermal expansion coefficient measuring device in the temperature range of 30 to 300°C.
  • Devitrification resistance was evaluated as follows. 100 g of glass film from each sample was placed in a platinum crucible and held at 1150°C for 24 hours, after which the presence of devitrified matter (gahnite) was confirmed by visual inspection. After that, the sample was held at 1400°C for 10 minutes, and if devitrified matter (gahnite) was not confirmed by visual inspection, it was marked as "Good”, and if devitrified matter (gahnite) was confirmed, it was marked as "Poor”. The devitrified matter was measured using an X-ray diffraction device and confirmed to be gahnite.
  • Samples Nos. 5 to 8 have too large Al 2 O 3 /(SiO 2 +ZnO) and therefore are considered to be glasses that are likely to cause problems in the melting process and have poor devitrification resistance.

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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

L'invention concerne un verre pour revêtir un élément semi-conducteur, le verre présentant une faible charge environnementale et étant peu susceptible de subir une dévitrification dans une étape de fusion.　Un verre pour revêtir un élément semi-conducteur selon la présente invention est caractérisé : en ce qu'il contient, en tant que composition de verre en % en moles, 40 à 75 % de SiO2+ZnO, 0 à 20 % de B2O3, 5 à 15 % d'Al2O3, et 8 à 22 % de MgO+CaO ; donnant un rapport molaire Al2O3/(SiO2+ZnO) qui est de 0,2 ou moins ; et en ce qu'il ne contient sensiblement pas de composant de plomb.
PCT/JP2024/020388 2023-06-08 2024-06-04 Verre pour revêtir un élément semi-conducteur et corps fritté pour revêtir un élément semi-conducteur Pending WO2024253096A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2025526116A JPWO2024253096A1 (fr) 2023-06-08 2024-06-04
CN202480037730.0A CN121335867A (zh) 2023-06-08 2024-06-04 半导体元件被覆用玻璃以及半导体元件被覆用烧结体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023094622 2023-06-08
JP2023-094622 2023-06-08

Publications (1)

Publication Number Publication Date
WO2024253096A1 true WO2024253096A1 (fr) 2024-12-12

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PCT/JP2024/020388 Pending WO2024253096A1 (fr) 2023-06-08 2024-06-04 Verre pour revêtir un élément semi-conducteur et corps fritté pour revêtir un élément semi-conducteur

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Country Link
JP (1) JPWO2024253096A1 (fr)
CN (1) CN121335867A (fr)
TW (1) TW202502677A (fr)
WO (1) WO2024253096A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03126639A (ja) * 1989-10-06 1991-05-29 Nippon Electric Glass Co Ltd 被覆用ガラス組成物
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
WO2018221426A1 (fr) * 2017-05-27 2018-12-06 日本山村硝子株式会社 Composition de verre d'encapsulation
JP2020055725A (ja) * 2018-10-04 2020-04-09 日本電気硝子株式会社 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
WO2020158187A1 (fr) * 2019-01-29 2020-08-06 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
WO2021149633A1 (fr) * 2020-01-21 2021-07-29 日本山村硝子株式会社 Verre d'étanchéité/revêtement à faible capacité de dilatation thermique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03126639A (ja) * 1989-10-06 1991-05-29 Nippon Electric Glass Co Ltd 被覆用ガラス組成物
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
WO2018221426A1 (fr) * 2017-05-27 2018-12-06 日本山村硝子株式会社 Composition de verre d'encapsulation
JP2020055725A (ja) * 2018-10-04 2020-04-09 日本電気硝子株式会社 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
WO2020158187A1 (fr) * 2019-01-29 2020-08-06 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
WO2021149633A1 (fr) * 2020-01-21 2021-07-29 日本山村硝子株式会社 Verre d'étanchéité/revêtement à faible capacité de dilatation thermique

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Publication number Publication date
CN121335867A (zh) 2026-01-13
TW202502677A (zh) 2025-01-16
JPWO2024253096A1 (fr) 2024-12-12

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