WO2011093177A1 - Glass for semiconductor coating and material for semiconductor coating using the same - Google Patents

Glass for semiconductor coating and material for semiconductor coating using the same Download PDF

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Publication number
WO2011093177A1
WO2011093177A1 PCT/JP2011/050808 JP2011050808W WO2011093177A1 WO 2011093177 A1 WO2011093177 A1 WO 2011093177A1 JP 2011050808 W JP2011050808 W JP 2011050808W WO 2011093177 A1 WO2011093177 A1 WO 2011093177A1
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WO
WIPO (PCT)
Prior art keywords
glass
semiconductor
semiconductor coating
coating
zno
Prior art date
Application number
PCT/JP2011/050808
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French (fr)
Japanese (ja)
Inventor
欣克 西川
Original Assignee
日本電気硝子株式会社
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Filing date
Publication date
Priority claimed from JP2010016552A external-priority patent/JP5565747B2/en
Priority claimed from JP2010195611A external-priority patent/JP5773327B2/en
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 CN201180007607.7A priority Critical patent/CN102741185B/en
Publication of WO2011093177A1 publication Critical patent/WO2011093177A1/en

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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
    • 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
    • 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
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds

Definitions

  • the present invention relates to glass used for coating a semiconductor device including a PN junction and a semiconductor coating material using the same.
  • the surface including the PN junction portion of the semiconductor element is covered with a material containing glass from the viewpoint of preventing contamination by outside air.
  • a material containing glass from the viewpoint of preventing contamination by outside air.
  • the characteristics required for glass used as a semiconductor coating material are as follows: (1) The thermal expansion coefficient of the semiconductor is such that cracks do not occur due to the difference in thermal expansion coefficient with the semiconductor element during coating. (2) In order to prevent deterioration of the characteristics of the semiconductor element, it can be coated at a low temperature (for example, 900 ° C. or less), (3) It does not contain impurities such as alkali components that adversely affect the surface of the semiconductor element, 4) Electrical characteristics after the surface coating of the semiconductor element include high reliability such as high reverse breakdown voltage and low leakage current.
  • zinc-based glass such as ZnO—B 2 O 3 —SiO 2 , PbO—SiO 2 —Al 2 O 3 or PbO—SiO 2 —Al 2 O 3 —B 2 O is used.
  • Lead glass such as 3 series is known.
  • lead-based glasses such as PbO—SiO 2 —Al 2 O 3 and PbO—SiO 2 —Al 2 O 3 —B 2 O 3 are mainly used from the viewpoint of workability (for example, patent documents). 1 to 4).
  • lead components such as PbO are harmful to the environment, their use in electric and electronic equipment is being prohibited in recent years, and lead-free materials are being developed.
  • Some zinc-based glasses such as ZnO—B 2 O 3 —SiO 2 described above cannot be used from the viewpoint of the environment because they contain a small amount of lead components.
  • ZnO—B 2 O 3 —SiO 2 described above cannot be used from the viewpoint of the environment because they contain a small amount of lead components.
  • even if it is a lead-free composition those having a low surface charge density after semiconductor surface coating are the mainstream, and it has been difficult to cope with semiconductor elements for high voltage resistance.
  • the first object of the present invention is to provide a glass for semiconductor coating having a high surface charge density after coating the semiconductor surface even if it does not contain a lead component.
  • zinc-based glass is inferior in chemical durability compared to lead-based glass, and its resistance to acids in the post-process after glass firing is relatively weak. Therefore, it was necessary to form a protective film on the surface of the coated glass and perform a subsequent process.
  • a second object of the present invention is to provide a glass for semiconductor coating having a high surface charge density after coating the semiconductor surface and excellent chemical durability even if it does not contain a lead component.
  • the present inventor has found that the first and second problems can be solved by using a ZnO—B 2 O 3 —SiO 2 glass having a characteristic composition, and proposes the present invention.
  • the glass for semiconductor coating of the present invention that solves the first problem is 50% by weight of ZnO, 19% to 28% of B 2 O 3 , 7% to 15% of SiO 2 , 3 % of Al 2 O 3 to 3% by weight.
  • the composition is 12%, Bi 2 O 3 0.1 to 5%, and contains substantially no lead component.
  • the glass for semiconductor coating of the present invention that solves the first problem contains a specific amount of Al 2 O 3 and Bi 2 O 3 with respect to ZnO—B 2 O 3 —SiO 2 glass, so that the semiconductor The surface charge density after surface coating is large, and it is suitable for coating a semiconductor device for high withstand voltage. Moreover, since the lead component is not substantially contained, the burden on the environment is small.
  • substantially does not contain a lead component means that it is not intentionally added as a glass component, and the impurities that are inevitably mixed are completely eliminated. It does not mean to be excluded. Objectively, it means that the content of lead components including impurities is less than 0.1% by mass.
  • the preferred embodiment of the glass for semiconductor coating of the present invention that solves the first problem further contains a composition of MnO 2 0 to 5%, Nb 2 O 5 0 to 5%, CeO 2 0 to 3%. It is characterized by that.
  • this invention relates to the glass powder for semiconductor coating comprised using the glass for semiconductor coating of this invention which solves said 1st subject, and the material for semiconductor coating.
  • the glass powder for semiconductor coating of the present invention having such a structure is characterized by comprising any one of the above glass for semiconductor coating.
  • the semiconductor coating glass is powdery, the semiconductor surface can be easily coated.
  • the semiconductor coating material of the present invention having such a structure is characterized in that it contains the semiconductor coating glass powder.
  • the preferred form of the semiconductor coating material of the present invention is selected from TiO 2 , ZrO 2 , ZnO, ZnO ⁇ B 2 O 3 and 2ZnO ⁇ SiO 2 with respect to 100 parts by mass of the glass powder for semiconductor coating. It is characterized by containing 0.01 to 5 parts by mass of at least one kind of inorganic powder.
  • the thermal expansion coefficients of glass and Si are close.
  • the thermal expansion coefficient of glass can be adjusted with the crystal component contained in glass, it is very difficult to control appropriately the quantity of the crystal which precipitates out of glass. Therefore, if the above-mentioned inorganic powder is appropriately added to the glass for semiconductor coating, these inorganic powders serve as nucleating agents, so that the amount of precipitated crystals can be controlled relatively easily. As a result, it is possible to easily adjust to a desired thermal expansion coefficient.
  • Another preferred embodiment of the semiconductor coating material of the present invention is characterized in that the surface charge density is 7 ⁇ 10 11 / cm 2 or more.
  • the glass for semiconductor coating of the present invention that solves the second problem is ZnO 40-60%, B 2 O 3 5-25%, SiO 2 15-35%, Al 2 O 3 3-12 in mass%. % Composition and substantially free of lead component.
  • the glass for semiconductor coating that solves the second problem of the present invention contains a specific amount of Al 2 O 3 with respect to ZnO—B 2 O 3 —SiO 2 glass, and the content of each component
  • substantially does not contain a lead component means that a lead component is not intentionally added as a glass component, and is unavoidable. This does not mean that impurities that are mixed in are completely eliminated. Objectively, it means that the content of lead components including impurities is less than 0.1% by mass.
  • preferred embodiments of the glass for semiconductor coating of the present invention that solves the second problem further include Bi 2 O 3 0-5%, MnO 2 0-5%, Nb 2 O 5 0-5%, CeO 2. It contains 0 to 3% composition.
  • this invention relates to the semiconductor coating material comprised using the glass for semiconductor coating which solves said 2nd subject.
  • the semiconductor coating material of the present invention having such a structure is characterized by containing glass powder made of the semiconductor coating glass.
  • the semiconductor surface can be easily coated by using the semiconductor coating material.
  • the preferred embodiment of a semiconductor coating material of the present invention with respect to the glass powder 100 parts by weight of at least one selected TiO 2, ZrO 2, ZnO, from ZnO ⁇ B 2 O 3, and 2ZnO ⁇ SiO 2 It is characterized by containing 0.01 to 5 parts by mass of various types of inorganic powders.
  • the thermal expansion coefficients of glass and Si are close.
  • the thermal expansion coefficient of glass can be adjusted with the crystal component contained in glass, it is very difficult to control appropriately the quantity of the crystal which precipitates out of glass. Therefore, if the above-mentioned inorganic powder is appropriately added to the glass for semiconductor coating, these inorganic powders serve as nucleating agents, so that the amount of precipitated crystals can be controlled relatively easily. As a result, it is possible to easily adjust to a desired thermal expansion coefficient.
  • a semiconductor-coated glass that solves the first problem will be described as a first embodiment of a semiconductor-coated glass that solves the first problem, and a semiconductor-coated glass powder and a semiconductor-coated material that are formed using the same. And the semiconductor coating material comprised using it is demonstrated as 2nd embodiment.
  • the glass for semiconductor coating of the first embodiment of the present invention is ZnO 50 to 65%, B 2 O 3 19 to 28%, SiO 2 7 to 15%, Al 2 O 3 3 to 12% by mass,
  • the composition contains 0.1 to 5% Bi 2 O 3 and contains substantially no lead component.
  • ZnO is a component that stabilizes glass.
  • the content of ZnO is preferably 50 to 65%, particularly 55 to 63%. If the ZnO content is less than 50%, the thermal expansion coefficient of the glass is increased, and cracking may occur due to a difference in thermal expansion from the semiconductor element when the semiconductor element is sealed. On the other hand, when the content of ZnO is more than 65%, crystallization proceeds rapidly, so that it is difficult to cover the surface of the semiconductor element due to insufficient fluidity of glass.
  • B 2 O 3 is a component for forming a network of glass and is a component for improving fluidity.
  • the content of B 2 O 3 is preferably 19 to 28%, particularly preferably 20 to 25%.
  • the content of B 2 O 3 is less than 19%, the crystallinity becomes strong, the fluidity is impaired, and it tends to be difficult to cover the surface of the semiconductor element.
  • the content of B 2 O 3 is more than 28%, the thermal expansion coefficient of the glass increases, and cracks occur due to the difference in thermal expansion from the semiconductor element when the semiconductor element is sealed. There is a fear.
  • SiO 2 is a component for forming a network of glass and is a component for improving acid resistance.
  • the SiO 2 content is preferably 7 to 15%, particularly preferably 9 to 14%.
  • the content of SiO 2 is less than 7%, the thermal expansion coefficient of the glass is increased, and cracking may occur due to a difference in thermal expansion from the semiconductor element when the semiconductor element is sealed. In addition, the chemical durability of the glass tends to decrease. If the content of SiO 2 is more than 15%, it becomes difficult to obtain a homogeneous glass.
  • Al 2 O 3 is a component that increases the surface charge density of the glass.
  • the content of Al 2 O 3 is preferably 3 to 12%, particularly preferably 5 to 10%. When the content of Al 2 O 3 is less than 3%, it is difficult to obtain the above effect. On the other hand, when the content of Al 2 O 3 is more than 12%, the glass tends to be devitrified.
  • Bi 2 O 3 is also a component that increases the surface charge density of the glass.
  • the content of Bi 2 O 3 is preferably 0.1 to 5%, particularly 0.5 to 3%. If the content of Bi 2 O 3 is less than 0.1%, the above effect is difficult to obtain. On the other hand, when the content of Bi 2 O 3 is more than 5%, the glass tends to devitrify.
  • Semiconductor coating glass of the present invention may contain MnO 2, Nb 2 O 5, CeO 2 in addition to the above components. These components have the effect of reducing the leakage current of the semiconductor element.
  • the MnO 2 content is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of MnO 2 is more than 5%, the melting property of the glass tends to decrease.
  • the content of Nb 2 O 5 is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of Nb 2 O 5 is more than 5%, the melting property of the glass tends to decrease.
  • the CeO 2 content is preferably 0 to 3%, particularly preferably 0.1 to 2%. If there is more CeO 2 than 3%, the crystallinity of the glass becomes too strong, and the fluidity of the glass tends to decrease.
  • the glass for semiconductor coating of this invention does not contain lead components (PbO etc.) substantially from an environmental viewpoint.
  • the glass for semiconductor coating of the present invention is preferably in the form of powder from the viewpoint of easily covering the surface of the semiconductor element.
  • the average particle diameter D 50 of the glass powder for the semiconductor coatings are 25 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • Semiconductor coated glass powder having an average particle diameter D 50 of is greater than 25 [mu] m, paste becomes difficult to uniformly coat the semiconductor surface becomes difficult. Also, coating by electrophoresis tends to be difficult.
  • the lower limit is not particularly limited, but is practically 0.1 ⁇ m or more.
  • the semiconductor coating material of the present invention comprises the glass powder for semiconductor coating.
  • the semiconductor coating material of the present invention has at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO ⁇ B 2 O 3 , and 2ZnO ⁇ SiO 2 as a core with respect to the glass powder for semiconductor coating. It may be contained as a forming agent.
  • the content of these inorganic powders is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the semiconductor coating glass powder.
  • the content of the inorganic powder is less than 0.01 parts by mass, the amount of precipitated crystals is small and it tends to be difficult to achieve a desired thermal expansion coefficient.
  • the content of the inorganic powder is more than 5 parts by mass, the amount of crystals to be precipitated tends to be too large, fluidity is impaired, and the semiconductor element surface tends to be difficult to coat.
  • the average particle diameter D 50 of the inorganic powder is 5 ⁇ m or less, in particular 3 ⁇ m or less. Although a minimum is not specifically limited, Actually, it is 0.1 micrometer or more.
  • the semiconductor device of the above 1500V is 10 ⁇ 10 11 / cm 2 or more.
  • the thermal expansion coefficient (30 to 300 ° C.) of the semiconductor coating material of the present invention is, for example, 20 to 60 ⁇ 10 ⁇ 7 / ° C., more preferably 30 to 50 ⁇ 10 ⁇ 7 / ° C., depending on the thermal expansion coefficient of the semiconductor element. It adjusts suitably in the range of ° C.
  • the glass for semiconductor coating of the present invention is obtained by blending raw material powders of each oxide component into a batch, melting it for about 1 hour at a temperature of about 1400 ° C., and vitrifying it, followed by molding, pulverization, and classification. Can do.
  • the glass for semiconductor coating according to the second embodiment of the present invention has a composition of mass%, ZnO 40-60%, B 2 O 3 5-25%, SiO 2 15-35%, Al 2 O 3 3-12. %, And the lead component is not substantially contained.
  • ZnO is a component that stabilizes glass.
  • the content of ZnO is preferably 40 to 60%, particularly 47 to 55%. When the content of ZnO is less than 40%, the devitrification at the time of glass melting becomes strong and melting becomes difficult. On the other hand, if the ZnO content is more than 60%, the acid resistance tends to be weak.
  • B 2 O 3 is a component for forming a network of glass and is a component for improving fluidity.
  • the content of B 2 O 3 is preferably 5 to 25%, particularly 7 to 18%. If the content of B 2 O 3 is less than 5%, the crystallinity becomes strong, the fluidity is impaired, and the coating on the surface of the semiconductor element becomes difficult. On the other hand, when the content of B 2 O 3 is more than 25%, the thermal expansion coefficient tends to increase. Moreover, there exists a tendency for chemical durability to fall.
  • SiO 2 is a component for forming a network of glass and is a component for improving acid resistance.
  • the SiO 2 content is preferably 15 to 35%, more preferably 20 to 33%.
  • the content of SiO 2 is less than 15%, the chemical durability tends to be inferior.
  • the content of SiO 2 is more than 35%, devitrification at the time of melting becomes strong, and it becomes difficult to obtain a homogeneous glass.
  • Al 2 O 3 is a component that increases the surface charge density of the glass.
  • the content of Al 2 O 3 is preferably 3 to 12%, particularly preferably 5 to 10%.
  • the content of Al 2 O 3 is less than 3%, it is difficult to obtain the above effect.
  • the content of Al 2 O 3 is more than 12%, devitrification easily occurs.
  • the glass for semiconductor coating of the present invention preferably further contains, as a composition, Bi 2 O 3 0-5%, MnO 2 0-5%, Nb 2 O 5 0-5%, CeO 2 0-3%. .
  • Bi 2 O 3 is a component that increases the surface charge density of the glass.
  • the content of Bi 2 O 3 is preferably 0 to 5%, particularly preferably 0.1 to 3%. If the content of Bi 2 O 3 is more than 5%, the glass tends to be devitrified.
  • MnO 2 , Nb 2 O 5 , and CeO 2 are components that reduce the leakage current of the semiconductor element.
  • the MnO 2 content is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of MnO 2 is more than 5%, the melting property of the glass tends to decrease.
  • the content of Nb 2 O 5 is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of Nb 2 O 5 is more than 5%, the melting property of the glass tends to decrease.
  • the CeO 2 content is preferably 0 to 3%, particularly preferably 0.1 to 2%. If there is more CeO 2 than 3%, the crystallinity of the glass becomes too strong, and the fluidity of the glass tends to decrease.
  • the glass for semiconductor coating of the present invention contains substantially no lead component (PbO or the like) from the viewpoint of the environment. Further, alkaline components adversely affecting the semiconductor device surface (Li 2 O, Na 2 O , K 2 O) is preferably free of.
  • the glass for semiconductor coating of the present invention is preferably in the form of powder from the viewpoint of easily covering the surface of the semiconductor element.
  • the average particle diameter D 50 of the glass powder is 25 ⁇ m or less, and particularly preferably 15 ⁇ m or less. And 25 ⁇ m greater than the average particle diameter D 50 of the glass powder, a paste for the glass coating becomes difficult. Also, electrophoretic coating becomes difficult.
  • the lower limit is not particularly limited, but is practically 0.1 ⁇ m or more.
  • the semiconductor coating material of the present invention comprises the glass powder for semiconductor coating.
  • the semiconductor coating material of the present invention has at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO ⁇ B 2 O 3 , and 2ZnO ⁇ SiO 2 as a core with respect to the glass powder for semiconductor coating. It may be contained as a forming agent.
  • the content of these inorganic powders is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the semiconductor coating glass powder.
  • the content of the inorganic powder is less than 0.01 parts by mass, the amount of precipitated crystals is small and it tends to be difficult to achieve a desired thermal expansion coefficient.
  • the content of the inorganic powder is more than 5 parts by mass, the amount of crystals to be precipitated tends to be too large, fluidity is impaired, and the semiconductor element surface tends to be difficult to coat.
  • the average particle diameter D 50 of the inorganic powder is 5 ⁇ m or less, in particular 3 ⁇ m or less. Although a minimum is not specifically limited, Actually, it is 0.1 micrometer or more.
  • the thermal expansion coefficient (30 to 300 ° C.) of the glass for semiconductor coating of the present invention is, for example, 20 to 60 ⁇ 10 ⁇ 7 / ° C., further 30 to 50 ⁇ 10 ⁇ 7 / ° C., depending on the thermal expansion coefficient of the semiconductor element. It adjusts suitably in the range of ° C.
  • the surface charge density of the semiconductor coating material of the present invention 7 ⁇ 10 11 / cm 2 or more in the semiconductor device of the voltage 1000V, it is preferable that the semiconductor device of the above 1500V is 10 ⁇ 10 11 / cm 2 or more.
  • the surface charge density is a value measured by the method described in the examples.
  • the glass for semiconductor coating of the present invention is prepared by blending raw material powders of each oxide component into a batch and melting it for about 1 hour at a temperature of about 1500 ° C., followed by molding (and then grinding if necessary, Classification).
  • Table 1 shows examples and comparative examples for the first embodiment of the present invention.
  • Each sample was produced as follows. First, raw material powders were blended so as to have the glass composition in the table to make a batch, and melted at a temperature of 1400 ° C. for 1 hour to be vitrified. Subsequently, the molten glass was formed into a film shape, pulverized with a ball mill, and classified using a 350 mesh sieve to obtain a glass powder for semiconductor coating (semiconductor coating material) (average particle diameter D 50 : 12 ⁇ m).
  • semiconductor coating semiconductor coating material
  • Example 6 The thermal expansion coefficient and surface charge density of the obtained glass powder for semiconductor coating were measured. In addition, in Example 6, it measured about what added 1 mass part of ZnO powder with respect to 100 mass parts of glass powder for semiconductor coating. The results are shown in Table 1.
  • the thermal expansion coefficient is a value measured in a temperature range of 30 to 300 ° C. using a dilatometer.
  • the surface charge density was measured as follows. First, the glass powder for semiconductor coating was dispersed in an organic solvent, adhered to the silicon surface by electrophoresis so as to have a constant film thickness, and then fired to form a glass layer. After forming an aluminum electrode on the glass layer, the change in electric capacity in the glass was measured using a CV meter, and the surface charge density was calculated.
  • the samples of Examples 1 to 6 had a high surface charge density of 8 to 18. This is almost the same surface charge density as PbO—SiO 2 —Al 2 O 3 or PbO—SiO 2 —Al 2 O 3 —B 2 O 3 lead glass. Therefore, the semiconductor coating materials of Examples 1 to 6 are suitable for coating a semiconductor device for high breakdown voltage.
  • Comparative Examples 1 and 2 have a low surface charge density and are not suitable for coating a semiconductor device for high voltage resistance.
  • Table 2 shows examples and comparative examples for the second embodiment of the present invention.
  • Each sample was produced as follows. First, raw material powders were prepared so as to have the glass composition shown in the table, and batchwise melted at 1500 ° C. for 1 hour to be vitrified. Subsequently, the molten glass was formed into a film shape, pulverized with a ball mill, and classified using a 350 mesh sieve to obtain a glass powder for semiconductor coating (average particle diameter D 50 : 12 ⁇ m).
  • the thermal expansion coefficient is a value measured in a temperature range of 30 to 300 ° C. using a dilatometer.
  • the surface charge density was measured as follows. First, glass powder was dispersed in an organic solvent, adhered to the silicon substrate surface by electrophoresis so as to have a constant film thickness, and then fired to form a glass layer. After forming an aluminum electrode on the glass layer, the change in electric capacity in the glass was measured using a CV meter, and the surface charge density was calculated.
  • Acid resistance was evaluated as follows. First, a glass powder is press-molded to a size of about 20 mm in diameter and 4 mm in thickness, and baked to prepare a pellet-shaped sample. The mass change per hit was calculated and the acid resistance was evaluated.
  • the samples of Examples 1 to 6 had a high surface charge density of 14 to 18. This is a surface charge density equal to or higher than that of lead-based glass such as PbO—SiO 2 —Al 2 O 3 or PbO—SiO 2 —Al 2 O 3 —B 2 O 3 . Moreover, the mass loss by an acid resistance test is 0.6 mg / cm ⁇ 2 > or less, and it turns out that it is excellent in acid resistance. Therefore, the semiconductor coating materials of Examples 1 to 6 are suitable for coating a semiconductor device for high breakdown voltage.
  • Comparative Examples 1 and 2 have a surface charge density as low as 6 or less and are not suitable for coating a semiconductor device for high breakdown voltage. Moreover, the mass loss by an acid resistance test was 3.5 mg / cm ⁇ 2 > or more, and the acid resistance was also inferior.

Abstract

Provided is a glass for semiconductor coating that causes little environmental stress and has a high surface charge density after semiconductor surface coating. The glass for semiconductor coating is either the following (1) or (2). The glass for semiconductor coating (2) causes little environmental stress, has a high surface charge density after semiconductor surface coating, and has excellent chemical resistance. The glass for semiconductor coating (1) is essentially lead-free and contains a composition comprising, by mass%, 50% to 65% ZnO, 19% to 28% B2O3, 7% to 15% SiO2, 3% to 12% Al2O3, and 0.1% to 5% Bi2O3, while the glass for semiconductor coating (2) is essentially lead-free and contains a composition comprising, by mass%, 40% to 60% ZnO, 5% to 25% B2O3, 15% to 35% SiO2, and 3% to 12% Al2O3.

Description

半導体被覆用ガラスおよびそれを用いてなる半導体被覆用材料Semiconductor coating glass and semiconductor coating material using the same
　本発明はＰ－Ｎ接合を含む半導体装置の被覆用として用いられるガラスおよびそれを用いてなる半導体被覆用材料に関するものである。 The present invention relates to glass used for coating a semiconductor device including a PN junction and a semiconductor coating material using the same.
　一般に、シリコンダイオードやトランジスタ等の半導体装置は、外気による汚染を防止する観点から半導体素子のＰ－Ｎ接合部を含む表面がガラスを含む材料により被覆される。これにより半導体素子表面が安定化され、経時的な特性劣化を抑制することができる。 Generally, in a semiconductor device such as a silicon diode or a transistor, the surface including the PN junction portion of the semiconductor element is covered with a material containing glass from the viewpoint of preventing contamination by outside air. As a result, the surface of the semiconductor element is stabilized and deterioration of characteristics over time can be suppressed.
　半導体被覆用材料として用いられるガラスに要求される特性として、（１）被覆時に半導体素子との熱膨張係数差が原因となってクラック等が発生しないように、熱膨張係数が半導体の熱膨張係数に適合すること、（２）半導体素子の特性劣化を防止するため、低温（例えば９００℃以下）で被覆できること、（３）半導体素子表面に悪影響を与えるアルカリ成分等の不純物を含まないこと、（４）半導体素子表面被覆後の電気特性として、逆耐圧が高く、漏れ電流が少ないなど高い信頼性を有すること、等が挙げられる。 The characteristics required for glass used as a semiconductor coating material are as follows: (1) The thermal expansion coefficient of the semiconductor is such that cracks do not occur due to the difference in thermal expansion coefficient with the semiconductor element during coating. (2) In order to prevent deterioration of the characteristics of the semiconductor element, it can be coated at a low temperature (for example, 900 ° C. or less), (3) It does not contain impurities such as alkali components that adversely affect the surface of the semiconductor element, 4) Electrical characteristics after the surface coating of the semiconductor element include high reliability such as high reverse breakdown voltage and low leakage current.
　従来、半導体被覆用ガラスとしては、ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系等の亜鉛系ガラスや、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３系或いはＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３系等の鉛系ガラスが知られている。中でも、作業性の観点から、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３系およびＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３系等の鉛系ガラスが主流となっている（例えば、特許文献１～４参照）。 Conventionally, as glass for semiconductor coating, zinc-based glass such as ZnO—B 2 O 3 —SiO 2 , PbO—SiO 2 —Al 2 O 3 or PbO—SiO 2 —Al 2 O 3 —B 2 O is used. Lead glass such as 3 series is known. Among these, lead-based glasses such as PbO—SiO 2 —Al 2 O 3 and PbO—SiO 2 —Al 2 O 3 —B 2 O 3 are mainly used from the viewpoint of workability (for example, patent documents). 1 to 4).
日本国特公平１－４９６５３号公報Japanese Patent Publication No. 1-49653 日本国特開昭５０－１２９１８１号公報Japanese Unexamined Patent Publication No. 50-129181 日本国特開昭４８－４３２７５号公報Japanese Unexamined Patent Publication No. 48-43275 日本国特開２００８－１６２８８１号公報Japanese Unexamined Patent Publication No. 2008-162881
　ＰｂＯ等の鉛成分は環境に対して有害な成分であることから、近年、電気および電子機器での使用が禁止されつつあり、各種材料の無鉛化が進んでいる。既述のＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系等の亜鉛系ガラスにも、少量の鉛成分を含有しているために環境の面から使用できないものがある。また、無鉛組成であっても、半導体表面被覆後の表面電荷密度が低いものが主流であり、高耐圧用の半導体素子に対応することが困難であった。 Since lead components such as PbO are harmful to the environment, their use in electric and electronic equipment is being prohibited in recent years, and lead-free materials are being developed. Some zinc-based glasses such as ZnO—B 2 O 3 —SiO 2 described above cannot be used from the viewpoint of the environment because they contain a small amount of lead components. Moreover, even if it is a lead-free composition, those having a low surface charge density after semiconductor surface coating are the mainstream, and it has been difficult to cope with semiconductor elements for high voltage resistance.
　したがって、本発明は、鉛成分を含有しなくても半導体表面被覆後の表面電荷密度が大きい半導体被覆用ガラスを提供することを第一の課題とする。 Therefore, the first object of the present invention is to provide a glass for semiconductor coating having a high surface charge density after coating the semiconductor surface even if it does not contain a lead component.
　さらに、亜鉛系ガラスは鉛系ガラスと比較して化学耐久性に劣り、ガラス焼成後の後工程での酸に対する耐性が比較的弱い。そのため、被覆ガラス表面にさらに保護膜を形成して後工程を行う必要があった。 Furthermore, zinc-based glass is inferior in chemical durability compared to lead-based glass, and its resistance to acids in the post-process after glass firing is relatively weak. Therefore, it was necessary to form a protective film on the surface of the coated glass and perform a subsequent process.
　そこで、本発明は、鉛成分を含有しなくても半導体表面被覆後の表面電荷密度が大きく、かつ化学耐久性に優れた半導体被覆用ガラスを提供することを第二の課題とする。 Therefore, a second object of the present invention is to provide a glass for semiconductor coating having a high surface charge density after coating the semiconductor surface and excellent chemical durability even if it does not contain a lead component.
　本発明者は、鋭意検討した結果、特性の組成を有するＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系ガラスにより前記第一および第二の課題を解決できることを見出し、本発明として提案するものである。 As a result of intensive studies, the present inventor has found that the first and second problems can be solved by using a ZnO—B 2 O 3 —SiO 2 glass having a characteristic composition, and proposes the present invention.
　すなわち、第一の課題を解決する本発明の半導体被覆用ガラスは、質量％で、ＺｎＯ　５０～６５％、Ｂ２Ｏ３　１９～２８％、ＳｉＯ２　７～１５％、Ａｌ２Ｏ３　３～１２％、Ｂｉ２Ｏ３　０．１～５％の組成を含有し、鉛成分を実質的に含有しないことを特徴とする。 That is, the glass for semiconductor coating of the present invention that solves the first problem is 50% by weight of ZnO, 19% to 28% of B 2 O 3 , 7% to 15% of SiO 2 , 3 % of Al 2 O 3 to 3% by weight. The composition is 12%, Bi 2 O 3 0.1 to 5%, and contains substantially no lead component.
　第一の課題を解決する本発明の半導体被覆用ガラスは、ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系ガラスに対して、Ａｌ２Ｏ３およびＢｉ２Ｏ３を特定量含有しているため、半導体表面被覆後の表面電荷密度が大きく高耐圧用の半導体素子の被覆に適したものである。また、鉛成分を実質的に含有しないため、環境への負担が小さい。 The glass for semiconductor coating of the present invention that solves the first problem contains a specific amount of Al 2 O 3 and Bi 2 O 3 with respect to ZnO—B 2 O 3 —SiO 2 glass, so that the semiconductor The surface charge density after surface coating is large, and it is suitable for coating a semiconductor device for high withstand voltage. Moreover, since the lead component is not substantially contained, the burden on the environment is small.
　なお、第一の課題を解決する本発明半導体被覆用ガラスにおいて、「鉛成分を実質的に含有しない」とはガラス成分として意図的に添加しないことを意味し、不可避的に混入する不純物まで完全に排除することを意味するものではない。客観的には、不純物を含めた鉛成分の含有量が０．１質量％未満であることを意味する。 In addition, in the glass for semiconductor coating of the present invention that solves the first problem, “substantially does not contain a lead component” means that it is not intentionally added as a glass component, and the impurities that are inevitably mixed are completely eliminated. It does not mean to be excluded. Objectively, it means that the content of lead components including impurities is less than 0.1% by mass.
　また、第一の課題を解決する本発明の半導体被覆用ガラスの好適形態は、さらに、ＭｎＯ２　０～５％、Ｎｂ２Ｏ５　０～５％、ＣｅＯ２　０～３％の組成を含有することを特徴とする。 Further, the preferred embodiment of the glass for semiconductor coating of the present invention that solves the first problem further contains a composition of MnO 2 0 to 5%, Nb 2 O 5 0 to 5%, CeO 2 0 to 3%. It is characterized by that.
　また、本発明は、上記第一の課題を解決する本発明の半導体被覆用ガラスを用いて構成される半導体被覆用ガラス粉末および半導体被覆用材料に関する。
　かかる構成の本発明の半導体被覆用ガラス粉末は、前記いずれかの半導体被覆用ガラスからなることを特徴とする。 Moreover, this invention relates to the glass powder for semiconductor coating comprised using the glass for semiconductor coating of this invention which solves said 1st subject, and the material for semiconductor coating.
The glass powder for semiconductor coating of the present invention having such a structure is characterized by comprising any one of the above glass for semiconductor coating.
　半導体被覆用ガラスが粉末状であることにより、半導体表面の被覆を容易に行うことができる。 Since the semiconductor coating glass is powdery, the semiconductor surface can be easily coated.
　また、かかる構成の本発明の半導体被覆用材料は、前記半導体被覆用ガラス粉末を含むことを特徴とする。 Further, the semiconductor coating material of the present invention having such a structure is characterized in that it contains the semiconductor coating glass powder.
　また、上記本発明の半導体被覆用材料の好適形態は、前記半導体被覆用ガラス粉末１００質量部に対して、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＺｎＯ・Ｂ２Ｏ３および２ＺｎＯ・ＳｉＯ２から選択される少なくとも１種類の無機粉末を０．０１～５質量部含有してなることを特徴とする。 Further, the preferred form of the semiconductor coating material of the present invention is selected from TiO 2 , ZrO 2 , ZnO, ZnO · B 2 O 3 and 2ZnO · SiO 2 with respect to 100 parts by mass of the glass powder for semiconductor coating. It is characterized by containing 0.01 to 5 parts by mass of at least one kind of inorganic powder.
　特に、Ｓｉ等の半導体素子とガラスの接触面積が非常に大きい場合には、ガラスとＳｉの熱膨張係数が近いことが望ましい。ガラスの熱膨張係数は、ガラス中に含まれる結晶成分により調整することができるが、ガラス中から析出する結晶の量を適切に制御することは非常に困難である。そこで、半導体被覆用ガラスに対して、上記の無機粉末を適宜添加すれば、これらの無機粉末が核形成剤の役割を果たすため、析出する結晶量を比較的容易に制御できる。結果として、所望の熱膨張係数に容易に調整することが可能となる。 In particular, when the contact area between a semiconductor element such as Si and glass is very large, it is desirable that the thermal expansion coefficients of glass and Si are close. Although the thermal expansion coefficient of glass can be adjusted with the crystal component contained in glass, it is very difficult to control appropriately the quantity of the crystal which precipitates out of glass. Therefore, if the above-mentioned inorganic powder is appropriately added to the glass for semiconductor coating, these inorganic powders serve as nucleating agents, so that the amount of precipitated crystals can be controlled relatively easily. As a result, it is possible to easily adjust to a desired thermal expansion coefficient.
　また、上記本発明の半導体被覆用材料の別の好適形態は、表面電荷密度が７×１０１１／ｃｍ２以上であることを特徴とする。 Another preferred embodiment of the semiconductor coating material of the present invention is characterized in that the surface charge density is 7 × 10 11 / cm 2 or more.
　さらに第二の課題を解決する本発明の半導体被覆用ガラスは、質量％で、ＺｎＯ　４０～６０％、Ｂ２Ｏ３　５～２５％、ＳｉＯ２　１５～３５％、Ａｌ２Ｏ３　３～１２％の組成を含有し、鉛成分を実質的に含有しないことを特徴とする。 Furthermore, the glass for semiconductor coating of the present invention that solves the second problem is ZnO 40-60%, B 2 O 3 5-25%, SiO 2 15-35%, Al 2 O 3 3-12 in mass%. % Composition and substantially free of lead component.
　本発明の第二の課題を解決する半導体被覆用ガラスは、ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系ガラスに対して、特定量のＡｌ２Ｏ３を含有するものであり、各成分の含有量を厳密に制限することにより、半導体表面被覆後の表面電荷密度が大きく高耐圧用の半導体素子の被覆に適したもので、かつ化学的耐久性が高いという特徴を有する。また、鉛成分を実質的に含有しないため、環境への負担が小さい。 The glass for semiconductor coating that solves the second problem of the present invention contains a specific amount of Al 2 O 3 with respect to ZnO—B 2 O 3 —SiO 2 glass, and the content of each component By strictly limiting the above, the surface charge density after the semiconductor surface coating is large and suitable for the coating of a semiconductor device for high withstand voltage, and the chemical durability is high. Moreover, since the lead component is not substantially contained, the burden on the environment is small.
　なお、本発明の第二の課題を解決する半導体被覆用ガラスにおいて、「鉛成分を実質的に含有しない」とは、ガラス成分として鉛成分を意図的に添加しないことを意味し、不可避的に混入する不純物まで完全に排除することを意味するものではない。客観的には、不純物を含めた鉛成分の含有量が０．１質量％未満であることを意味する。 In addition, in the glass for semiconductor coating that solves the second problem of the present invention, “substantially does not contain a lead component” means that a lead component is not intentionally added as a glass component, and is unavoidable. This does not mean that impurities that are mixed in are completely eliminated. Objectively, it means that the content of lead components including impurities is less than 0.1% by mass.
　また、第二の課題を解決する本発明の半導体被覆用ガラスの好適形態は、さらに、Ｂｉ２Ｏ３　０～５％、ＭｎＯ２　０～５％、Ｎｂ２Ｏ５　０～５％、ＣｅＯ２　０～３％の組成を含有することを特徴とする。 Further, preferred embodiments of the glass for semiconductor coating of the present invention that solves the second problem further include Bi 2 O 3 0-5%, MnO 2 0-5%, Nb 2 O 5 0-5%, CeO 2. It contains 0 to 3% composition.
　また、本発明は、上記第二の課題を解決する半導体被覆用ガラスを用いて構成される半導体被覆用材料に関する。
　かかる構成の本発明の半導体被覆用材料は、前記半導体被覆用ガラスからなるガラス粉末を含むことを特徴とする。 Moreover, this invention relates to the semiconductor coating material comprised using the glass for semiconductor coating which solves said 2nd subject.
The semiconductor coating material of the present invention having such a structure is characterized by containing glass powder made of the semiconductor coating glass.
　当該半導体被覆用材料を用いることにより、半導体表面の被覆を容易に行うことができる。 The semiconductor surface can be easily coated by using the semiconductor coating material.
　また、上記本発明の半導体被覆用材料の好適形態は、前記ガラス粉末１００質量部に対して、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＺｎＯ・Ｂ２Ｏ３および２ＺｎＯ・ＳｉＯ２から選択される少なくとも１種類の無機粉末を０．０１～５質量部含有してなることを特徴とする。 Further, the preferred embodiment of a semiconductor coating material of the present invention, with respect to the glass powder 100 parts by weight of at least one selected TiO 2, ZrO 2, ZnO, from ZnO · B 2 O 3, and 2ZnO · SiO 2 It is characterized by containing 0.01 to 5 parts by mass of various types of inorganic powders.
　特に、Ｓｉ等の半導体素子とガラスの接触面積が非常に大きい場合には、ガラスとＳｉの熱膨張係数が近いことが望ましい。ガラスの熱膨張係数は、ガラス中に含まれる結晶成分により調整することができるが、ガラス中から析出する結晶の量を適切に制御することは非常に困難である。そこで、半導体被覆用ガラスに対して、上記の無機粉末を適宜添加すれば、これらの無機粉末が核形成剤の役割を果たすため、析出する結晶量を比較的容易に制御できる。結果として、所望の熱膨張係数に容易に調整することが可能となる。 In particular, when the contact area between a semiconductor element such as Si and glass is very large, it is desirable that the thermal expansion coefficients of glass and Si are close. Although the thermal expansion coefficient of glass can be adjusted with the crystal component contained in glass, it is very difficult to control appropriately the quantity of the crystal which precipitates out of glass. Therefore, if the above-mentioned inorganic powder is appropriately added to the glass for semiconductor coating, these inorganic powders serve as nucleating agents, so that the amount of precipitated crystals can be controlled relatively easily. As a result, it is possible to easily adjust to a desired thermal expansion coefficient.
　以下、本発明の半導体被覆用ガラスにおいて、各成分を上記の通り規定した理由を説明する。なお、以下の説明において、「％」は特に断りのない限り「質量％」を意味する。 Hereinafter, the reason why each component is defined as described above in the glass for semiconductor coating of the present invention will be described. In the following description, “%” means “% by mass” unless otherwise specified.
　以下、第一の課題を解決する半導体被覆ガラス並びにそれを用いて構成される半導体被覆用ガラス粉末および半導体被覆用材料を第一の実施形態として説明し、第二の課題を解決する半導体被覆ガラスおよびそれを用いて構成される半導体被覆用材料を第二の実施形態として説明する。 Hereinafter, a semiconductor-coated glass that solves the first problem will be described as a first embodiment of a semiconductor-coated glass that solves the first problem, and a semiconductor-coated glass powder and a semiconductor-coated material that are formed using the same. And the semiconductor coating material comprised using it is demonstrated as 2nd embodiment.
（第一の実施形態）
　本発明の第一の実施形態の半導体被覆用ガラスは、質量％で、ＺｎＯ　５０～６５％、Ｂ２Ｏ３　１９～２８％、ＳｉＯ２　７～１５％、Ａｌ２Ｏ３　３～１２％、Ｂｉ２Ｏ３　０．１～５％の組成を含有し、鉛成分を実質的に含有しないことを特徴とする。 (First embodiment)
The glass for semiconductor coating of the first embodiment of the present invention is ZnO 50 to 65%, B 2 O 3 19 to 28%, SiO 2 7 to 15%, Al 2 O 3 3 to 12% by mass, The composition contains 0.1 to 5% Bi 2 O 3 and contains substantially no lead component.
　ＺｎＯはガラスを安定化する成分である。ＺｎＯの含有量は５０～６５％、特に５５～６３％であることが好ましい。ＺｎＯの含有量が５０％より少ないと、ガラスの熱膨張係数が大きくなって、半導体素子を封止した際に半導体素子との熱膨張差が原因となってクラックが発生するおそれがある。一方、ＺｎＯの含有量が６５％より多いと、結晶化が急速に進行するため、ガラスの流動性不足により半導体素子表面を被覆することが困難になる傾向がある。 ZnO is a component that stabilizes glass. The content of ZnO is preferably 50 to 65%, particularly 55 to 63%. If the ZnO content is less than 50%, the thermal expansion coefficient of the glass is increased, and cracking may occur due to a difference in thermal expansion from the semiconductor element when the semiconductor element is sealed. On the other hand, when the content of ZnO is more than 65%, crystallization proceeds rapidly, so that it is difficult to cover the surface of the semiconductor element due to insufficient fluidity of glass.
　Ｂ２Ｏ３はガラスの網目形成成分で、流動性を高める成分である。Ｂ２Ｏ３の含有量は１９～２８％、特に２０～２５％であることが好ましい。Ｂ２Ｏ３の含有量が１９％より少ないと、結晶性が強くなって流動性が損なわれ、半導体素子表面を被覆することが困難になる傾向がある。一方、Ｂ２Ｏ３の含有量が２８％より多いと、ガラスの熱膨張係数が大きくなって、半導体素子を封止した際に半導体素子との熱膨張差が原因となってクラックが発生するおそれがある。 B 2 O 3 is a component for forming a network of glass and is a component for improving fluidity. The content of B 2 O 3 is preferably 19 to 28%, particularly preferably 20 to 25%. When the content of B 2 O 3 is less than 19%, the crystallinity becomes strong, the fluidity is impaired, and it tends to be difficult to cover the surface of the semiconductor element. On the other hand, when the content of B 2 O 3 is more than 28%, the thermal expansion coefficient of the glass increases, and cracks occur due to the difference in thermal expansion from the semiconductor element when the semiconductor element is sealed. There is a fear.
　ＳｉＯ２はガラスの網目形成成分であり、耐酸性を高める成分である。ＳｉＯ２の含有量は７～１５％、特に９～１４％であることが好ましい。ＳｉＯ２の含有量が７％より少ないと、ガラスの熱膨張係数が大きくなって、半導体素子を封止した際に半導体素子との熱膨張差が原因となってクラックが発生するおそれがある。また、ガラスの化学耐久性が低下しやすくなる。ＳｉＯ２の含有量が１５％より多いと、均質なガラスが得られにくくなる。 SiO 2 is a component for forming a network of glass and is a component for improving acid resistance. The SiO 2 content is preferably 7 to 15%, particularly preferably 9 to 14%. When the content of SiO 2 is less than 7%, the thermal expansion coefficient of the glass is increased, and cracking may occur due to a difference in thermal expansion from the semiconductor element when the semiconductor element is sealed. In addition, the chemical durability of the glass tends to decrease. If the content of SiO 2 is more than 15%, it becomes difficult to obtain a homogeneous glass.
　Ａｌ２Ｏ３はガラスの表面電荷密度を大きくする成分である。Ａｌ２Ｏ３の含有量は３～１２％、特に５～１０％であることが好ましい。Ａｌ２Ｏ３の含有量が３％より少ないと、前記効果が得られにくい。一方、Ａｌ２Ｏ３の含有量が１２％より多いと、ガラスが失透しやすくなる。 Al 2 O 3 is a component that increases the surface charge density of the glass. The content of Al 2 O 3 is preferably 3 to 12%, particularly preferably 5 to 10%. When the content of Al 2 O 3 is less than 3%, it is difficult to obtain the above effect. On the other hand, when the content of Al 2 O 3 is more than 12%, the glass tends to be devitrified.
　Ｂｉ２Ｏ３もガラスの表面電荷密度を高くする成分である。Ｂｉ２Ｏ３の含有量は０．１～５％、特に０．５～３％であることが好ましい。Ｂｉ２Ｏ３の含有量が０．１％より少ないと、前記効果が得られにくい。一方、Ｂｉ２Ｏ３の含有量が５％より多いと、ガラスが失透しやすくなる。 Bi 2 O 3 is also a component that increases the surface charge density of the glass. The content of Bi 2 O 3 is preferably 0.1 to 5%, particularly 0.5 to 3%. If the content of Bi 2 O 3 is less than 0.1%, the above effect is difficult to obtain. On the other hand, when the content of Bi 2 O 3 is more than 5%, the glass tends to devitrify.
　本発明の半導体被覆用ガラスは、上記成分以外にＭｎＯ２、Ｎｂ２Ｏ５、ＣｅＯ２を含有することができる。これらの成分は半導体素子の漏れ電流を低下させる効果がある。 Semiconductor coating glass of the present invention may contain MnO 2, Nb 2 O 5, CeO 2 in addition to the above components. These components have the effect of reducing the leakage current of the semiconductor element.
　ＭｎＯ２の含有量は０～５％、特に０．１～３％であることが好ましい。ＭｎＯ２の含有量が５％より多いと、ガラスの溶融性が低下する傾向がある。 The MnO 2 content is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of MnO 2 is more than 5%, the melting property of the glass tends to decrease.
　Ｎｂ２Ｏ５の含有量は０～５％、特に０．１～３％であることが好ましい。Ｎｂ２Ｏ５の含有量が５％より多いと、ガラスの溶融性が低下する傾向がある。 The content of Nb 2 O 5 is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of Nb 2 O 5 is more than 5%, the melting property of the glass tends to decrease.
　ＣｅＯ２の含有量は０～３％、特に０．１～２％であることが好ましい。ＣｅＯ２が３％より多いと、ガラスの結晶性が強くなりすぎてガラスの流動性が低下する傾向がある。 The CeO 2 content is preferably 0 to 3%, particularly preferably 0.1 to 2%. If there is more CeO 2 than 3%, the crystallinity of the glass becomes too strong, and the fluidity of the glass tends to decrease.
　なお本発明の半導体被覆用ガラスは、環境面の観点から実質的に鉛成分（ＰｂＯ等）を含有しない。 In addition, the glass for semiconductor coating of this invention does not contain lead components (PbO etc.) substantially from an environmental viewpoint.
　本発明の半導体被覆用ガラスは、半導体素子表面の被覆を容易に行える観点から、粉末状であることが好ましい。半導体被覆用ガラス粉末の平均粒径Ｄ５０は２５μｍ以下、特に１５μｍ以下であることが好ましい。半導体被覆用ガラス粉末の平均粒径Ｄ５０が２５μｍより大きいと、ペースト化が困難になり半導体表面に均一に被覆しにくくなる。また、電気泳動による被覆も困難になる傾向がある。なお下限は特に限定されないが、現実的には０．１μｍ以上である。 The glass for semiconductor coating of the present invention is preferably in the form of powder from the viewpoint of easily covering the surface of the semiconductor element. The average particle diameter D 50 of the glass powder for the semiconductor coatings are 25μm or less, and particularly preferably 15μm or less. Semiconductor coated glass powder having an average particle diameter D 50 of is greater than 25 [mu] m, paste becomes difficult to uniformly coat the semiconductor surface becomes difficult. Also, coating by electrophoresis tends to be difficult. The lower limit is not particularly limited, but is practically 0.1 μm or more.
　本発明の半導体被覆用材料は前記半導体被覆用ガラス粉末を含んでなるものである。なお本発明の半導体被覆用材料は、前記半導体被覆用ガラス粉末に対し、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＺｎＯ・Ｂ２Ｏ３、２ＺｎＯ・ＳｉＯ２から選択された少なくとも１種類の無機粉末を核形成剤として含有してなるものであってもよい。これらの無機粉末の含有量は、半導体被覆用ガラス粉末１００質量部に対して０．０１～５質量部、特に０．１～３質量部であることが好ましい。無機粉末の含有量が０．０１質量部より少ないと、析出する結晶量が少なく所望の熱膨張係数を達成することが困難となる傾向がある。無機粉末の含有量が５質量部より多いと、析出する結晶量が多くなりすぎて流動性が損なわれ、半導体素子表面の被覆が困難となる傾向がある。 The semiconductor coating material of the present invention comprises the glass powder for semiconductor coating. In addition, the semiconductor coating material of the present invention has at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO · B 2 O 3 , and 2ZnO · SiO 2 as a core with respect to the glass powder for semiconductor coating. It may be contained as a forming agent. The content of these inorganic powders is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the semiconductor coating glass powder. When the content of the inorganic powder is less than 0.01 parts by mass, the amount of precipitated crystals is small and it tends to be difficult to achieve a desired thermal expansion coefficient. When the content of the inorganic powder is more than 5 parts by mass, the amount of crystals to be precipitated tends to be too large, fluidity is impaired, and the semiconductor element surface tends to be difficult to coat.
　なお上記無機粉末の粒度が小さいほど、ガラスから析出する結晶の粒径が小さくなり機械的強度が大きくなる傾向がある。したがって、無機粉末の平均粒径Ｄ５０は５μｍ以下、特に３μｍ以下が好ましい。下限は特に限定されないが、現実的には０．１μｍ以上である。 In addition, there exists a tendency for the particle size of the crystal | crystallization which precipitates from glass to become small and the mechanical strength to become large, so that the particle size of the said inorganic powder is small. Therefore, the average particle diameter D 50 of the inorganic powder is 5μm or less, in particular 3μm or less. Although a minimum is not specifically limited, Actually, it is 0.1 micrometer or more.
　本発明の半導体被覆用材料の表面電荷密度は、電圧１０００Ｖの半導体装置には７×１０１１／ｃｍ２以上、１５００Ｖ以上の半導体装置には１０×１０１１／ｃｍ２以上であることが好ましい。 Surface charge density of the semiconductor coating material of the present invention, 7 × 10 11 / cm 2 or more in the semiconductor device of the voltage 1000V, it is preferable that the semiconductor device of the above 1500V is 10 × 10 11 / cm 2 or more.
　本発明の半導体被覆用材料の熱膨張係数（３０～３００℃）は、半導体素子の熱膨張係数に応じて、例えば２０～６０×１０－７／℃、さらには３０～５０×１０－７／℃の範囲で適宜調整される。 The thermal expansion coefficient (30 to 300 ° C.) of the semiconductor coating material of the present invention is, for example, 20 to 60 × 10 −7 / ° C., more preferably 30 to 50 × 10 −7 / ° C., depending on the thermal expansion coefficient of the semiconductor element. It adjusts suitably in the range of ° C.
　本発明の半導体被覆用ガラスは、各酸化物成分の原料粉末を調合してバッチとし、１４００℃前後の温度で約１時間溶融してガラス化した後、成形、粉砕、分級することによって得ることができる。 The glass for semiconductor coating of the present invention is obtained by blending raw material powders of each oxide component into a batch, melting it for about 1 hour at a temperature of about 1400 ° C., and vitrifying it, followed by molding, pulverization, and classification. Can do.
（第二の実施形態）
　本発明の第二の実施形態の半導体被覆用ガラスは、組成として質量％で、ＺｎＯ　４０～６０％、Ｂ２Ｏ３　５～２５％、ＳｉＯ２　１５～３５％、Ａｌ２Ｏ３　３～１２％を含有し、鉛成分を実質的に含有しないことを特徴とする。 (Second embodiment)
The glass for semiconductor coating according to the second embodiment of the present invention has a composition of mass%, ZnO 40-60%, B 2 O 3 5-25%, SiO 2 15-35%, Al 2 O 3 3-12. %, And the lead component is not substantially contained.
　ＺｎＯはガラスを安定化する成分である。ＺｎＯの含有量は４０～６０％、特に４７～５５％であることが好ましい。ＺｎＯの含有量が４０％より少ないと、ガラス溶融時の失透性が強くなり溶融が困難となる。一方、ＺｎＯの含有量が６０％より多いと、耐酸性が弱くなる傾向がある。 ZnO is a component that stabilizes glass. The content of ZnO is preferably 40 to 60%, particularly 47 to 55%. When the content of ZnO is less than 40%, the devitrification at the time of glass melting becomes strong and melting becomes difficult. On the other hand, if the ZnO content is more than 60%, the acid resistance tends to be weak.
　Ｂ２Ｏ３はガラスの網目形成成分で、流動性を高める成分である。Ｂ２Ｏ３の含有量は５～２５％、特に７～１８％であることが好ましい。Ｂ２Ｏ３の含有量が５％より少ないと、結晶性が強くなって流動性が損なわれ、半導体素子表面への被覆が困難になる。一方、Ｂ２Ｏ３の含有量が２５％より多いと、熱膨張係数が大きくなる傾向がある。また、化学耐久性が低下する傾向がある。 B 2 O 3 is a component for forming a network of glass and is a component for improving fluidity. The content of B 2 O 3 is preferably 5 to 25%, particularly 7 to 18%. If the content of B 2 O 3 is less than 5%, the crystallinity becomes strong, the fluidity is impaired, and the coating on the surface of the semiconductor element becomes difficult. On the other hand, when the content of B 2 O 3 is more than 25%, the thermal expansion coefficient tends to increase. Moreover, there exists a tendency for chemical durability to fall.
　ＳｉＯ２はガラスの網目形成成分であり、耐酸性を高める成分である。ＳｉＯ２の含有量は１５～３５％、特に２０～３３％であることが好ましい。ＳｉＯ２の含有量が１５％より少ないと、化学耐久性に劣る傾向がある。一方、ＳｉＯ２の含有量が３５％より多いと、溶融時の失透性が強くなり、均質なガラスが得られにくくなる。 SiO 2 is a component for forming a network of glass and is a component for improving acid resistance. The SiO 2 content is preferably 15 to 35%, more preferably 20 to 33%. When the content of SiO 2 is less than 15%, the chemical durability tends to be inferior. On the other hand, when the content of SiO 2 is more than 35%, devitrification at the time of melting becomes strong, and it becomes difficult to obtain a homogeneous glass.
　Ａｌ２Ｏ３はガラスの表面電荷密度を高くする成分である。Ａｌ２Ｏ３の含有量は３～１２％、特に５～１０％であることが好ましい。Ａｌ２Ｏ３の含有量が３％より少ないと、前記効果が得られにくい。一方、Ａｌ２Ｏ３の含有量が１２％より多いと失透しやすくなる。 Al 2 O 3 is a component that increases the surface charge density of the glass. The content of Al 2 O 3 is preferably 3 to 12%, particularly preferably 5 to 10%. When the content of Al 2 O 3 is less than 3%, it is difficult to obtain the above effect. On the other hand, when the content of Al 2 O 3 is more than 12%, devitrification easily occurs.
　本発明の半導体被覆用ガラスは、さらに組成として、Ｂｉ２Ｏ３　０～５％、ＭｎＯ２　０～５％、Ｎｂ２Ｏ５　０～５％、ＣｅＯ２　０～３％を含有することが好ましい。 The glass for semiconductor coating of the present invention preferably further contains, as a composition, Bi 2 O 3 0-5%, MnO 2 0-5%, Nb 2 O 5 0-5%, CeO 2 0-3%. .
　Ｂｉ２Ｏ３はガラスの表面電荷密度を高くする成分である。Ｂｉ２Ｏ３の含有量は０～５％、特に０．１～３％であることが好ましい。Ｂｉ２Ｏ３の含有量が５％より多いと、ガラスが失透しやすくなる。 Bi 2 O 3 is a component that increases the surface charge density of the glass. The content of Bi 2 O 3 is preferably 0 to 5%, particularly preferably 0.1 to 3%. If the content of Bi 2 O 3 is more than 5%, the glass tends to be devitrified.
　ＭｎＯ２、Ｎｂ２Ｏ５、ＣｅＯ２は半導体素子の漏れ電流を低下させる成分である。 MnO 2 , Nb 2 O 5 , and CeO 2 are components that reduce the leakage current of the semiconductor element.
　ＭｎＯ２の含有量は０～５％、特に０．１～３％であることが好ましい。ＭｎＯ２の含有量が５％より多いと、ガラスの溶融性が低下する傾向がある。 The MnO 2 content is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of MnO 2 is more than 5%, the melting property of the glass tends to decrease.
　Ｎｂ２Ｏ５の含有量は０～５％、特に０．１～３％であることが好ましい。Ｎｂ２Ｏ５の含有量が５％より多いと、ガラスの溶融性が低下する傾向がある。 The content of Nb 2 O 5 is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of Nb 2 O 5 is more than 5%, the melting property of the glass tends to decrease.
　ＣｅＯ２の含有量は０～３％、特に０．１～２％であることが好ましい。ＣｅＯ２が３％より多いと、ガラスの結晶性が強くなりすぎてガラスの流動性が低下する傾向がある。 The CeO 2 content is preferably 0 to 3%, particularly preferably 0.1 to 2%. If there is more CeO 2 than 3%, the crystallinity of the glass becomes too strong, and the fluidity of the glass tends to decrease.
　本発明の半導体被覆用ガラスは、環境面の観点から実質的に鉛成分（ＰｂＯ等）を含有しない。また、半導体素子表面に悪影響を与えるアルカリ成分（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）を含まないことが好ましい。 The glass for semiconductor coating of the present invention contains substantially no lead component (PbO or the like) from the viewpoint of the environment. Further, alkaline components adversely affecting the semiconductor device surface (Li 2 O, Na 2 O , K 2 O) is preferably free of.
　本発明の半導体被覆用ガラスは、半導体素子表面の被覆を容易に行える観点から、粉末状であることが好ましい。この場合、ガラス粉末の平均粒径Ｄ５０は２５μｍ以下、特に１５μｍ以下であることが好ましい。ガラス粉末の平均粒径Ｄ５０が２５μｍより大きいと、ガラス塗布のためのペースト化が困難になる。また、電気泳動塗布も困難になる。なお下限は特に限定されないが、現実的には０．１μｍ以上である。 The glass for semiconductor coating of the present invention is preferably in the form of powder from the viewpoint of easily covering the surface of the semiconductor element. In this case, the average particle diameter D 50 of the glass powder is 25μm or less, and particularly preferably 15μm or less. And 25μm greater than the average particle diameter D 50 of the glass powder, a paste for the glass coating becomes difficult. Also, electrophoretic coating becomes difficult. The lower limit is not particularly limited, but is practically 0.1 μm or more.
　本発明の半導体被覆用材料は前記半導体被覆用ガラス粉末を含んでなるものである。なお本発明の半導体被覆用材料は、前記半導体被覆用ガラス粉末に対し、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＺｎＯ・Ｂ２Ｏ３、２ＺｎＯ・ＳｉＯ２から選択された少なくとも１種類の無機粉末を核形成剤として含有してなるものであってもよい。これらの無機粉末の含有量は、半導体被覆用ガラス粉末１００質量部に対して０．０１～５質量部、特に０．１～３質量部であることが好ましい。無機粉末の含有量が０．０１質量部より少ないと、析出する結晶量が少なく所望の熱膨張係数を達成することが困難となる傾向がある。無機粉末の含有量が５質量部より多いと、析出する結晶量が多くなりすぎて流動性が損なわれ、半導体素子表面の被覆が困難となる傾向がある。 The semiconductor coating material of the present invention comprises the glass powder for semiconductor coating. The semiconductor coating material of the present invention has at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO · B 2 O 3 , and 2ZnO · SiO 2 as a core with respect to the glass powder for semiconductor coating. It may be contained as a forming agent. The content of these inorganic powders is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the semiconductor coating glass powder. When the content of the inorganic powder is less than 0.01 parts by mass, the amount of precipitated crystals is small and it tends to be difficult to achieve a desired thermal expansion coefficient. When the content of the inorganic powder is more than 5 parts by mass, the amount of crystals to be precipitated tends to be too large, fluidity is impaired, and the semiconductor element surface tends to be difficult to coat.
　なお上記無機粉末の粒度が小さいほど、ガラスから析出する結晶の粒径が小さくなり機械的強度が大きくなる傾向がある。したがって、無機粉末の平均粒径Ｄ５０は５μｍ以下、特に３μｍ以下が好ましい。下限は特に限定されないが、現実的には０．１μｍ以上である。 In addition, there exists a tendency for the particle size of the crystal | crystallization which precipitates from glass to become small and the mechanical strength to become large, so that the particle size of the said inorganic powder is small. Therefore, the average particle diameter D 50 of the inorganic powder is 5μm or less, in particular 3μm or less. Although a minimum is not specifically limited, Actually, it is 0.1 micrometer or more.
　本発明の半導体被覆用ガラスの熱膨張係数（３０～３００℃）は、半導体素子の熱膨張係数に応じて、例えば２０～６０×１０－７／℃、さらには３０～５０×１０－７／℃の範囲で適宜調整される。 The thermal expansion coefficient (30 to 300 ° C.) of the glass for semiconductor coating of the present invention is, for example, 20 to 60 × 10 −7 / ° C., further 30 to 50 × 10 −7 / ° C., depending on the thermal expansion coefficient of the semiconductor element. It adjusts suitably in the range of ° C.
　本発明の半導体被覆用材料の表面電荷密度は、電圧１０００Ｖの半導体装置には７×１０１１／ｃｍ２以上、１５００Ｖ以上の半導体装置には１０×１０１１／ｃｍ２以上であることが好ましい。なお、表面電荷密度は実施例に記載の方法によって測定した値を指す。 Surface charge density of the semiconductor coating material of the present invention, 7 × 10 11 / cm 2 or more in the semiconductor device of the voltage 1000V, it is preferable that the semiconductor device of the above 1500V is 10 × 10 11 / cm 2 or more. The surface charge density is a value measured by the method described in the examples.
　本発明の半導体被覆用ガラスは、各酸化物成分の原料粉末を調合してバッチとし、１５００℃前後の温度で約１時間溶融してガラス化した後、成形（その後、必要に応じて粉砕、分級）することによって得ることができる。 The glass for semiconductor coating of the present invention is prepared by blending raw material powders of each oxide component into a batch and melting it for about 1 hour at a temperature of about 1500 ° C., followed by molding (and then grinding if necessary, Classification).
　以下、実施例に基づいて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.
（第一の実施形態）
　表１は本発明の第一の実施形態についての実施例および比較例を示している。 (First embodiment)
Table 1 shows examples and comparative examples for the first embodiment of the present invention.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　以下のようにして各試料を作製した。まず表中のガラス組成となるように原料粉末を調合してバッチとし、１４００℃の温度で１時間溶融してガラス化した。続いてこの溶融ガラスをフィルム状に成形した後、ボールミルにて粉砕し、３５０メッシュの篩を用いて分級し、半導体被覆用ガラス粉末（半導体被覆用材料）を得た（平均粒径Ｄ５０：１２μｍ）。 Each sample was produced as follows. First, raw material powders were blended so as to have the glass composition in the table to make a batch, and melted at a temperature of 1400 ° C. for 1 hour to be vitrified. Subsequently, the molten glass was formed into a film shape, pulverized with a ball mill, and classified using a 350 mesh sieve to obtain a glass powder for semiconductor coating (semiconductor coating material) (average particle diameter D 50 : 12 μm).
　得られた半導体被覆用ガラス粉末について熱膨張係数と表面電荷密度を測定した。なお、実施例６では、半導体被覆用ガラス粉末１００質量部に対してＺｎＯ粉末を１質量部添加したものについて測定した。結果を表１に示す。 The thermal expansion coefficient and surface charge density of the obtained glass powder for semiconductor coating were measured. In addition, in Example 6, it measured about what added 1 mass part of ZnO powder with respect to 100 mass parts of glass powder for semiconductor coating. The results are shown in Table 1.
　熱膨張係数はディラトメーターを用いて３０～３００℃の温度範囲にて測定した値を示す。 The thermal expansion coefficient is a value measured in a temperature range of 30 to 300 ° C. using a dilatometer.
　表面電荷密度は次のようにして測定した。まず、半導体被覆用ガラス粉末を有機溶媒中に分散し、電気泳動によってシリコン表面に一定の膜厚になるように付着させ、次いで焼成を行いガラス層を形成した。ガラス層の上にアルミニウム電極を形成後、ガラス中の電気容量の変化をＣ－Ｖメータを用いて測定し、表面電荷密度を算出した。 The surface charge density was measured as follows. First, the glass powder for semiconductor coating was dispersed in an organic solvent, adhered to the silicon surface by electrophoresis so as to have a constant film thickness, and then fired to form a glass layer. After forming an aluminum electrode on the glass layer, the change in electric capacity in the glass was measured using a CV meter, and the surface charge density was calculated.
　表１から明らかなように、実施例１～６の試料は表面電荷密度が８～１８と高かった。これは、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３系或いはＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３系の鉛系ガラスとほぼ同等の表面電荷密度である。したがって、実施例１～６の半導体被覆用材料は高耐圧用の半導体素子の被覆に適したものである。 As is apparent from Table 1, the samples of Examples 1 to 6 had a high surface charge density of 8 to 18. This is almost the same surface charge density as PbO—SiO 2 —Al 2 O 3 or PbO—SiO 2 —Al 2 O 3 —B 2 O 3 lead glass. Therefore, the semiconductor coating materials of Examples 1 to 6 are suitable for coating a semiconductor device for high breakdown voltage.
　一方、比較例１および２の試料は表面電荷密度が低く、高耐圧用の半導体素子の被覆に適さないことがわかる。 On the other hand, it can be seen that the samples of Comparative Examples 1 and 2 have a low surface charge density and are not suitable for coating a semiconductor device for high voltage resistance.
（第二の実施形態）
　表２は本発明の第二の実施形態についての実施例および比較例を示している。 (Second embodiment)
Table 2 shows examples and comparative examples for the second embodiment of the present invention.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　各試料は以下のようにして作製した。まず表中のガラス組成となるように原料粉末を調合してバッチとし、１５００℃で１時間溶融してガラス化した。続いて、この溶融ガラスをフィルム状に成形した後、ボールミルにて粉砕し、３５０メッシュの篩を用いて分級し、半導体被覆用ガラス粉末（平均粒径Ｄ５０：１２μｍ）を得た。 Each sample was produced as follows. First, raw material powders were prepared so as to have the glass composition shown in the table, and batchwise melted at 1500 ° C. for 1 hour to be vitrified. Subsequently, the molten glass was formed into a film shape, pulverized with a ball mill, and classified using a 350 mesh sieve to obtain a glass powder for semiconductor coating (average particle diameter D 50 : 12 μm).
　得られた半導体被覆用ガラス粉末について熱膨張係数、表面電荷密度、耐酸性を測定した。結果を表２に示す。 The thermal expansion coefficient, surface charge density, and acid resistance of the obtained glass powder for semiconductor coating were measured. The results are shown in Table 2.
　熱膨張係数はディラトメーターを用いて３０～３００℃の温度範囲にて測定した値を示す。 The thermal expansion coefficient is a value measured in a temperature range of 30 to 300 ° C. using a dilatometer.
　表面電荷密度は次のようにして測定した。まず、ガラス粉末を有機溶媒中に分散し、電気泳動によってシリコン基板表面に一定の膜厚になるように付着させ、次いで焼成してガラス層を形成した。ガラス層の上にアルミニウム電極を形成後、ガラス中の電気容量の変化をＣ－Ｖメータを用いて測定し、表面電荷密度を算出した。 The surface charge density was measured as follows. First, glass powder was dispersed in an organic solvent, adhered to the silicon substrate surface by electrophoresis so as to have a constant film thickness, and then fired to form a glass layer. After forming an aluminum electrode on the glass layer, the change in electric capacity in the glass was measured using a CV meter, and the surface charge density was calculated.
　耐酸性は次のようにして評価した。まず、ガラス粉末を直径２０ｍｍ、厚み４ｍｍ程度大きさにプレス成型し、焼成してペレット状試料を作製し、この試料を３０％硝酸中に２５℃、１分浸漬した後の質量減から単位面積当たりの質量変化を算出し、耐酸性を評価した。 Acid resistance was evaluated as follows. First, a glass powder is press-molded to a size of about 20 mm in diameter and 4 mm in thickness, and baked to prepare a pellet-shaped sample. The mass change per hit was calculated and the acid resistance was evaluated.
　表１から明らかなように、実施例１～６の試料は表面電荷密度が１４～１８と高かった。これは、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３系あるいはＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３系等の鉛系ガラスと同等以上の表面電荷密度である。また、耐酸性試験による質量減は０．６ｍｇ／ｃｍ２以下であり、耐酸性に優れていることがわかる。したがって、実施例１～６の半導体被覆用材料は高耐圧用の半導体素子の被覆に適したものである。 As is apparent from Table 1, the samples of Examples 1 to 6 had a high surface charge density of 14 to 18. This is a surface charge density equal to or higher than that of lead-based glass such as PbO—SiO 2 —Al 2 O 3 or PbO—SiO 2 —Al 2 O 3 —B 2 O 3 . Moreover, the mass loss by an acid resistance test is 0.6 mg / cm < 2 > or less, and it turns out that it is excellent in acid resistance. Therefore, the semiconductor coating materials of Examples 1 to 6 are suitable for coating a semiconductor device for high breakdown voltage.
　一方、比較例１および２の試料は表面電荷密度が６以下と低く、高耐圧用の半導体素子の被覆に適していないことがわかる。また、耐酸性試験による質量減は３．５ｍｇ／ｃｍ２以上であり、耐酸性にも劣っていた。 On the other hand, it can be seen that the samples of Comparative Examples 1 and 2 have a surface charge density as low as 6 or less and are not suitable for coating a semiconductor device for high breakdown voltage. Moreover, the mass loss by an acid resistance test was 3.5 mg / cm < 2 > or more, and the acid resistance was also inferior.
　本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
　なお、本出願は、２０１０年１月２８日付で出願された日本特許出願（特願２０１０－０１６５５２）および２０１０年９月１日付で出願された日本特許出願（特願２０１０－１９５６１１）に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
  Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2010-016552) filed on January 28, 2010 and a Japanese patent application (Japanese Patent Application No. 2010-195611) filed on September 1, 2010. Which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (10)

  1. 　質量％で、ＺｎＯ　５０～６５％、Ｂ２Ｏ３　１９～２８％、ＳｉＯ２　７～１５％、Ａｌ２Ｏ３　３～１２％、Ｂｉ２Ｏ３　０．１～５％の組成を含有し、鉛成分を実質的に含有しないことを特徴とする半導体被覆用ガラス。 Contains by mass% ZnO 50-65%, B 2 O 3 19-28%, SiO 2 7-15%, Al 2 O 3 3-12%, Bi 2 O 3 0.1-5% A glass for semiconductor coating characterized by substantially not containing a lead component.
  2. 　さらに、ＭｎＯ２　０～５％、Ｎｂ２Ｏ５　０～５％、ＣｅＯ２　０～３％の組成を含有することを特徴とする請求項１に記載の半導体被覆用ガラス。 The glass for semiconductor coating according to claim 1, further comprising a composition of MnO 2 0 to 5%, Nb 2 O 5 0 to 5%, and CeO 2 0 to 3%.
  3. 　請求項１または２に記載の半導体被覆用ガラスからなることを特徴とする半導体被覆用ガラス粉末。 A glass powder for semiconductor coating, comprising the glass for semiconductor coating according to claim 1 or 2.
  4. 　請求項３に記載の半導体被覆用ガラス粉末を含むことを特徴とする半導体被覆用材料。 A semiconductor coating material comprising the glass powder for semiconductor coating according to claim 3.
  5. 　請求項３に記載の半導体被覆用ガラス粉末１００質量部に対して、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＺｎＯ・Ｂ２Ｏ３および２ＺｎＯ・ＳｉＯ２から選択される少なくとも１種類の無機粉末を０．０１～５質量部含有してなることを特徴とする半導体被覆用材料。 The inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO · B 2 O 3 and 2ZnO · SiO 2 is added to 0.1 parts by mass with respect to 100 parts by mass of the glass powder for semiconductor coating according to claim 3. A semiconductor coating material comprising 01 to 5 parts by mass.
  6. 　表面電荷密度が７×１０１１／ｃｍ２以上であることを特徴とする請求項４または５に記載の半導体被覆用材料。 6. The semiconductor coating material according to claim 4, wherein the surface charge density is 7 × 10 11 / cm 2 or more.
  7. 　質量％で、ＺｎＯ　４０～６０％、Ｂ２Ｏ３　５～２５％、ＳｉＯ２　１５～３５％、Ａｌ２Ｏ３　３～１２％の組成を含有し、鉛成分を実質的に含有しないことを特徴とする半導体被覆用ガラス。 It contains 40% to 60% ZnO, 5 to 25% B 2 O 3 , 15 to 35% SiO 2 , and 3 to 12% Al 2 O 3 , and contains substantially no lead component. Characteristic glass for semiconductor coating.
  8. 　さらに、Ｂｉ２Ｏ３　０～５％、ＭｎＯ２　０～５％、Ｎｂ２Ｏ５　０～５％、ＣｅＯ２　０～３％の組成を含有することを特徴とする請求項７に記載の半導体被覆用ガラス。 The semiconductor according to claim 7, further comprising a composition of Bi 2 O 3 0 to 5%, MnO 2 0 to 5%, Nb 2 O 5 0 to 5%, CeO 2 0 to 3%. Glass for coating.
  9. 　請求項７または８に記載の半導体被覆用ガラスからなるガラス粉末を含むことを特徴とする半導体被覆用材料。 A semiconductor coating material comprising a glass powder comprising the glass for semiconductor coating according to claim 7 or 8.
  10. 　前記ガラス粉末１００質量部に対して、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＺｎＯ・Ｂ２Ｏ３および２ＺｎＯ・ＳｉＯ２から選択される少なくとも１種類の無機粉末を０．０１～５質量部含有してなることを特徴とする請求項９に記載の半導体被覆用材料。 0.01 to 5 parts by mass of at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO · B 2 O 3 and 2ZnO · SiO 2 is contained with respect to 100 parts by mass of the glass powder. The semiconductor coating material according to claim 9, wherein:
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JP2013060353A (en) * 2011-08-25 2013-04-04 Nippon Electric Glass Co Ltd Glass for covering semiconductor element
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