WO2020071093A1 - Semiconductor element coating glass and semiconductor coating material using same - Google Patents

Semiconductor element coating glass and semiconductor coating material using same

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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
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Prior art keywords
glass
semiconductor element
coating
semiconductor
content
Prior art date
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PCT/JP2019/036160
Other languages
French (fr)
Japanese (ja)
Inventor
将行 廣瀬
Original Assignee
日本電気硝子株式会社
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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/en
Publication of WO2020071093A1 publication Critical patent/WO2020071093A1/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
    • 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.

Abstract

This semiconductor element coating glass is characterized by having a glass composition that contains, by mol%, 18%–43% of SiO2, 5%–21% of B2O3, 8%–21% of Al2O3, 10%–25% of ZnO, and 10%–25% of MgO+CaO and does not substantially contain a lead component.

Description

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Glass for semiconductor element coating and semiconductor coating material using the same
　本発明は、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に関する。 The present invention relates to a glass for coating a semiconductor element and a material for coating a semiconductor using the glass.
　シリコンダイオード、トランジスタ等の半導体素子は、一般的に、半導体素子のＰ－Ｎ接合部を含む表面がガラスにより被覆される。これにより、半導体素子表面の安定化を図り、経時的な特性劣化を抑制することができる。 半導体 In general, 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.
　半導体素子被覆用ガラスに要求される特性として、（１）半導体素子との熱膨張係数差によるクラック等が発生しないように、熱膨張係数が半導体素子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）で被覆可能であること、（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等が挙げられる。 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.
　従来から、半導体素子被覆用ガラスとして、ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系等の亜鉛系ガラス、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３系ガラス、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３系ガラス等の鉛系ガラスが知られているが、現在では、作業性の観点から、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３系ガラス、ＰｂＯ－ＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３系ガラス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 element coating, 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 is known, but at present, from the viewpoint of workability, 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).
特開昭４８－４３２７５号公報JP-A-48-43275 特開昭５０－１２９１８１号公報JP-A-50-129181 特公平１－４９６５３号公報Japanese Patent Publication No. 1-49653 特開２００８－１６２８８１号公報JP 2008-162881 A
　しかし、鉛系ガラスの鉛成分は、環境に対して有害な成分である。上記の亜鉛系ガラスは、少量の鉛成分やビスマス成分を含むため、環境に対して完全に無害であるとは言い切れない。 However, 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.
　また、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、被覆層を形成した後の酸処理工程で侵食され易いという問題がある。このため、被覆層の表面に更に保護膜を形成して酸処理を行う必要があった。 亜 鉛 In addition, 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.
　一方、ガラス組成中のＳｉＯ２の含有量を多くすると、耐酸性が向上すると共に、半導体素子の逆電圧が向上するが、半導体素子の逆漏れ電流が大きくなるという不具合が生じる。特に、低耐圧用の半導体素子では、逆電圧の向上よりも、逆漏れ電流を抑制して、表面電化密度を低減することが優先されるため、上記不具合がより問題になる。 On the other hand, when the content of SiO 2 in the glass composition is increased, the acid resistance is improved, and the reverse voltage of the semiconductor element is improved, but the reverse leakage current of the semiconductor element is disadvantageously increased. In particular, in the case of a semiconductor element for low withstand voltage, it is more important to suppress the reverse leakage current and reduce the surface electrification density than to improve the reverse voltage.
　そこで、本発明は、上記事情に鑑みなされたものであり、その技術的課題は、環境負荷が小さく、耐酸性に優れ、且つ表面電荷密度が低い半導体素子被覆用ガラスを提供することである。 Accordingly, 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.
　本発明者は、鋭意検討した結果、特定のガラス組成を有するＳｉＯ２－Ｂ２Ｏ３－Ａｌ２Ｏ３－ＺｎＯ系ガラスを用いることにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明の半導体素子被覆用ガラスは、ガラス組成として、モル％で、ＳｉＯ２　１８～４３％、Ｂ２Ｏ３　５～２１％、Ａｌ２Ｏ３　８～２１％、ＺｎＯ　１０～２５％、ＭｇＯ＋ＣａＯ　１０～２５％を含有し、実質的に鉛成分を含有しないことを特徴とする。ここで、「ＭｇＯ＋ＣａＯ」は、ＭｇＯとＣａＯの合量を指す。また、「実質的に～を含有しない」とは、ガラス成分として該当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。具体的には、不純物を含めた該当成分の含有量が０．１質量％未満であることを意味する。 As a result of intensive studies, 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. Here, “MgO + CaO” indicates the total amount of MgO and CaO. Further, “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.
　本発明の半導体素子被覆用ガラスは、上記の通り、各成分の含有範囲を規制している、これにより、環境負荷が小さく、耐酸性が向上すると共に、表面電荷密度が低下する。結果として、低耐圧用の半導体素子の被覆に好適に使用可能になる。 半導体 As described above, 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.
　また、本発明の半導体素子被覆用材料では、上記の半導体素子被覆用ガラスからなるガラス粉末　７５～１００質量％、セラミック粉末　０～２５％を含有することが好ましい。 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.
　また、本発明の半導体素子被覆用材料では、３０～３００℃の温度範囲における熱膨張係数が２０×１０－７／℃以上、且つ５５×１０－７／℃以下であることが好ましい。ここで、「３０～３００℃の温度範囲における熱膨張係数」は、押し棒式熱膨張係数測定装置により測定した値を指す。 Further, in the semiconductor element coating material of the present invention, 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. Here, “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.
　本発明の半導体素子被覆用ガラスは、ガラス組成として、モル％で、ＳｉＯ２　１８～４３％、Ｂ２Ｏ３　５～２１％、Ａｌ２Ｏ３　８～２１％、ＺｎＯ　１０～２５％、ＭｇＯ＋ＣａＯ　１０～２５％を含有し、実質的に鉛成分を含有しないことを特徴とする。各成分の含有量を限定した理由を以下に説明する。なお、以下の各成分の含有量の説明において、％表示は、特に断りのない限り、モル％を意味する。 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.
　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１８～４３％であり、好ましくは２０～４０％、特に２２～３６％である。ＳｉＯ２の含有量が少な過ぎると、耐酸性が低下する傾向がある。一方、ＳｉＯ２の含有量が多過ぎると、溶融時の失透性が強くなり、均質なガラスが得られ難くなる。 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.
　Ｂ２Ｏ３は、ガラスの網目形成成分であり、軟化流動性を高める成分である。Ｂ２Ｏ３の含有量は５～２１％であり、好ましくは５～１８％、特に７～１５％である。Ｂ２Ｏ３の含有量が少な過ぎると、結晶性が強くなるため、被覆時に軟化流動性が損なわれて、半導体素子表面への均一な被覆が困難になる。一方、Ｂ２Ｏ３の含有量が多過ぎると、熱膨張係数が不当に高くなったり、耐酸性が低下する傾向がある。 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.
　Ａｌ２Ｏ３は、ガラスを安定化すると共に、表面電荷密度を調整する成分である。Ａｌ２Ｏ３の含有量は８～２１％であり、好ましくは５～２０％、特に８～１８％である。Ａｌ２Ｏ３の含有量が少な過ぎると、ガラスが失透し易くなる。一方、Ａｌ２Ｏ３の含有量が多過ぎると、表面電荷密度が大きくなり過ぎる虞がある。 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は、ガラスを安定化する成分である。ＺｎＯの含有量は１０～２５％であり、好ましくは１２～２２％である。ＺｎＯの含有量が少な過ぎると、溶融時の失透性が強くなり、均質なガラスが得られ難くなる。一方、ＺｎＯの含有量が多過ぎると、耐酸性が低下し易くなる。 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とＣａＯは、ガラスの粘性を下げる成分である。ＭｇＯとＣａＯの合量は１０～２５％であり、好ましくは１２～２０％である。ＭｇＯとＣａＯの合量が少な過ぎると、ガラスの焼成温度が上昇し易くなる。一方、ＭｇＯとＣａＯの合量が多過ぎると、熱膨張係数が高くなり過ぎたり、耐酸性が低下したり、絶縁性が低下する虞がある。なお、ＭｇＯの含有量は、好ましくは０～２０％、特に０～５％である。ＣａＯの含有量は、好ましくは１～２５％、特に１０～２０％である。 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. Note that 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%.
　上記成分以外にも、他の成分（例えば、ＳｒＯ、ＢａＯ、ＭｎＯ２、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、ＣｅＯ２、Ｓｂ２Ｏ３等）を７％まで（好ましくは３％まで）含有してもよい。 In addition to the above components, other components (e.g., SrO, BaO, MnO 2, Ta 2 O 5, Nb 2 O 5, CeO 2, Sb 2 O 3 , etc.) to 7% (preferably up to 3%) containing May be.
　環境面の観点から、実質的に鉛成分（例えばＰｂＯ等）を含有せず、実質的にＢｉ２Ｏ３、Ｆ、Ｃｌも含有しないことが好ましい。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及びＫ２Ｏ）も実質的に含有しないことが好ましい。 From an environmental point of view, it is preferable that 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.
　本発明の半導体素子被覆用ガラスは、粉末状であること、つまりガラス粉末であることが好ましい。ガラス粉末に加工すれば、例えば、ペースト法、電気泳動塗布法等を用いて半導体素子表面の被覆を容易に行うことができる。 半導体 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.
　ガラス粉末の平均粒子径Ｄ５０は、好ましくは２５μｍ以下、特に１５μｍ以下である。ガラス粉末の平均粒子径Ｄ５０が大き過ぎると、ペースト化が困難になる。また、電気泳動法による粉末付着も困難になる。なお、ガラス粉末の平均粒子径Ｄ５０の下限は特に限定されないが、現実的には０．１μｍ以上である。なお、「平均粒子径Ｄ５０」は、体積基準で測定した値であり、レーザー回折法で測定した値を指す。 The average of the glass powder the particle diameter D 50 is preferably 25μm or less, particularly 15μm or less. When the average particle diameter D 50 of the glass powder is too large, pasting becomes difficult. Also, powder adhesion by electrophoresis becomes difficult. The lower limit of the average particle diameter D 50 of the glass powder is not particularly limited, in practice it is 0.1μm 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.
　本発明の半導体素子被覆用ガラスは、例えば、各酸化物成分の原料粉末を調合してバッチとし、１５００℃程度で約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 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).
　本発明の半導体素子被覆用材料は、前記半導体素子被覆用ガラスからなるガラス粉末を含むが、必要に応じて、セラミック粉末と混合し、複合粉末としてもよい。セラミック粉末を添加すれば、熱膨張係数を調整し易くなる。 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.
　セラミック粉末は、ガラス粉末１００質量部に対して、２５％未満、特に２０％未満であることが好ましい。セラミック粉末の含有量が多過ぎると、ガラスの軟化流動性が損なわれて、半導体素子表面の被覆が困難になる。 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.
　セラミック粉末の平均粒子径Ｄ５０は、好ましくは３０μｍ以下、特に２０μｍ以下である。セラミック粉末の平均粒子径Ｄ５０が大き過ぎると、被覆層の表面平滑性が低下し易くなる。セラミック粉末の平均粒子径Ｄ５０の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 average particle diameter D 50 of the ceramic powder is preferably 30μm or less, particularly 20μm 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 0.1μm or more.
　本発明の半導体素子被覆用材料において、３０～３００℃の温度範囲における熱膨張係数は、好ましくは２０×１０－７／℃以上、５５×１０－７／℃以下、特に３０×１０－７／℃以上、５０×１０－７／℃以下である。熱膨張係数が上記範囲外になると、半導体素子との熱膨張係数差によるクラック、反り等が発生し易くなる。 In the material for coating a semiconductor element of the present invention, 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. When 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.
　本発明の半導体素子被覆用材料において、表面電荷密度は、例えば１０００Ｖ以下の半導体素子表面を被覆する場合、好ましくは６×１０１１／ｃｍ２以下、特に５×１０１１／ｃｍ２以下である。表面電荷密度が高過ぎると、耐圧が高くなるが、同時に漏れ電流も大きくなる傾向がある。なお、「表面電荷密度」は、後述する実施例の欄に記載の方法によって測定した値を指す。 In the semiconductor element coating material of the present invention, 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.
以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は、単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described in detail based on examples. The following embodiments are merely examples. The present invention is not limited to the following examples.
　表１は、本発明の実施例（試料Ｎｏ．１～４）と比較例（試料Ｎｏ．５、６）を示している。 Table 1 shows Examples (Samples Nos. 1 to 4) of the present invention and Comparative Examples (Samples Nos. 5 and 6).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　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、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、平均粒子径Ｄ５０が１２μｍとなるガラス粉末を得た。なお、試料Ｎｏ．４では、得られたガラス粉末に対して、コーディエライト粉末（平均粒子径Ｄ５０：１２μｍ）を１５質量％添加して、複合粉末とした。 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 μm) was added to the obtained glass powder in an amount of 15% by mass to obtain a composite powder.
　各試料について、熱膨張係数、表面電荷密度及び耐酸性を評価した。その結果を表１に示す。 Each sample was evaluated for thermal expansion coefficient, surface charge density and acid resistance. Table 1 shows the results.
　熱膨張係数は、押し棒式熱膨張係数測定装置を用いて、３０～３００℃の温度範囲にて測定した値である。 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.
　表面電荷密度は、次のようにして測定した。まず、各試料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た後、焼成して被覆層を形成した。次に、被覆層の表面にアルミニウム電極を形成した後、被覆層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, 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.
　耐酸性は次のようにして評価した。各試料を直径２０ｍｍ、厚み４ｍｍ程度の大きさにプレス成型した後、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、耐酸性の指標とした。なお、単位面積当たりの質量変化が１．０ｍｇ/ｃｍ２未満を「○」、１．０ｍｇ/ｃｍ２以上を「×」とした。 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 "×".
　表１から明らかなように、試料Ｎｏ．１～４は、表面電荷密度が６×１０１１／ｃｍ２以下であり、且つ耐酸性の評価も良好であった。よって、試料Ｎｏ．１～４は、低耐圧用半導体素子の被覆に用いる半導体素子被覆用材料として好適であると考えられる。 As is clear from Table 1, 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.
　一方、試料Ｎｏ．５、６は、耐酸性試験の評価が不良であった。更に、試料Ｎｏ．６は、熱膨張係数が高く、また表面電荷密度も高かった。 On the other hand, sample No. In Nos. 5 and 6, the evaluation in the acid resistance test was poor. Further, the sample No. Sample No. 6 had a high coefficient of thermal expansion and a high surface charge density.

Claims (3)

  1. 　ガラス組成として、モル％で、ＳｉＯ２　１８～４３％、Ｂ２Ｏ３　５～２１％、Ａｌ２Ｏ３　８～２１％、ＺｎＯ　１０～２５％、ＭｇＯ＋ＣａＯ　１０～２５％を含有し、実質的に鉛成分を含有しないことを特徴とする半導体素子被覆用ガラス。 The glass composition contains, by mol%, 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 10 to 25% of MgO + CaO. A glass for coating a semiconductor element, wherein the glass does not contain a lead component.
  2. 　請求項１に記載の半導体素子被覆用ガラスからなるガラス粉末　７５～１００質量％、セラミック粉末　０～２５％を含有することを特徴とする半導体素子被覆用材料。 A material for coating a semiconductor element, comprising: glass powder comprising the glass for coating a semiconductor element according to claim 1 素 子 75 to 100% by mass; and ceramic powder 0 to 25%.
  3. 　３０～３００℃の温度範囲における熱膨張係数が２０×１０－７／℃以上、且つ５５×１０－７／℃以下であることを特徴とする請求項２に記載の半導体素子被覆用材料。 3. The material for coating a semiconductor element according to claim 2, wherein the thermal expansion coefficient in a temperature range of 30 to 300 ° C. is 20 × 10 −7 / ° C. or more and 55 × 10 −7 / ° C. or less.
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CN112512982A (en) 2021-03-16
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