WO2024253096A1 - Glass for coating semiconductor element and sintered body for coating semiconductor element - Google Patents
Glass for coating semiconductor element and sintered body for coating semiconductor element Download PDFInfo
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- WO2024253096A1 WO2024253096A1 PCT/JP2024/020388 JP2024020388W WO2024253096A1 WO 2024253096 A1 WO2024253096 A1 WO 2024253096A1 JP 2024020388 W JP2024020388 W JP 2024020388W WO 2024253096 A1 WO2024253096 A1 WO 2024253096A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W74/00—Encapsulations, e.g. protective coatings
- H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W74/00—Encapsulations, e.g. protective coatings
- H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
Definitions
- the present invention relates to glass for covering semiconductor elements and sintered bodies for covering semiconductor elements.
- Semiconductor elements such as silicon diodes and transistors generally have their surfaces, including the P-N junctions, covered with glass. This stabilizes the surface of the semiconductor element and prevents deterioration of characteristics over time.
- the properties required for glass used to cover semiconductor elements include (1) a thermal expansion coefficient that matches that of the semiconductor element to prevent cracks due to differences in thermal expansion coefficients with the semiconductor element, (2) the ability to cover the semiconductor element at low temperatures (e.g., 900°C or lower) to prevent deterioration of the characteristics of the semiconductor element, and (3) the absence of impurities such as alkaline components that adversely affect the surface of the semiconductor element.
- zinc-based glasses such as ZnO-B 2 O 3 -SiO 2- based glasses and lead-based glasses such as PbO-SiO 2 -Al 2 O 3 -based glasses and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 -based glasses have been known as glasses for covering semiconductor elements.
- lead-based glasses such as PbO-SiO 2 -Al 2 O 3- based glasses and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 -based glasses are becoming mainstream (for example, see Patent Documents 1 to 4).
- the lead component in lead-based glass is harmful to the environment.
- the zinc-based glass mentioned above contains small amounts of lead and bismuth, so it cannot be said to be completely harmless to the environment.
- Another problem is that zinc-based glass is more susceptible to devitrification during the melting process than lead-based glass.
- the present invention was developed in consideration of the above circumstances, and its technical objective is to provide a glass for covering semiconductor elements that has a small environmental impact and is less susceptible to devitrification during the melting process.
- the devitrified material generated in the glass melting process is gahnite (ZnAl 2 O 4 ), and that by regulating the ratio of the content of Al 2 O 3 to the total content of SiO 2 and ZnO in SiO 2 -ZnO-Al 2 O 3 based glass, gahnite is less likely to be generated in the glass melting process, and propose this invention.
- the glass for covering semiconductor elements of the present invention contains, in mole percent, SiO 2 +ZnO 40-75%, B 2 O 3 0-20%, Al 2 O 3 5-15%, and MgO + CaO 8-22%, and is characterized in that, in mole ratio, Al 2 O 3 /(SiO 2 +ZnO) is 0.2 or less, and is substantially free of lead components.
- SiO 2 +ZnO refers to the total content of SiO 2 and ZnO.
- MgO+CaO is the total content of MgO and CaO.
- Al 2 O 3 /(SiO 2 +ZnO) is the value obtained by dividing the content of Al 2 O 3 by the total content of SiO 2 and ZnO.
- Substantially free of means that the component is not intentionally added as a glass component, and does not mean that even unavoidable impurities are completely excluded. Specifically, it means that the content of the component, including impurities, is less than 0.1 mass%.
- the glass for covering semiconductor elements of the present invention preferably has a thermal expansion coefficient of 20 to 55 ⁇ 10 -7 /° C. in the temperature range of 30 to 300° C.
- the "thermal expansion coefficient in the temperature range of 30 to 300° C.” refers to a value measured using a push rod type thermal expansion coefficient measuring device.
- the present invention makes it possible to provide glass for covering semiconductor elements that has a small environmental impact and is less susceptible to devitrification during the melting process.
- the glass for covering semiconductor elements of the present invention is characterized in that it contains, in mole percent, SiO 2 +ZnO 40-75%, B 2 O 3 0-20%, Al 2 O 3 5-15%, and MgO + CaO 8-22% as a glass composition, and that the molar ratio Al 2 O 3 /(SiO 2 +ZnO) is 0.2 or less, and it is substantially free of lead components.
- % means mol % unless otherwise specified.
- the numerical range indicated by "to” means a range including the numerical values before and after "to” as the minimum and maximum values, respectively.
- SiO2 and ZnO are components that stabilize glass.
- SiO2 + ZnO is 40 to 75%, preferably 45 to 70%, 50 to 68%, 53 to 65%, and particularly preferably 55 to 64%. If the amount of SiO2 + ZnO is too small, gahnite is likely to precipitate in the melting process. On the other hand, if the amount of SiO2 + ZnO is too large, the softening point of the glass is likely to increase significantly.
- the SiO2 content is preferably 25 to 40%, 22 to 38%, 24 to 36%, particularly preferably 26 to 34%.
- the ZnO content is preferably 15-40%, 22-38%, 24-36%, and particularly preferably 26-34%.
- B 2 O 3 is a component for forming a glass network and for increasing the softening fluidity.
- the content of B 2 O 3 is 0 to 20%, preferably 0 to 18%, and particularly preferably 0 to 16%. If the content of B 2 O 3 is too high, the thermal expansion coefficient tends to be unduly high and the acid resistance tends to be reduced.
- Al 2 O 3 is a component that stabilizes glass.
- the content of Al 2 O 3 is 5 to 15%, and preferably 6 to 14%, 7 to 13%, 8 to 12%, 8 to 11%, and particularly preferably 9 to 10%. If the content of Al 2 O 3 is too low, vitrification becomes difficult. On the other hand, if the content of Al 2 O 3 is too high, gahnite is likely to precipitate in the melting process. In addition, the softening point of the glass is likely to increase significantly.
- Al2O3 /( SiO2 +ZnO) is 0.2 or less, preferably 0.19 or less, and particularly preferably 0.18 or less. If Al2O3 /( SiO2 +ZnO) is too large, gahnite tends to precipitate in the melting process. There is no particular lower limit for Al2O3 /( SiO2 + ZnO), but it is practically 0.07 or more.
- MgO and CaO are components that lower the viscosity of glass.
- the MgO + CaO content is 8-22%, and preferably 10-20%. If the MgO + CaO content is too low, the softening temperature of the glass tends to increase. On the other hand, if the MgO + CaO content is too high, the thermal expansion coefficient may become too high, acid resistance may decrease, and insulation properties may decrease.
- the MgO content is preferably 2-20%, 3-15%, and especially 4-13%.
- the CaO content is preferably 2-20%, 3-15%, and particularly preferably 4-13%.
- other components e.g., SrO, BaO, MnO2 , Ta2O5 , Nb2O5 , CeO2 , Sb2O3 , etc.
- other components e.g., SrO, BaO, MnO2 , Ta2O5 , Nb2O5 , CeO2 , Sb2O3 , etc.
- the material contains substantially no lead components (e.g., PbO, etc.) and substantially no Bi 2 O 3 , F, or Cl. It is also preferable that the material contains substantially no alkaline components (Li 2 O, Na 2 O, and K 2 O) that adversely affect the surface of semiconductor elements.
- lead components e.g., PbO, etc.
- Bi 2 O 3 e.g., F, or Cl.
- alkaline components Li 2 O, Na 2 O, and K 2 O
- the glass for covering a semiconductor element of the present invention preferably has a thermal expansion coefficient of 20 to 55 ⁇ 10 ⁇ 7 /° C., particularly 30 to 50 ⁇ 10 ⁇ 7 /° C., in the temperature range of 30 to 300° C. If the thermal expansion coefficient is outside the above range, cracks, warping, etc. are likely to occur due to the difference in thermal expansion coefficient with the semiconductor element.
- the glass for coating semiconductor elements of the present invention is preferably in powder form. If it is processed into powder form, it can be easily used to coat the surface of a semiconductor element using, for example, a paste method or an electrophoretic coating method.
- the average particle diameter D50 of the glass powder is preferably 25 ⁇ m or less, particularly 15 ⁇ m or less. If the average particle diameter D50 of the glass powder is too large, it becomes difficult to make a paste. In addition, it becomes difficult to apply the paste by electrophoresis.
- the lower limit of the average particle diameter D50 of the glass powder is not particularly limited, but in reality, it is 0.1 ⁇ m or more.
- the "average particle diameter D50" is a value measured on a volume basis, and refers to a value measured by a laser diffraction method.
- the glass for covering semiconductor elements of the present invention may be mixed with ceramic powder to form a composite powder, if necessary. Adding ceramic powder makes it easier to adjust the thermal expansion coefficient.
- the amount of ceramic powder is less than 25 parts by mass, and especially less than 20 parts by mass, per 100 parts by mass of glass powder. If the ceramic powder content is too high, the softening fluidity of the glass is impaired, making it difficult to coat the surface of the semiconductor element.
- the average particle diameter D50 of the ceramic powder is preferably 30 ⁇ m or less, particularly 20 ⁇ m or less. If the average particle diameter D50 of the ceramic powder is too large, the surface smoothness of the coating layer is likely to decrease.
- the lower limit of the average particle diameter D50 of the ceramic powder is not particularly limited, but is practically 0.1 ⁇ m or more.
- raw material powders mixed to obtain the desired glass composition are melted at 1300-1550°C for 1-2 hours until a homogeneous glass is obtained.
- the resulting molten glass is then formed into a film or other shape, which is then crushed and classified to produce powdered glass for coating semiconductor elements.
- the surface of the semiconductor element is coated with powdered glass for covering semiconductor elements, for example, by using a paste method, electrophoretic coating method, or the like.
- the glass for covering semiconductor elements that has covered the surface of the semiconductor element becomes a sintered body for covering semiconductor elements in which no crystals are precipitated.
- the sintered body for covering semiconductor elements has the same composition range as the glass composition of the glass for covering semiconductor elements.
- Table 1 shows examples of the present invention (samples No. 1-4, 9, 10) and comparative examples (samples No. 5-8).
- Each sample was prepared as follows: First, raw material powders were mixed to obtain the glass composition shown in the table, and the mixture was melted at 1500° C. for 1 hour to vitrify the glass. The molten glass was then formed into a film, which was then pulverized in a ball mill and classified using a 350 mesh sieve to obtain a glass powder with an average particle size D50 of 12 ⁇ m.
- the thermal expansion coefficient was measured using a push rod type thermal expansion coefficient measuring device in the temperature range of 30 to 300°C.
- Devitrification resistance was evaluated as follows. 100 g of glass film from each sample was placed in a platinum crucible and held at 1150°C for 24 hours, after which the presence of devitrified matter (gahnite) was confirmed by visual inspection. After that, the sample was held at 1400°C for 10 minutes, and if devitrified matter (gahnite) was not confirmed by visual inspection, it was marked as "Good”, and if devitrified matter (gahnite) was confirmed, it was marked as "Poor”. The devitrified matter was measured using an X-ray diffraction device and confirmed to be gahnite.
- Samples Nos. 5 to 8 have too large Al 2 O 3 /(SiO 2 +ZnO) and therefore are considered to be glasses that are likely to cause problems in the melting process and have poor devitrification resistance.
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Abstract
Description
本発明は、半導体素子被覆用ガラス、及び半導体素子被覆用焼結体に関する。 The present invention relates to glass for covering semiconductor elements and sintered bodies for covering semiconductor elements.
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。 Semiconductor elements such as silicon diodes and transistors generally have their surfaces, including the P-N junctions, covered with glass. This stabilizes the surface of the semiconductor element and prevents deterioration of characteristics over time.
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 properties required for glass used to cover semiconductor elements include (1) a thermal expansion coefficient that matches that of the semiconductor element to prevent cracks due to differences in thermal expansion coefficients with the semiconductor element, (2) the ability to cover the semiconductor element at low temperatures (e.g., 900°C or lower) to prevent deterioration of the characteristics of the semiconductor element, and (3) the absence of impurities such as alkaline components that adversely affect the surface of the semiconductor element.
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, zinc-based glasses such as ZnO-B 2 O 3 -SiO 2- based glasses and lead-based glasses such as PbO-SiO 2 -Al 2 O 3 -based glasses and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 -based glasses have been known as glasses for covering semiconductor elements. However, at present, from the viewpoint of workability, lead-based glasses such as PbO-SiO 2 -Al 2 O 3- based glasses and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 -based glasses are becoming mainstream (for example, see Patent Documents 1 to 4).
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 in lead-based glass is harmful to the environment. The zinc-based glass mentioned above contains small amounts of lead and bismuth, so it cannot be said to be completely harmless to the environment.
また、亜鉛系ガラスは、鉛系ガラスと比較して、溶融工程において失透し易いという問題があった。 Another problem is that zinc-based glass is more susceptible to devitrification during the melting process than lead-based glass.
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、溶融工程において失透し難い半導体素子被覆用ガラスを提供することである。 The present invention was developed in consideration of the above circumstances, and its technical objective is to provide a glass for covering semiconductor elements that has a small environmental impact and is less susceptible to devitrification during the melting process.
本発明者は、鋭意検討した結果、ガラス溶融工程において発生する失透物がガーナイト（ＺｎＡｌ２Ｏ４）であり、ＳｉＯ２－ＺｎＯ－Ａｌ２Ｏ３系ガラスにおいて、Ａｌ２Ｏ３の含有量とＳｉＯ２及びＺｎＯの含有量の合量との比率を規制することにより、ガラス溶融工程においてガーナイトが発生し難くなることを見出し、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、モル％で、ＳｉＯ２＋ＺｎＯ ４０～７５％、Ｂ２Ｏ３ ０～２０％、Ａｌ２Ｏ３ ５～１５％、ＭｇＯ＋ＣａＯ ８～２２％を含有し、且つモル比で、Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）が０．２以下であり、実質的に鉛成分を含有しないことを特徴とする。ここで、「ＳｉＯ２＋ＺｎＯ」とはＳｉＯ２及びＺｎＯの含有量の合量である。「ＭｇＯ＋ＣａＯ」とは、ＭｇＯ及びＣａＯの含有量の合量である。「Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）」とは、Ａｌ２Ｏ３の含有量をＳｉＯ２及びＺｎＯの含有量の合量で除した値である。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 research, the inventors found that the devitrified material generated in the glass melting process is gahnite (ZnAl 2 O 4 ), and that by regulating the ratio of the content of Al 2 O 3 to the total content of SiO 2 and ZnO in SiO 2 -ZnO-Al 2 O 3 based glass, gahnite is less likely to be generated in the glass melting process, and propose this invention. That is, the glass for covering semiconductor elements of the present invention contains, in mole percent, SiO 2 +ZnO 40-75%, B 2 O 3 0-20%, Al 2 O 3 5-15%, and MgO + CaO 8-22%, and is characterized in that, in mole ratio, Al 2 O 3 /(SiO 2 +ZnO) is 0.2 or less, and is substantially free of lead components. Here, "SiO 2 +ZnO" refers to the total content of SiO 2 and ZnO. "MgO+CaO" is the total content of MgO and CaO. "Al 2 O 3 /(SiO 2 +ZnO)" is the value obtained by dividing the content of Al 2 O 3 by the total content of SiO 2 and ZnO. "Substantially free of..." means that the component is not intentionally added as a glass component, and does not mean that even unavoidable impurities are completely excluded. Specifically, it means that the content of the component, including impurities, is less than 0.1 mass%.
本発明の半導体素子被覆用ガラスは、３０～３００℃の温度範囲における熱膨張係数が２０～５５×１０－７／℃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。 The glass for covering semiconductor elements of the present invention preferably has a thermal expansion coefficient of 20 to 55 × 10 -7 /° C. in the temperature range of 30 to 300° C. Here, the "thermal expansion coefficient in the temperature range of 30 to 300° C." refers to a value measured using a push rod type thermal expansion coefficient measuring device.
本発明によれば、環境負荷が小さく、溶融工程において失透し難い半導体素子被覆用ガラスを提供することができる。 The present invention makes it possible to provide glass for covering semiconductor elements that has a small environmental impact and is less susceptible to devitrification during the melting process.
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＋ＺｎＯ ４０～７５％、Ｂ２Ｏ３ ０～２０％、Ａｌ２Ｏ３ ５～１５％、ＭｇＯ＋ＣａＯ ８～２２％を含有し、且つモル比で、Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）が０．２以下であり、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。本明細書において「～」を用いて示された数値範囲は、「～」の前後に記載の数値を最小値及び最大値としてそれぞれ含む範囲を意味する。 The glass for covering semiconductor elements of the present invention is characterized in that it contains, in mole percent, SiO 2 +ZnO 40-75%, B 2 O 3 0-20%, Al 2 O 3 5-15%, and MgO + CaO 8-22% as a glass composition, and that the molar ratio Al 2 O 3 /(SiO 2 +ZnO) is 0.2 or less, and it is substantially free of lead components. The reasons for limiting the content of each component are explained below. In the following explanation of the content of each component, % means mol % unless otherwise specified. In this specification, the numerical range indicated by "to" means a range including the numerical values before and after "to" as the minimum and maximum values, respectively.
ＳｉＯ２及びＺｎＯは、ガラスを安定化させる成分である。ＳｉＯ２＋ＺｎＯは、４０～７５％であり、４５～７０％、５０～６８％、５３～６５％、特に５５～６４％であることが好ましい。ＳｉＯ２＋ＺｎＯが少な過ぎると、溶融工程においてガーナイトが析出し易くなる。一方、ＳｉＯ２＋ＺｎＯが多過ぎると、ガラスの軟化点が大幅に上昇し易くなる。 SiO2 and ZnO are components that stabilize glass. SiO2 + ZnO is 40 to 75%, preferably 45 to 70%, 50 to 68%, 53 to 65%, and particularly preferably 55 to 64%. If the amount of SiO2 + ZnO is too small, gahnite is likely to precipitate in the melting process. On the other hand, if the amount of SiO2 + ZnO is too large, the softening point of the glass is likely to increase significantly.
ＳｉＯ２の含有量は、２５～４０％、２２～３８％、２４～３６％、特に２６～３４％であることが好ましい。 The SiO2 content is preferably 25 to 40%, 22 to 38%, 24 to 36%, particularly preferably 26 to 34%.
ＺｎＯの含有量は、１５～４０％、２２～３８％、２４～３６％、特に２６～３４％であることが好ましい。 The ZnO content is preferably 15-40%, 22-38%, 24-36%, and particularly preferably 26-34%.
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０～２０％であり、０～１８％、特に０～１６％であることが好ましい。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 component for forming a glass network and for increasing the softening fluidity. The content of B 2 O 3 is 0 to 20%, preferably 0 to 18%, and particularly preferably 0 to 16%. If the content of B 2 O 3 is too high, the thermal expansion coefficient tends to be unduly high and the acid resistance tends to be reduced.
Ａｌ２Ｏ３は、ガラスを安定化する成分である。Ａｌ２Ｏ３の含有量は５～１５％であり、６～１４％、７～１３％、８～１２％、８～１１％、特に９～１０％であることが好ましい。Ａｌ２Ｏ３の含有量が少な過ぎると、ガラス化し難くなる。一方、Ａｌ２Ｏ３の含有量が多過ぎると、溶融工程においてガーナイトが析出し易くなる。また、ガラスの軟化点が大幅に上昇し易くなる。 Al 2 O 3 is a component that stabilizes glass. The content of Al 2 O 3 is 5 to 15%, and preferably 6 to 14%, 7 to 13%, 8 to 12%, 8 to 11%, and particularly preferably 9 to 10%. If the content of Al 2 O 3 is too low, vitrification becomes difficult. On the other hand, if the content of Al 2 O 3 is too high, gahnite is likely to precipitate in the melting process. In addition, the softening point of the glass is likely to increase significantly.
モル比で、Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）は０．２以下であり、０．１９以下、特に０．１８以下であることが好ましい。Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）が大き過ぎると、溶融工程においてガーナイトが析出し易くなる。Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）の下限は特に限定されないが、現実的には０．０７以上である。 In terms of molar ratio, Al2O3 /( SiO2 +ZnO) is 0.2 or less, preferably 0.19 or less, and particularly preferably 0.18 or less. If Al2O3 /( SiO2 +ZnO) is too large, gahnite tends to precipitate in the melting process. There is no particular lower limit for Al2O3 /( SiO2 + ZnO), but it is practically 0.07 or more.
ＭｇＯ及びＣａＯは、ガラスの粘性を下げる成分である。ＭｇＯ＋ＣａＯは８～２２％であり、特に１０～２０％であることが好ましい。ＭｇＯ＋ＣａＯが少な過ぎると、ガラスの軟化温度が上昇し易くなる。一方、ＭｇＯ＋ＣａＯの含有量が多過ぎると、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。 MgO and CaO are components that lower the viscosity of glass. The MgO + CaO content is 8-22%, and preferably 10-20%. If the MgO + CaO content is too low, the softening temperature of the glass tends to increase. On the other hand, if the MgO + CaO content is too high, the thermal expansion coefficient may become too high, acid resistance may decrease, and insulation properties may decrease.
ＭｇＯの含有量は、２～２０％、３～１５％、特に４～１３％であることが好ましい。 The MgO content is preferably 2-20%, 3-15%, and especially 4-13%.
ＣａＯの含有量は、２～２０％、３～１５％、特に４～１３％であることが好ましい。 The CaO content is preferably 2-20%, 3-15%, and particularly preferably 4-13%.
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, MnO2 , Ta2O5 , Nb2O5 , CeO2 , Sb2O3 , etc. ) may be contained up to 7% (preferably up to 3%).
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 standpoint, it is preferable that the material contains substantially no lead components (e.g., PbO, etc.) and substantially no Bi 2 O 3 , F, or Cl. It is also preferable that the material contains substantially no alkaline components (Li 2 O, Na 2 O, and K 2 O) that adversely affect the surface of semiconductor elements.
本発明の半導体素子被覆用ガラスは、３０～３００℃の温度範囲における熱膨張係数は、２０～５５×１０－７／℃、特に３０～５０×１０－７／℃であることが好ましい。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。 The glass for covering a semiconductor element of the present invention preferably has a thermal expansion coefficient of 20 to 55×10 −7 /° C., particularly 30 to 50×10 −7 /° C., in the temperature range of 30 to 300° C. If the thermal expansion coefficient is outside the above range, cracks, warping, etc. are likely to occur due to the difference in thermal expansion coefficient with the semiconductor element.
本発明の半導体素子被覆用ガラスは、粉末状であることが好ましい。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。 The glass for coating semiconductor elements of the present invention is preferably in powder form. If it is processed into powder form, it can be easily used to coat the surface of a semiconductor element using, for example, a paste method or an electrophoretic coating method.
ガラス粉末の平均粒子径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、電気泳動法によるペースト塗布も困難になる。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 particle diameter D50 of the glass powder is preferably 25 μm or less, particularly 15 μm or less. If the average particle diameter D50 of the glass powder is too large, it becomes difficult to make a paste. In addition, it becomes difficult to apply the paste by electrophoresis. The lower limit of the average particle diameter D50 of the glass powder is not particularly limited, but in reality, it is 0.1 μm or more. The "average particle diameter D50 " is a value measured on a volume basis, and refers to a value measured by a laser diffraction method.
本発明の半導体素子被覆用ガラスは、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 glass for covering semiconductor elements of the present invention may be mixed with ceramic powder to form a composite powder, if necessary. Adding ceramic powder makes it easier to adjust the thermal expansion coefficient.
セラミック粉末は、ガラス粉末１００質量部に対して、２５質量部未満、特に２０質量部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。 It is preferable that the amount of ceramic powder is less than 25 parts by mass, and especially less than 20 parts by mass, per 100 parts by mass of glass powder. If the ceramic powder content is too high, the softening fluidity of the glass is impaired, making it difficult to coat the surface of the semiconductor element.
セラミック粉末の平均粒子径Ｄ５０は、３０μｍ以下、特に２０μｍ以下であることが好ましい。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 D50 of the ceramic powder is preferably 30 μm or less, particularly 20 μm or less. If the average particle diameter D50 of the ceramic powder is too large, the surface smoothness of the coating layer is likely to decrease. The lower limit of the average particle diameter D50 of the ceramic powder is not particularly limited, but is practically 0.1 μm or more.
次に、本発明に係る半導体素子被覆用ガラス、半導体素子被覆用焼結体の製造方法の一例を説明する。 Next, an example of a method for producing the glass for covering semiconductor elements and the sintered body for covering semiconductor elements according to the present invention will be described.
まず、所望のガラス組成となるように調合した原料粉末を１３００～１５５０℃で１～２時間、均質なガラスが得られるまで溶融する。次いで、得られた溶融ガラスをフィルム状等に成形した後、粉砕し、分級することにより、粉末状の半導体素子被覆用ガラスを作製する。 First, raw material powders mixed to obtain the desired glass composition are melted at 1300-1550°C for 1-2 hours until a homogeneous glass is obtained. The resulting molten glass is then formed into a film or other shape, which is then crushed and classified to produce powdered glass for coating semiconductor elements.
次に、例えば、ペースト法、電気泳動塗布法等を用いて、粉末状の半導体素子被覆用ガラスを半導体素子表面に被覆する。その後、熱処理を行うことにより、半導体素子表面を被覆した半導体素子被覆用ガラスは、結晶の析出していない半導体素子被覆用焼結体となる。なお、半導体素子被覆用焼結体は、半導体素子被覆用ガラスのガラス組成と同一の組成範囲を有することが好ましい。 Next, the surface of the semiconductor element is coated with powdered glass for covering semiconductor elements, for example, by using a paste method, electrophoretic coating method, or the like. After that, by carrying out a heat treatment, the glass for covering semiconductor elements that has covered the surface of the semiconductor element becomes a sintered body for covering semiconductor elements in which no crystals are precipitated. Note that it is preferable that the sintered body for covering semiconductor elements has the same composition range as the glass composition of the glass for covering semiconductor elements.
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。 The present invention will be described in detail below based on examples. Note that the following examples are merely illustrative. The present invention is not limited to the following examples in any way.
表１は、本発明の実施例（試料Ｎｏ．１～４、９、１０）と比較例（試料Ｎｏ．５～８）を示している。 Table 1 shows examples of the present invention (samples No. 1-4, 9, 10) and comparative examples (samples No. 5-8).
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。 Each sample was prepared as follows: First, raw material powders were mixed to obtain the glass composition shown in the table, and the mixture was melted at 1500° C. for 1 hour to vitrify the glass. The molten glass was then formed into a film, which was then pulverized in a ball mill and classified using a 350 mesh sieve to obtain a glass powder with an average particle size D50 of 12 μm.
各試料について、熱膨張係数、耐失透性を評価した。その結果を表１に示す。 The thermal expansion coefficient and devitrification resistance of each sample were evaluated. The results are shown in Table 1.
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 was measured using a push rod type thermal expansion coefficient measuring device in the temperature range of 30 to 300°C.
耐失透性は次のようにして評価した。各試料のガラスフィルム１００ｇを白金るつぼに入れ、１１５０℃にて２４時間保持後、目視にて失透物（ガーナイト）が析出していることを確認した。その後、１４００℃にて１０分間保持し、目視にて失透物（ガーナイト）が確認されなければ「〇」、失透物（ガーナイト）が確認されれば「×」とした。なお、失透物をＸ線回折装置にて測定し、ガーナイトであることを確認した。 Devitrification resistance was evaluated as follows. 100 g of glass film from each sample was placed in a platinum crucible and held at 1150°C for 24 hours, after which the presence of devitrified matter (gahnite) was confirmed by visual inspection. After that, the sample was held at 1400°C for 10 minutes, and if devitrified matter (gahnite) was not confirmed by visual inspection, it was marked as "Good", and if devitrified matter (gahnite) was confirmed, it was marked as "Poor". The devitrified matter was measured using an X-ray diffraction device and confirmed to be gahnite.
表１から明らかなように、試料Ｎｏ．１～４、９、１０は、耐失透性が〇であり、熱膨張係数も２０～５５×１０－７／℃であった。なお、試料Ｎｏ．１～４を表に記載の温度で１０分間焼成したところ、結晶は析出していなかった。 As is clear from Table 1, Samples Nos. 1 to 4, 9, and 10 had a resistance to devitrification of ◯ and a thermal expansion coefficient of 20 to 55×10 −7 /° C. When Samples Nos. 1 to 4 were fired for 10 minutes at the temperatures shown in the table, no crystals were precipitated.
一方、試料Ｎｏ．５～８は、Ａｌ２Ｏ３／（ＳｉＯ２＋ＺｎＯ）が大き過ぎるため、耐失透性が×であり、溶融工程に支障を来たす虞のあるガラスであると考えられる。 On the other hand, Samples Nos. 5 to 8 have too large Al 2 O 3 /(SiO 2 +ZnO) and therefore are considered to be glasses that are likely to cause problems in the melting process and have poor devitrification resistance.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03126639A (en) * | 1989-10-06 | 1991-05-29 | Nippon Electric Glass Co Ltd | Glass composition for coating |
| WO2013168236A1 (en) * | 2012-05-08 | 2013-11-14 | 新電元工業株式会社 | Resin-sealed semiconductor device and production method for resin-sealed semiconductor device |
| WO2018221426A1 (en) * | 2017-05-27 | 2018-12-06 | 日本山村硝子株式会社 | Encapsulating glass composition |
| JP2020055725A (en) * | 2018-10-04 | 2020-04-09 | 日本電気硝子株式会社 | Semiconductor element coating glass and semiconductor coating material using same |
| WO2020158187A1 (en) * | 2019-01-29 | 2020-08-06 | 日本電気硝子株式会社 | Glass for semiconductor element coating and material for semiconductor coating using same |
| WO2021149633A1 (en) * | 2020-01-21 | 2021-07-29 | 日本山村硝子株式会社 | Sealing/coating glass with low thermal expandability |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03126639A (en) * | 1989-10-06 | 1991-05-29 | Nippon Electric Glass Co Ltd | Glass composition for coating |
| WO2013168236A1 (en) * | 2012-05-08 | 2013-11-14 | 新電元工業株式会社 | Resin-sealed semiconductor device and production method for resin-sealed semiconductor device |
| WO2018221426A1 (en) * | 2017-05-27 | 2018-12-06 | 日本山村硝子株式会社 | Encapsulating glass composition |
| JP2020055725A (en) * | 2018-10-04 | 2020-04-09 | 日本電気硝子株式会社 | Semiconductor element coating glass and semiconductor coating material using same |
| WO2020158187A1 (en) * | 2019-01-29 | 2020-08-06 | 日本電気硝子株式会社 | Glass for semiconductor element coating and material for semiconductor coating using same |
| WO2021149633A1 (en) * | 2020-01-21 | 2021-07-29 | 日本山村硝子株式会社 | Sealing/coating glass with low thermal expandability |
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