TW201134780A - 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 PDFInfo
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- TW201134780A TW201134780A TW100102341A TW100102341A TW201134780A TW 201134780 A TW201134780 A TW 201134780A TW 100102341 A TW100102341 A TW 100102341A TW 100102341 A TW100102341 A TW 100102341A TW 201134780 A TW201134780 A TW 201134780A
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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
- 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
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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
- 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
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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
- 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
Abstract
Description
201134780 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種作為含有p_N接面之半導體裝置之被 覆用而使用之玻璃及使用其之半導體被覆用材料。 【先前技術】 一般而言，於矽二極體或電晶體等半導體裝置中，自防 止外部氣體污染之觀點而言，使半導體元件之含有厂N接 面部之表面藉由含有玻璃之材料而被覆。由此使半導體元 件表面得以穩定化，可抑制隨時間之特性劣化。 作為用作半導體被覆用材料之玻璃所要求之特性，可舉 出下述特性等.（1)熱膨脹係數適合於半導體之熱膨脹係 數，以免於被覆時因與半導體元件之熱膨脹係數差而產生 龜裂等；（2)能以低溫（例如9〇〇〇c以下）進行被覆，以防止 半導體元件之特性劣化；（3)不含有對半導體元件表面造成 不良影響之鹼成分等雜質；（4)作為半導體元件表面被覆後 之電氣特性，具有反向耐壓較高、漏電流較少等之高可靠 性。 先刚’作為半導體被覆用玻璃，已知Zn〇_B2〇3_Si〇2系 等鋅系玻璃、Pb0-Si02-Al203 系或 Pb0-Si02-Al203-B203 系 等錯系玻璃。其中’自作業性之觀點而言，pb〇_si〇2_ Α!2〇3系及PbO-Si〇2-Al2〇3-B2〇3系等鉛系玻璃成為主流（例 如’參照專利文獻1〜4)。 先行技術文獻 專利文獻 153709.doc 201134780 專利文獻1:日本專利特公平1-49653號公報 專利文獻2:日本專利特開昭50-129181號公報 專利文獻3 .日本專利特開昭48_43275號公報 專利文獻4 .日本專利特開2〇〇8·16288ΐ號公報 【發明内容】 發明所欲解決之問題[Technical Field] The present invention relates to a glass used as a coating for a semiconductor device including a p_N junction and a semiconductor coating material using the same. [Prior Art] In general, in a semiconductor device such as a bismuth diode or a transistor, the surface of the semiconductor device containing the N surface of the surface is covered by a material containing glass from the viewpoint of preventing external gas contamination. . Thereby, the surface of the semiconductor element is stabilized, and deterioration of characteristics with time can be suppressed. The characteristics required for the glass used as the material for semiconductor coating include the following characteristics. (1) The thermal expansion coefficient is suitable for the thermal expansion coefficient of the semiconductor so as not to cause cracking due to a difference in thermal expansion coefficient from the semiconductor element during coating. (2) It can be coated at a low temperature (for example, 9 〇〇〇c or less) to prevent deterioration of characteristics of the semiconductor element; (3) It does not contain impurities such as alkali components which adversely affect the surface of the semiconductor element; (4) The electrical characteristics after the surface of the semiconductor element is covered have high reliability such as high reverse breakdown voltage and low leakage current. First, as the glass for semiconductor coating, a zinc-based glass such as a Zn〇_B2〇3_Si〇2 system, a Pb0-SiO2-Al203 system or a Pb0-SiO2-Al203-B203 system is known. Among them, from the viewpoint of workability, lead-based glasses such as pb〇_si〇2_Α!2〇3 series and PbO-Si〇2-Al2〇3-B2〇3 series have become mainstream (for example, 'Reference Patent Document 1> ~4). Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 4. Japanese Patent Laid-Open No. 2,8,16,288, the disclosure of the invention, the problem to be solved by the invention
PbO等鉛成分為對環境有害之成分，因此近年來，禁止 其用於電氣及電子機器中，並正在推進各種材料之無錯化 發展。對於上述之Zn〇_B2〇3_Si〇2系等鋅系玻璃，亦由於 含有少量之鉛成分從而自環境方面考慮為不能使用者。 又，即便為無鉛組成，但由於半導體表面被覆後之表面電 荷密度以低密度為主流，故難以應對高耐壓用之半導體元 件。 因此本發明之第一課題在於，提供一種即便不含有紐 成分但半導體表面被覆後之表面電荷密度亦較大之半導體 被覆用玻璃。 進而，與鉛系玻璃相比，鋅系玻璃之化學耐久性較差， 於玻璃煅燒後之後步驟中對於酸之耐受性相對較弱。因 此，有必要於被覆玻璃表面進而形成保護膜而執行後步 驟。 因此，本發明之第二課題在於，提供一種即便不含有錯 成分但半導體表面被覆後之表面電荷密度亦較大、且化學 耐久性亦優異之半導體被覆用玻璃。 解決問題之技術手段 153709.doc 201134780 本發明者經積極研究後發現，藉由具有特性之組成之Lead components such as PbO are environmentally harmful components. Therefore, in recent years, they have been banned from use in electrical and electronic equipment, and various materials have been promoted without error. The zinc-based glass such as the above-mentioned Zn〇_B2〇3_Si〇2 system also has a small amount of lead component and is not user-friendly from the viewpoint of the environment. Further, even if it is a lead-free composition, since the surface charge density after coating the semiconductor surface is low in density, it is difficult to cope with a semiconductor element for high withstand voltage. Therefore, a first object of the present invention is to provide a semiconductor-coated glass which has a large surface charge density after coating a semiconductor surface without containing a button component. Further, the zinc-based glass is inferior in chemical durability as compared with the lead-based glass, and is relatively weak in resistance to acid in the subsequent steps after the glass is calcined. Therefore, it is necessary to perform the subsequent steps on the surface of the coated glass to form a protective film. In view of the above, it is a second object of the present invention to provide a semiconductor-coated glass which has a large surface charge density after being coated with a semiconductor surface and which is excellent in chemical durability, even if it does not contain a component. Technical means for solving the problem 153709.doc 201134780 The inventors have found through active research that they have a characteristic composition.
ZnO-B2〇3-Si〇2系玻璃可解決上述第一及第二課題，從而 提出作為本發明。 即，解決第一課題之本發明之半導體被覆用玻璃之特徵 在於.含有以質量。/。計為5〇〜65%之211〇、19〜28%之ΙΟ]、 7〜15%之Si〇2、3〜12%之Al2〇3、〇丨〜5%之Bi2〇3的組成， 且實質不含有鉛成分。 解決第一課題之本發明之半導體被覆用玻璃中，相對於 Zn〇-B2〇3-Si〇A玻璃而含有特定量之Ai2〇3及出办因而 这半導體被覆用玻璃係半導體表面被覆後之表面電荷密度 較大、適合高耐壓用之半導體元件之被覆者…由於； 質不含有鉛成分，故對環境造成之負擔較小。 再者，於解決第一課題之本發明半導體被覆用玻璃中， 所謂「實質不含有鉛成分」’並非係指未試圖添加鉛成分 作2玻璃成分’且並非係指甚至連不可避免地混入之雜質 亦元全排除。客觀而言’係指含有雜質之雜成分之含量未 滿0.1質量％。 又’解決第-課題之本發明之半導體被覆用玻璃之較佳 形態為，更含有0〜5%之Mn〇2、〇〜5%之灿2〇5、〇〜3%之 C e Ο 2的組成。 又:本發明係關於一種使用解決上述第一課題之本發明 之半導體被覆用玻璃所構成之半導體被覆用玻璃粉末、及 半導體被覆用材料。 該構成之本發明之半導料w麵粉末之特徵在於： 153709.doc 201134780 其係包含上述任一半導體被覆用玻璃。 由於半導體被覆用玻璃為粉末狀，故可容易進行半導體 表面之被覆。 又’該構成之本發明之半導體被覆用材料之特徵在於： 其含有上述半導體被覆用玻璃粉末。 又’上述本發明之半導體被覆用材料之較佳形態為，相 對於上述半導體被覆用玻璃粉末1〇〇質量份，含有選自 Ti〇2、Zr〇2、ZnO、ZnO-B2〇3 及 2ZnO-Si〇2中之至少 1種無 機粉末0.01〜5質量份。 尤其於Si等半導體元件與玻璃之接觸面積非常大之情形 時，較理想的是玻璃與Si之熱膨脹係數相近。玻璃之熱膨 脹係數係可根據玻璃中所含之結晶成分而調整，但對自玻 璃中析出之結晶之量非常難以進行適當控制。因此，若對 半導體被覆用玻璃適當添加上述無機粉末，則由於該 機粉末發揮晶核形成劑之作用，故可較容易地控制所析出 之結晶量》其結果可容易調整至所需之熱膨脹係數。 又，上述本發明之半導體被覆用材料之另一較佳形態， 其特徵為表面電荷密度為7x10〗]/cm2以上。 進而，解決第二課題之本發明之半導體被覆用玻璃之特 徵在於：含有以質量％計為40〜60%之ZnO、5〜25%之 B2〇3、15〜3 5。/〇之Si〇2、3〜12。/〇之Al2〇3的組成，且實質不 含有鉛成分。 本發明之解決第二課題之半導體被覆用玻璃具有下述特 徵.其係相對於ZnO-B2〇3_Si〇2系玻璃而含有特定量之 153709.doc 201134780The ZnO-B2〇3-Si〇2 glass can solve the above first and second problems, and has been proposed as the present invention. In other words, the semiconductor-coated glass of the present invention which solves the first problem is characterized in that it contains a mass. /. It is composed of 5〇~65% of 211〇, 19~28%ΙΟ], 7~15% of Si〇2, 3~12% of Al2〇3, and 〇丨~5% of Bi2〇3, and It does not contain lead in essence. In the semiconductor-coated glass of the present invention which solves the first problem, a specific amount of Ai2〇3 is contained in the Zn〇-B2〇3-Si〇A glass, and the glass-based semiconductor surface of the semiconductor coating is coated. The surface charge density is large, and it is suitable for the coating of the semiconductor element for high withstand voltage... Since the quality does not contain the lead component, the burden on the environment is small. Further, in the semiconductor-coated glass of the present invention which solves the first problem, the term "substantially does not contain a lead component" does not mean that no attempt is made to add a lead component as a "glass component" and that it does not even mean that it is inevitably mixed. Impurities are also excluded. Objectively, it means that the content of the impurity containing impurities is less than 0.1% by mass. Further, a preferred embodiment of the glass for semiconductor coating of the present invention which solves the first problem is that it further contains 0 to 5% of Mn〇2, 〇~5% of 〇2〇5, 〇~3% of C e Ο 2 Composition. Further, the present invention relates to a semiconductor coating glass powder comprising the semiconductor-coated glass of the present invention which solves the above-mentioned first problem, and a semiconductor coating material. The semiconductive w-side powder of the present invention having such a constitution is characterized in that: 153709. doc 201134780 includes any of the above-described semiconductor coating glasses. Since the glass for semiconductor coating is in a powder form, coating of the semiconductor surface can be easily performed. Further, the semiconductor coating material of the present invention is characterized in that it contains the above-mentioned glass powder for semiconductor coating. Further, a preferred embodiment of the material for semiconductor coating of the present invention contains at least 1 part by mass of the glass powder for semiconductor coating, and is selected from the group consisting of Ti〇2, Zr〇2, ZnO, ZnO-B2〇3, and 2ZnO. At least one inorganic powder of -Si〇2 is 0.01 to 5 parts by mass. Particularly in the case where the contact area between the semiconductor element such as Si and the glass is very large, it is preferable that the thermal expansion coefficient of the glass and Si be similar. The coefficient of thermal expansion of the glass can be adjusted according to the crystal component contained in the glass, but it is very difficult to appropriately control the amount of crystals precipitated from the glass. Therefore, when the inorganic powder is appropriately added to the glass for semiconductor coating, since the powder of the machine functions as a nucleating agent, the amount of crystals precipitated can be easily controlled. The result can be easily adjusted to a desired thermal expansion coefficient. . Further, another preferred embodiment of the semiconductor coating material of the present invention is characterized in that the surface charge density is 7 x 10 Å / cm 2 or more. Further, the semiconductor-coated glass of the present invention which solves the second problem is characterized in that it contains 40 to 60% by mass of ZnO, and 5 to 25% of B2〇3 and 15 to 3 5 by mass%. /〇Si〇2, 3~12. The composition of Al2〇3 is not contained in the substance. The semiconductor-coated glass according to the second aspect of the present invention has the following characteristics: it contains a specific amount of 153709.doc 201134780 with respect to ZnO-B2〇3_Si〇2-based glass.
Al2〇3者’係藉由嚴格限制各成分之含量而使半導體表面 被覆後之表面電荷密度增大、適合高财㈣之半導體元件 之被覆者，且化學耐久性較高…由於實質不含 分，故對環境造成之負擔較小。 再者，於本發明之解決第二課題之半導體#覆用玻璃 中，所謂「實質不含有錄成分」，係指未刻意添加紐成分 作為玻璃成分，而非係指甚至連不可避地混入之雜質亦完 全排除。客觀而言，係指包含雜質之鉛成分之含量未滿 0.1質量％。 4 又，解決第二課題之本發明之半導體被覆用玻璃之較佳 形態之特徵為，更含有〇〜5%之則2〇3、〇〜5%iMn〇2、 0〜5%之Nb205、〇〜3%之Ce〇W組成。 又，本發明係關於一種使用解決上述第二課題之半導體 被覆用玻璃所構成之半導體被覆用材料。 該構成之本發明之半導體被覆用材料之特徵在於：其係 含有包含上述半導體被覆用玻璃之玻璃粉末。 藉由使用該半導體被覆用材料而可容易進行半導體表面 之被覆。 又，上述本發明之半導體被覆用材料之較佳形態之特徵 為’相對於上述玻璃粉末100質量份，含有選自Ti〇2、The Al2〇3 is a coating of a semiconductor element that is coated with a semiconductor surface by strictly limiting the content of each component, and is suitable for coatings of semiconductor components of the high-tech (4), and has high chemical durability... Therefore, the burden on the environment is small. Further, in the semiconductor #coated glass which solves the second problem of the present invention, the term "substantially does not contain a recorded component" means that a component is not intentionally added as a glass component, and not an impurity which is inevitably mixed. Also completely excluded. Objectively speaking, it means that the content of the lead component containing impurities is less than 0.1% by mass. Further, a preferred aspect of the semiconductor-coated glass of the present invention which solves the second problem is characterized in that it further contains 2〇3, 〇~5% iMn〇2, 0~5% Nb205 of 〇~5%, 〇~3% of Ce〇W composition. Moreover, the present invention relates to a semiconductor coating material comprising the semiconductor coating glass which solves the above second problem. The semiconductor coating material of the present invention is characterized in that it contains a glass powder containing the above-mentioned semiconductor coating glass. The coating of the semiconductor surface can be easily performed by using the material for semiconductor coating. Further, a preferred embodiment of the material for semiconductor coating of the present invention is characterized in that it is selected from the group consisting of Ti 〇 2 with respect to 100 parts by mass of the glass powder.
Zr〇2、Ζη0、Ζη〇·Β2〇3 及 2Zn〇_Si〇2 中之至少 i 種無機 J 末 0·01〜5質量份。 特別於Si等半導體元件與玻璃之接觸面積非常大之情形 時，較理想的是玻璃與Si之熱膨脹係數相近。玻璃之熱膨 153709.doc 201134780 知數係可根據玻璃中所含之結晶成分而調整，但對自玻 中析出之結晶之量非常難以進行適當的控制。因此，若 對半導體被覆用玻璃適當添加上述無機粉末，則由於該等 無機粉末發揮晶核形成劑之作用，故可較容易地控制所析 出之、乡。曰曰量。其結果可容易調整至所需之熱膨脹係數。 【實施方式】 以下，對本發明之半導體被覆用玻璃中之各成分按以上 述進行規疋之理由加以說明。再者，於以下說明令，只要 事先無特別說明，則「％」係指「質量％」。 以下，將解決第一課題之半導體被覆玻璃、以及使用其 所構成之半導體被覆用玻璃粉末及半導體被覆用材料作為 第一貫施形態進行說明，將解決第二課題之半導體被覆玻 璃及使用其所構成之半導體被覆用材料作為第二實施形態 進行說明。 (第一實施形態） 本發明第一實施形態之半導體被覆用玻璃之特徵在於： 含有以質量％計為50~65%之ZnO、19〜28%之B2〇3、7〜1 5% 之Si02、3~12%之AI2O3、0.1〜5%之Bi2〇3的組成，且實質 不含有船成分。 ΖηΟ為使玻璃穩定化之成分。ΖηΟ之含量較佳為 50〜65% ’尤佳為55~63%。若ΖηΟ之含量少於50%，則玻璃 之熱膨脹係數變大，於密封半導體元件時會有因與半導體 元件之熱膨脹差而產生龜裂之虞。另一方面，若ΖηΟ之含 量多於65% ’則結晶化會急速推進，故玻璃之流動性不 153709.doc 201134780 足’從而具有難以被覆半導體元件表面之傾向。 B2〇3為玻璃之網狀形成成分，且為提高流動性之成分。 B2〇3之含量較佳為19〜28%，尤佳為20〜25% »若B2〇3之含 $少於19% ’則結晶性變強而破壞流動性，從而具有難以 被覆半導體το件表面之傾向。另一方面若ίο;之含量多 於28% ’則玻璃之熱膨脹係數變大，於密封半導體元件時 會有因與半導體元件之熱膨脹差而產生龜裂之虞。At least one kind of inorganic J at the end of Zr〇2, Ζη0, Ζη〇·Β2〇3 and 2Zn〇_Si〇2 is 0·01~5 parts by mass. Particularly in the case where the contact area between the semiconductor element such as Si and the glass is very large, it is preferable that the thermal expansion coefficient of the glass and Si be similar. Thermal expansion of glass 153709.doc 201134780 The number of crystals can be adjusted according to the crystal components contained in the glass, but it is very difficult to appropriately control the amount of crystals precipitated from the glass. Therefore, when the inorganic powder is appropriately added to the glass for semiconductor coating, the inorganic powder functions as a nucleating agent, so that the precipitated soil can be easily controlled. Quantity. The result can be easily adjusted to the desired coefficient of thermal expansion. [Embodiment] Hereinafter, the reason why each component in the glass for semiconductor coating of the present invention is regulated as described above will be described. In addition, in the following explanation, "%" means "% by mass" unless otherwise specified. In the following, the semiconductor-coated glass of the first problem and the semiconductor-coated glass powder and the semiconductor-coated material which are used in the first embodiment will be described as a first embodiment, and the semiconductor-coated glass which solves the second problem and the use thereof will be described. The semiconductor coating material configured as described above will be described as a second embodiment. (First Embodiment) The semiconductor-coated glass according to the first embodiment of the present invention is characterized in that it contains 50 to 65% by mass of ZnO, 19 to 28% of B2〇3, and 7 to 15% of SiO2. 3~12% of AI2O3, 0.1~5% of Bi2〇3, and does not contain ship components. ΖηΟ is a component that stabilizes the glass. The content of ΖηΟ is preferably 50 to 65% Å, preferably 55 to 63%. When the content of ΖηΟ is less than 50%, the coefficient of thermal expansion of the glass becomes large, and when the semiconductor element is sealed, cracks may occur due to a difference in thermal expansion from the semiconductor element. On the other hand, if the content of ΖηΟ is more than 65% ', the crystallization proceeds rapidly, so the fluidity of the glass does not tend to cover the surface of the semiconductor element. B2〇3 is a network forming component of glass and is a component for improving fluidity. The content of B2〇3 is preferably 19 to 28%, particularly preferably 20 to 25%. If the content of B2〇3 is less than 19%, the crystallinity becomes strong and the fluidity is broken, so that it is difficult to coat the semiconductor. The tendency of the surface. On the other hand, if the content of ίο; is more than 28%', the coefficient of thermal expansion of the glass becomes large, and when the semiconductor element is sealed, cracks may occur due to a difference in thermal expansion from the semiconductor element.
Si02為玻璃之網狀形成成分，且為提高耐酸性之成分。 Si〇2之含量較佳為7〜15%，尤佳為9〜。若“ο】之含量 少於7 /〇’則玻璃之熱膨脹係數變大，於密封半導體元件 時會有因與半導體元件之熱膨脹差而產生龜裂之虞。又， 玻璃之化學耐久性易降低。若⑽之含量多於15%，則難 以獲得均質之玻璃。Si02 is a network forming component of glass and is a component for improving acid resistance. The content of Si〇2 is preferably 7 to 15%, particularly preferably 9 to. If the content of "ο] is less than 7 /〇', the coefficient of thermal expansion of the glass becomes large, and when the semiconductor element is sealed, cracks may occur due to a difference in thermal expansion from the semiconductor element. Moreover, the chemical durability of the glass is liable to lower. If the content of (10) is more than 15%, it is difficult to obtain a homogeneous glass.
Al2〇3為增大玻璃之表面電荷密度之成分。之含量 較佳為3〜12%，尤佳為5〜1〇%。若Al2〇3之含量少於， 則難以取知上述效果。另一方面’若Ah。〗之含量多於 12% ’則玻璃易失透^Al2〇3 is a component that increases the surface charge density of the glass. The content is preferably from 3 to 12%, particularly preferably from 5 to 1% by weight. If the content of Al2〇3 is less than that, it is difficult to know the above effects. On the other hand, 'If Ah. 〗 The content of more than 12% ’ glass is easy to lose
Bi2〇3亦為提兩玻璃之表面電荷密度之成分。之含 量較佳為0.1〜5%，尤佳為〇 5〜3%。若則2〇3之含量少於 ο」％，則難以取得上述效果。另—方面，若Bi2〇3之含量 多於5%，則玻璃易失透。 本發明之半導體被覆用玻璃除上述成分外可含有Bi2〇3 is also a component of the surface charge density of the two glasses. The content is preferably from 0.1 to 5%, more preferably from 5 to 3%. If the content of 2〇3 is less than ο"%, it is difficult to achieve the above effect. On the other hand, if the content of Bi2〇3 is more than 5%, the glass is easily devitrified. The semiconductor coating glass of the present invention may contain, in addition to the above components,
Mn〇2、Nb2〇5、及Ce〇2。該等成分具有使半導體元件之漏 電流降低之效果。 I53709.doc 201134780 Μη02之含量較佳為〇〜5%，尤佳為〇 u%。若Μη〇2之含 量多於5°/。，則具有玻璃之熔融性降低之傾向。Mn〇2, Nb2〇5, and Ce〇2. These components have an effect of lowering the leakage current of the semiconductor element. I53709.doc 201134780 The content of Μη02 is preferably 〇~5%, and particularly preferably 〇u%. If Μη〇2 is more than 5°/. Then, there is a tendency that the meltability of the glass is lowered.
Nb205之含量較佳為〇〜5%，尤佳為〇丨—3%。若Nb2〇5之 含量多於5。/。，則具有玻璃之熔融性降低之傾向。The content of Nb205 is preferably 〇~5%, and particularly preferably 〇丨-3%. If the content of Nb2〇5 is more than 5. /. Then, there is a tendency that the meltability of the glass is lowered.
Ce〇2之含量較佳為〇〜3% ’尤佳為〇。若Ce〇2之含 量多於3%，則玻璃之結晶性過強而具有玻璃之流動性降 低之傾向。 再者’本發明之半導體被覆用玻璃自環境方面之觀點而 言係實質不含有鉛成分（PbO等）。 自可容易進行半導體元件表面之被覆之觀點而言，本發 明之半導體被覆用玻璃較佳為粉末狀。半導體被覆用玻璃 粉末之平均粒徑Dm較佳為25 μιη以下，尤佳為15 μηι& 下。若半導體被覆用玻璃粉末之平均粒徑d5g大於25 pm， 則難以實現糊膠化，從而難以均勻地被覆於半導體表面。 又，具有藉由電泳之被覆亦變得困難之傾向。再者，平均 粒徑Dm之下限雖無特別限定，但實際為〇1 以上。 本發月之半導體被覆用材料係含有上述半冑體被覆用玻 璃粉末者。再者，本發明之半導體被覆用材料亦可係相對 於上述半導體被覆用玻璃粉末而含有選自Ti〇2、心…、 ZnO、ZnO-B2〇3、2Zn〇-Si〇2中之至少1種無機粉末作為日 核形成劑者。料线粉末之含量㈣於半導體被覆用: 璃粉末100質量份較佳為〇 ()1〜5質量份，尤佳為〇卜3質旦 伤。若無機粉末之含量少於GG1 f量份，則析出之結晶量 孝乂少而具有難以達成所需之熱膨脹係數之傾向。若無機於 153709.doc 201134780 末之3量多於5質量份，則析出之結晶量過多而破壞流動 I·生從而具有難以進行半導體元件表面之被覆之傾向。 再者’具有下述傾肖：若上述無機粉末之粒度越小，則 自玻璃析出之結晶之粒徑越小且機械強度越大。因此，無 機叙末之平均粒徑Dm較佳為5 pm以下，尤佳為3 pm以 下。平均粒徑Dm之下限雖無特別限定，但實際為〇1 μ〇ι以 上。 本發明之半導體被覆用材料之表面電荷密度較佳為對 於電壓1000 V之半導體裝置為7xl〇u/cm2以上，對於電壓 1500 V以上之半導體裝置為1〇xl〇11/cm2以上。 本發明之半導體被覆用材料之熱膨脹係數（3〇〜3〇〇。〇）係 對應半導體元件之熱膨脹係數而於例如2〇〜6〇χ丨、進 而30〜5〇xl〇-VC之範圍内適當調整。 本發明之半導體被覆用玻璃係可藉由以下方法獲得：調 &各氧化物成分之原料粉末而作為一次投料量，以14〇〇。〇 左右之溫度進行約1小時熔融以使其玻璃化後，進行成 形、粉碎、分級。 (第二實施形態） 本發明第二實施形態之半導體被覆用玻璃之特徵在於： 作為組成，含有以質量％計為40〜60%之ZnO、5〜25%之 B2〇3、15〜35%之Si〇2、3~12°/〇之Al2〇3，且實質不含有鉛 成分。The content of Ce〇2 is preferably 〇~3% ‘especially 〇. When the content of Ce〇2 is more than 3%, the crystallinity of the glass is too strong, and the fluidity of the glass tends to decrease. Further, the glass for semiconductor coating of the present invention does not substantially contain a lead component (PbO or the like) from the viewpoint of the environment. The semiconductor coating glass of the present invention is preferably in the form of a powder from the viewpoint that the surface of the semiconductor element can be easily coated. The average particle diameter Dm of the glass powder for semiconductor coating is preferably 25 μm or less, and more preferably 15 μm·m. When the average particle diameter d5g of the glass powder for semiconductor coating is more than 25 pm, it is difficult to achieve gelatinization, and it is difficult to uniformly coat the surface of the semiconductor. Moreover, it is also difficult to have coating by electrophoresis. Further, the lower limit of the average particle diameter Dm is not particularly limited, but is actually 〇1 or more. The semiconductor coating material of the present month is the one containing the glass powder for the above-described semiconductor coating. Furthermore, the semiconductor coating material of the present invention may contain at least one selected from the group consisting of Ti〇2, core, ZnO, ZnO-B2〇3, and 2Zn〇-Si〇2 with respect to the glass powder for semiconductor coating. An inorganic powder is used as a nucleating agent. Content of the powder of the yarn (4) For coating of the semiconductor: 100 parts by mass of the glass powder is preferably 〇 () 1 to 5 parts by mass, and particularly preferably 3 denier. When the content of the inorganic powder is less than the amount of GG1 f, the amount of crystals precipitated is less, and it is difficult to achieve a desired thermal expansion coefficient. If the inorganic amount is more than 5 parts by mass at the end of 153709.doc 201134780, the amount of crystals precipitated is too large to break the flow, and it tends to be difficult to coat the surface of the semiconductor element. Further, 'there is a lower angle: the smaller the particle size of the inorganic powder, the smaller the particle diameter of the crystal precipitated from the glass and the higher the mechanical strength. Therefore, the average particle diameter Dm at the end of the inorganic phase is preferably 5 pm or less, and more preferably 3 pm or less. The lower limit of the average particle diameter Dm is not particularly limited, but is actually 〇1 μ〇ι or more. The surface charge density of the semiconductor coating material of the present invention is preferably 7 x 1 〇 u / cm 2 or more for a semiconductor device having a voltage of 1000 V, and 1 〇 x l 〇 11 / cm 2 or more for a semiconductor device having a voltage of 1500 V or more. The coefficient of thermal expansion (3 〇 3 〇〇 〇) of the semiconductor coating material of the present invention is in the range of, for example, 2 〇 to 6 〇χ丨, and further 30 to 5 〇 x 〇 VC VC, depending on the thermal expansion coefficient of the semiconductor element. Appropriate adjustments. The glass for semiconductor coating of the present invention can be obtained by adjusting the raw material powder of each oxide component as a single charge to 14 Torr. 〇 The left and right temperatures are melted for about 1 hour to be vitrified, and then formed, pulverized, and classified. (Second Embodiment) The glass for semiconductor coating according to the second embodiment of the present invention is characterized in that it contains 40 to 60% by mass of ZnO, 5 to 25% of B2〇3, and 15 to 35% by mass. Si〇2, 3~12°/〇Al2〇3, and does not contain lead component in essence.
ZnO為使玻璃穩定化之成分。ZnO之含量較佳為 40〜60%，尤佳為47〜55%。若ZnO之含量少於40%，則玻璃 153709.doc 201134780 熔融時之失透性變強而難以熔融。另一方面，若Zn0之含 量多於6〇% ’則具有耐酸性減弱之傾向。 B2〇3為玻璃之網狀形成成分，且為提高流動性之成分。 之含量較佳為5〜25%，尤佳為7〜18%。若B2〇3之含量 >、於5 /〇，則結晶性變強而破壞流動性，從而難以進行對 半導體元件表面之被覆。另一方面，若b2〇3之含量多於 25%，則具有熱膨脹係數變大之傾向。又，具有化學耐久 性降低之傾向。ZnO is a component that stabilizes glass. The content of ZnO is preferably from 40 to 60%, particularly preferably from 47 to 55%. When the content of ZnO is less than 40%, the devitrification property of the glass 153709.doc 201134780 becomes strong and it is difficult to melt. On the other hand, if the content of Zn0 is more than 6% by weight, the acid resistance tends to be weakened. B2〇3 is a network forming component of glass and is a component for improving fluidity. The content is preferably from 5 to 25%, particularly preferably from 7 to 18%. When the content of B2〇3 > is 5/〇, the crystallinity becomes strong and the fluidity is deteriorated, so that it is difficult to coat the surface of the semiconductor element. On the other hand, when the content of b2〇3 is more than 25%, the coefficient of thermal expansion tends to increase. Further, it has a tendency to reduce chemical durability.
Si〇2為玻璃之網狀形成成分，且為提高耐酸性之成分。Si〇2 is a network forming component of glass and is a component for improving acid resistance.
Si02之含量較佳為15〜35%，尤佳為2〇〜33%。若Si02之含 量少於15°/。，則具有化學耐久性較差之傾向。另一方面， 若Si〇2之含量多於35%，則熔融時之失透性變強，從而難 以獲得均質之玻璃。The content of Si02 is preferably from 15 to 35%, particularly preferably from 2 to 33%. If the content of SiO 2 is less than 15 ° /. , it has a tendency to be less chemically durable. On the other hand, if the content of Si〇2 is more than 35%, the devitrification property at the time of melting becomes strong, and it is difficult to obtain a homogeneous glass.
AhO3為提高玻璃之表面電荷密度之成分。Al2〇3之含量 較佳為3〜12%，尤佳為5~1〇%。若a12〇3之含量少於3 %， 則難以取得上述效果。另一方面，若Ai2〇3之含量多於 12%，則易失透。 本發明之半導體被覆用玻璃中，作為組成，更佳為含有 0〜5% 之 Bi203、〇~5% 之 Μη02、〇〜5%iNb2〇5、〇〜3% 之 Ce〇2 0AhO3 is a component that increases the surface charge density of glass. The content of Al2〇3 is preferably from 3 to 12%, particularly preferably from 5 to 1%. If the content of a12〇3 is less than 3%, it is difficult to achieve the above effects. On the other hand, if the content of Ai2〇3 is more than 12%, it is easily devitrified. In the glass for semiconductor coating of the present invention, more preferably, it contains 0 to 5% of Bi203, 〇~5% of Μη02, 〇~5%iNb2〇5, and 〇~3% of Ce〇2 0 .
Bi2〇3為提局玻璃之表面電荷密度之成分。Bi2〇3之含量 較佳為0〜5%，尤佳為〇. 1〜3%。若則2〇3之含量多於5%，則 玻璃易失透。Bi2〇3 is a component of the surface charge density of the glass. The content of Bi2〇3 is preferably 0 to 5%, more preferably 〇. 1 to 3%. If the content of 2〇3 is more than 5%, the glass is easily devitrified.
MnCb、Nb2〇5、Ce〇2為使半導體元件之漏電流降低之成 153709.doc - 12· 201134780 分。 Μη02之含量較佳為0〜5°/。’尤佳為〇」〜3%。*Mn〇2之含 量多於5%，則具有玻璃之熔融性降低之傾向。MnCb, Nb2〇5, and Ce〇2 are used to reduce the leakage current of the semiconductor element to 153709.doc - 12·201134780. The content of Μη02 is preferably 0 to 5 ° /. ‘Youjia is 〇” ~3%. * When the content of Mn 〇 2 is more than 5%, the meltability of glass tends to decrease.
Nb205之含量較佳為〇~5%，尤佳為〇 1〜3%。若Nb2〇5之 含量多於5%，則具有玻璃之熔融性降低之傾向。The content of Nb205 is preferably 〇~5%, and particularly preferably 〇1 to 3%. When the content of Nb2〇5 is more than 5%, the meltability of the glass tends to decrease.
Ce〇2之含量較佳為〇〜3%，尤佳為〇· 1〜2%。若Ce〇2之含 量多於3%，則玻璃之結晶性過強而具有玻璃之流動性降 低之傾向。 本發明之半導體被覆用玻璃自環境方面之觀點而言係實 質不含有鉛成分（PbO等）。又，較佳為不含有對半導體元 件表面造成不良影響之鹼成分（Li2〇、Na20、κ20>。 本發明之半導體被覆用玻璃自可容易進行半導體元件表 面之被覆之觀點而言，較佳為粉末狀。此時，玻璃粉末之 平均粒徑Dsq較佳為25 μπι以下，尤佳為15 μπι以下。若玻 璃粉末之平均粒徑Dm大於25 μηι，則難以實現用以進行玻 璃塗佈之糊膠化。又，電泳塗佈亦變得困難。再者平均 粒徑Dm之下限雖無特別限定，但實際為〇.丨以上。 本發明之半導體被覆用材料係含有上述半導體被覆用玻 璃粉末者。再者，本發明之半導體被覆用材料亦可係相對 於上述半導體被覆用玻璃粉末而含有選自Ti02、Zr02、 ZnO、Zn〇-B2〇3、2Zn0_Si〇2中之至少！種無機粉末作為晶 核形成劑者。該等無機粉末之含量相對於半導體被覆用玻 璃粉末100質量份較佳為〇.〇1〜5質量份，尤佳為〇丨〜3質量 份。若無機粉末之含量少於0.01質量份，則析出之結晶量 153709.doc •13· 201134780 較少，從而具有難以達成所需之熱膨脹係數之傾向。若無 機粉末之含量多於5質量份’則析出之結晶量過多而破壞 流動性，從而具有難以進行半導體元件表面之被覆之傾 向。 再者，具有下述傾向：若上述無機粉末之粒度越小，則 自玻璃析出之結晶之粒徑越小且機械強度越大。因此，無 機粉末之平均粒徑Dm較佳為5 μπι以下，尤佳為3 μηι以 下。平均粒徑Dso之下限雖無特別限定，但實際為〇 1 μη1以 上。 本發明之半導體被覆用玻璃之熱膨脹係數（3〇〜3〇〇<>c )係 對應半導體元件之熱膨脹係數而於例如2〇〜6〇x 1〇-7/t：、進 而30〜5〇xl〇-VC之範圍内適當調整。 本發明之半導體被覆用材料之表面電荷密度較佳為，對 於電壓1〇〇〇 v之半導體裝置為7xl〇II/cm2以上對於電壓 〇〇 V以上之半導體裝置為1〇xl〇n/cm2以上。再者，表面 電何密度係、指藉由實施例中記載之方法而測定之值。 本發明之半導體被覆用玻璃係可藉由以下方法獲得：調 合各氧化物成分之原料粉末而作為—次投料量，以150(rc 左右之溫度進行約1小時熔融以使其玻璃化後，進行成形 (其後，視需要而進行粉碎、分級）。 實施例 但本發明並不限定於 以下，根據實施例而說明本發明 S亥荨實施例β (第一實施形態） I53709.doc 201134780 表1表示本發明第一實施形態之實施例及比較例。 [表1] 實施例 比較例 玻 璃 組 成 Zn〇 B2〇3 Si〇2 ai2o3 Bi2〇3 Mn02 Ce02 Nb205 PbO 1 2 3 4 5 6 1 2 59 23 12 5 1 59 20.5 11 7 2 0.5 58 21.5 12 8 0.5 61 21.5 10 5 2 0.5 60 21 10 7 1 0.5 0.5 58 21.5 12 7 1 0.5 59 23 10 0.5 2 0.5 5 63 23 11 1.5 0.5 1 晶核形成劑 ZnO 1質量份 _ 热膠脹係數 (X10*7/°C) 43.5 44 42.5 44.5 43.5 42 44 45 表面電荷密度 Cxl〇"/cm2) 1 8 18 14 —. 17 14 14 5 2 以如下方法製作各試樣。首先，以成為表中之玻璃組成 之方式調合原料粉末而作為一次投料量，以140(rc之溫度 進行1小時熔融以使其玻璃化。繼而，將該熔融玻璃成形 為膜狀之後，於球磨機中粉碎，使用350網眼之篩進行分 級’獲付半導體被覆用玻璃粉末(半導體被覆用材料K平均 粒徑 D5〇 : 12 μηι)。 對所獲得之半導體被覆用玻璃粉末測定熱膨脹係數與表 面電何密度。再者’於實施例6中’丨則定對半導體被覆用 玻璃粉末⑽質量份添W質量份Ζη〇粉末而成者。將其钟 果示於表1。 熱膨脹係數表不使用膨脹劑而於3〇〜3〇〇c>c之溫度範圍内 所測定之值。 表面電荷密度係以如下方法進㈣定。首先，將半導體 153709.doc •15- 201134780 被覆用玻璃粉末分散於有機溶媒中，藉由電泳而使其附著 於夕表面以成為固定之膜厚’繼而進行煅燒而形成玻璃 層於玻璃層上形成銘電極後，使用c-v儀（電容-電麼儀） 測定玻璃中電容之變化，計算表面電荷密度。 由表1顯然可知，實施例1〜6之試樣之表面電荷密度高達 8〜18。此係大致等同於pb〇 Si〇2_Ai2〇3系或pb〇 Si〇2-The content of Ce〇2 is preferably 〇~3%, and particularly preferably 〇·1~2%. When the content of Ce〇2 is more than 3%, the crystallinity of the glass is too strong, and the fluidity of the glass tends to decrease. The glass for semiconductor coating of the present invention does not substantially contain a lead component (PbO or the like) from the viewpoint of the environment. Further, it is preferable that the alkali component (Li2〇, Na20, κ20) which does not adversely affect the surface of the semiconductor element is contained. From the viewpoint of easily covering the surface of the semiconductor element, the semiconductor-coated glass of the present invention is preferably In this case, the average particle diameter Dsq of the glass powder is preferably 25 μm or less, and particularly preferably 15 μm or less. If the average particle diameter Dm of the glass powder is more than 25 μm, it is difficult to achieve a paste for glass coating. In addition, it is difficult to carry out electrophoretic coating. The lower limit of the average particle diameter Dm is not particularly limited, but is actually more than 丨.丨. The semiconductor coating material of the present invention contains the glass powder for semiconductor coating. Furthermore, the semiconductor coating material of the present invention may contain at least one kind of inorganic powder selected from the group consisting of TiO 2 , ZrO 2 , ZnO, Zn 〇-B 2 〇 3 and 2 Zn _ 〇 〇 2 with respect to the glass powder for semiconductor coating. The content of the inorganic powder is preferably 1 to 5 parts by mass, more preferably 〇丨 to 3 parts by mass, per 100 parts by mass of the glass powder for semiconductor coating. If the content of the inorganic powder is less than 0.01 parts by mass, the amount of crystals precipitated is 153709.doc •13·201134780, which is less likely to achieve a desired coefficient of thermal expansion. If the content of the inorganic powder is more than 5 parts by mass, then When the amount of precipitated crystals is too large to impair the fluidity, it tends to be difficult to coat the surface of the semiconductor element. Further, when the particle size of the inorganic powder is smaller, the particle size of crystals precipitated from the glass is smaller. The average particle diameter Dm of the inorganic powder is preferably 5 μm or less, and more preferably 3 μm or less. The lower limit of the average particle diameter Dso is not particularly limited, but is actually 〇1 μη1 or more. The coefficient of thermal expansion of the semiconductor-coated glass (3 〇 to 3 〇〇 <>c) corresponds to the thermal expansion coefficient of the semiconductor element, for example, 2 〇 to 6 〇 x 1 〇 -7 / t: and further 30 to 5 〇 The surface charge density of the semiconductor coating material of the present invention is preferably 7 x 1 〇 II / cm 2 or more for a voltage of 1 〇〇〇 v for a voltage of 1 〇〇〇 v for a semiconductor device. The semiconductor device having a thickness of 〇V or more is 1 〇xl 〇n/cm 2 or more. Further, the surface electrical density is a value measured by the method described in the examples. The glass for semiconductor coating of the present invention can be used by In the following method, the raw material powder of each oxide component is blended, and the amount of the raw material powder is adjusted to 150° (about rc for about 1 hour to be vitrified, and then formed, and then pulverized, if necessary, The present invention is not limited to the following, and the present invention is described in accordance with an embodiment of the present invention. (First Embodiment) I53709.doc 201134780 Table 1 shows an embodiment of the first embodiment of the present invention and Comparative example. [Table 1] Example Comparative Example Glass Composition Zn〇B2〇3 Si〇2 ai2o3 Bi2〇3 Mn02 Ce02 Nb205 PbO 1 2 3 4 5 6 1 2 59 23 12 5 1 59 20.5 11 7 2 0.5 58 21.5 12 8 0.5 61 21.5 10 5 2 0.5 60 21 10 7 1 0.5 0.5 58 21.5 12 7 1 0.5 59 23 10 0.5 2 0.5 5 63 23 11 1.5 0.5 1 Nucleating agent ZnO 1 part by mass _ Thermal expansion coefficient (X10*7/ °C) 43.5 44 42.5 44.5 43.5 42 44 45 Surface charge density Cxl〇"/cm2) 1 8 18 14 —. 17 14 14 5 2 Each sample was prepared as follows. First, the raw material powder is blended so as to have a glass composition in the table, and is melted at 140 (rc temperature for one hour to be vitrified as a primary charge amount. Then, the molten glass is formed into a film shape, and then in a ball mill. The pulverization was carried out by using a sieve of 350 mesh to obtain a glass powder for semiconductor coating (average particle diameter D5 of semiconductor coating material: 12 μηι). The thermal expansion coefficient and surface electric power of the obtained glass powder for semiconductor coating were measured. In addition, in the case of the sixth embodiment, the powder for the semiconductor coating glass powder (10) parts by weight is added with W mass parts of Ζη〇 powder. The clock results are shown in Table 1. The thermal expansion coefficient table does not use the expansion agent. The value measured in the temperature range of 3〇~3〇〇c>c. The surface charge density is determined by the following method. (IV) First, the semiconductor 153709.doc •15-201134780 coated glass powder is dispersed in the organic solvent. In the middle, the film is adhered to the outer surface by electrophoresis to be a fixed film thickness, and then calcined to form a glass layer to form an electrode on the glass layer, and then cv is used. (Capacitor-Electric Instrument) The change in capacitance in the glass was measured to calculate the surface charge density. It is apparent from Table 1 that the surface charge density of the samples of Examples 1 to 6 was as high as 8 to 18. This is roughly equivalent to pb〇Si. 〇2_Ai2〇3 series or pb〇Si〇2-
Al2〇rB2〇3系之鉛系玻璃之表面電荷密度。因此，實施例 1〜6之半導體被覆用材料係適合高耐壓用之半導體元件之 被覆者。 另一方面可知，比較例丨及2之試樣之表面電荷密度較 低’故不適合高耐壓用之半導體元件之被覆。 (第二實施形態） 表2表示本發明之第二實施形態之實施例及比較例。 [表2] 實施例 比j 统例 1 2 3 4 5 6 1 2 玻 璃 組 質 量 % ZnO B2O3 Si02 AI2O3 47 25 20 7 55 12 25 7 55 17 20 7 55 5 31.5 8 51 17 25 6 52 21.5 18 7 60 24 10.5 3 62 22.5 11 1.5 Bl2〇3 Mn〇2 Ce〇2 Nb205 0.5 0.5 1 0.5 0.5 0.5 0.5 0.5 1 0.5 2 0.5 1 1 1 晶核形成劑 浓0内為添加量(質量 份） ZnO (1) 熱膨脹係數(Xl0_7/°C) 41 40 43 38 39 42 44 45 表面電荷密度 (x10n/cm2) 16 15 17 18 14 17 6 2 耐酸性試驗引起之質 量減少(mg/cm2) 0.5 0.4 0.5 0.2 0.4 0.6 3.5 4.1 153709.doc -16 * 201134780 、各試樣係以如下方式製作。首先，以成為表中之玻璃組 、 式調13原料粉末而作為一次投料量，以1500。(：之溫 ，進行1小時熔融而使其玻璃化。繼而，將該熔融玻璃成 》二臈狀之後，於球磨機中粉碎，使用3 5 〇網眼之篩進行 刀’及獲知半導體被覆用玻璃粉末（平均粒徑d5〇 : 12 μιη)。 對所獲得之半導體被覆用玻璃粉末測定熱膨脹係數、表 面電荷密度、及耐酸性。將其結果示於表2。 ‘„、私脹係數表示使用膨膜劑而於〜之溫度範圍内 所測定之值。 表面電荷密度係以如下方法測定。首先，將玻璃粉末分 散於有機溶媒中，藉由電泳而使其附著於矽基板表面以成 為固定之膜厚，繼而進行煅燒而形成玻璃層。於玻璃層上 形成紹電極後，使用C-V儀測定玻璃中電容之變化，計算 表面電荷密度。 耐酸性係以如下方式進行評價。首先，將玻璃粉末壓製 成型為直徑20 mm、厚度4 mm左右之大小，並烺燒而製作 顆粒狀試樣，將該試樣於30%硝酸中以25。(：浸潰1分鐘 後’根據質量減少而計算每單位面積之質量變化，評價耐 酸性。 由表1顯然可知，實施例1〜6之試樣之表面電荷密度高達 14〜18。此係等同於或大於卩1)0-8丨〇2-八1203系或？13〇-$丨〇2_ ai2〇3-b2o3系等之鉛系玻璃之表面電荷密度。又可知，而才 酸性試驗引起之質量減少為0.6 mg/cm2以下，故耐酸性優 153709.doc •17· 201134780 異。因此’實施例1〜6之半導體被覆用材料係適合高耐壓 用之半導體元件之被覆者。 另一方面可知，比較例1及2之試樣之表面電荷密度低至 6以下’故不適合高耐壓用之半導體元件之被覆。又，耐 酸性試驗引起之質量減少為3.5 mg/cm2以上，故耐酸性亦 較差。 以上參照特定之態樣詳細說明了本發明，但本領域技術 人員明確瞭解，不脫離本發明之精神及範圍而可進行各種 變更及修正。 再者’本申請案係基於2〇 1 〇年1月28曰申請之曰本專利 申請（特願2010-016552)及2010年9月1曰申請之日本專利申 请（特願2010-19561 1)，其全部内容因引用而被援用。又， 此處引用之全部參照整體併入本文中。 153709.docThe surface charge density of the lead glass of the Al2〇rB2〇3 system. Therefore, the materials for semiconductor coating of Examples 1 to 6 are suitable for those of semiconductor elements for high withstand voltage. On the other hand, it is understood that the samples of Comparative Examples 2 and 2 have a low surface charge density, and thus are not suitable for coating of a semiconductor element for high withstand voltage. (Second embodiment) Table 2 shows an example and a comparative example of the second embodiment of the present invention. [Table 2] Example ratio j Example 1 2 3 4 5 6 1 2 Glass group mass % ZnO B2O3 Si02 AI2O3 47 25 20 7 55 12 25 7 55 17 20 7 55 5 31.5 8 51 17 25 6 52 21.5 18 7 60 24 10.5 3 62 22.5 11 1.5 Bl2〇3 Mn〇2 Ce〇2 Nb205 0.5 0.5 1 0.5 0.5 0.5 0.5 0.5 1 0.5 2 0.5 1 1 1 Nucleation agent is added in the concentration of 0 (parts by mass) ZnO (1 ) Thermal expansion coefficient (Xl0_7/°C) 41 40 43 38 39 42 44 45 Surface charge density (x10n/cm2) 16 15 17 18 14 17 6 2 Mass loss due to acid resistance test (mg/cm2) 0.5 0.4 0.5 0.2 0.4 0.6 3.5 4.1 153709.doc -16 * 201134780 Each sample was produced as follows. First, the raw material powder of the glass group and the formula 13 in the table was used as a single charge amount, and it was 1,500. (When it is heated, it is melted for 1 hour to be vitrified. Then, the molten glass is formed into a shape of a crucible, and then pulverized in a ball mill, and a knife is used for a blade of 3' mesh, and a glass for semiconductor coating is known. Powder (average particle diameter d5 〇: 12 μηη) 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. '„, the coefficient of private expansion indicates expansion. The value measured by the film in the temperature range of ~. The surface charge density is measured by the following method. First, the glass powder is dispersed in an organic solvent, and is attached to the surface of the ruthenium substrate by electrophoresis to form a fixed film. Thickness, followed by calcination to form a glass layer. After the electrode was formed on the glass layer, the change in capacitance in the glass was measured by a CV meter to calculate the surface charge density. The acid resistance was evaluated as follows. First, the glass powder was compression molded. A sample having a diameter of 20 mm and a thickness of about 4 mm and simmering was used to prepare a granular sample, which was 25 in 30% nitric acid (: 1 minute of dipping) 'The change in mass per unit area was calculated based on the mass reduction, and the acid resistance was evaluated. It is apparent from Table 1 that the surface charge density of the samples of Examples 1 to 6 was as high as 14 to 18. This is equivalent to or greater than 卩1)0. The surface charge density of lead-based glass such as -8丨〇2-八1203 or ?13〇-$丨〇2_ ai2〇3-b2o3, etc. It is also known that the mass reduction caused by acidity test is 0.6 mg/cm2. In the following, the materials for semiconductor coating of Examples 1 to 6 are suitable for the coating of semiconductor elements for high withstand voltage. On the other hand, Comparative Examples 1 and 2 are known. Since the surface charge density of the sample is as low as 6 or less, it is not suitable for the coating of the semiconductor element for high withstand voltage. Moreover, the quality reduction by the acid resistance test is 3.5 mg/cm2 or more, so the acid resistance is also poor. The present invention has been described in detail, but it is understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. Further, the application is based on the application of January 28, 2002. Patent application Japanese Patent Application (Japanese Patent Application No. 2010-19561 1) filed on Sep. 1, 2010, the entire contents of which is hereby incorporated by reference. Medium. 153709.doc
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| JPH03126639A (en) * | 1989-10-06 | 1991-05-29 | Nippon Electric Glass Co Ltd | Glass composition for coating |
| JP3534257B2 (en) * | 1993-12-28 | 2004-06-07 | 日本電気硝子株式会社 | Sealing material |
| JP2001139345A (en) * | 1999-11-10 | 2001-05-22 | Asahi Glass Co Ltd | Leadless low melting point glass and glass frit |
| JP3619996B2 (en) * | 2001-03-14 | 2005-02-16 | 三菱マテリアル神戸ツールズ株式会社 | Surface coated cemented carbide end mill with excellent chipping resistance in high speed heavy cutting |
| JP5029014B2 (en) * | 2004-09-29 | 2012-09-19 | 日本電気硝子株式会社 | Semiconductor sealing glass, semiconductor sealing outer tube, and semiconductor electronic component |
| DE102005031658B4 (en) * | 2005-07-05 | 2011-12-08 | Schott Ag | Lead-free glass for electronic components |
| DE102006062428B4 (en) * | 2006-12-27 | 2012-10-18 | Schott Ag | A method of manufacturing a lead-free glass passivated electronic component and an electronic component with lead-free glass applied and the use thereof |
-
2011
- 2011-01-19 CN CN201180007607.7A patent/CN102741185B/en active Active
- 2011-01-19 CN CN201510366918.2A patent/CN105152532A/en active Pending
- 2011-01-19 WO PCT/JP2011/050808 patent/WO2011093177A1/en active Application Filing
- 2011-01-21 TW TW100102341A patent/TWI501933B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TWI501933B (en) | 2015-10-01 |
| CN102741185B (en) | 2015-11-25 |
| WO2011093177A1 (en) | 2011-08-04 |
| CN105152532A (en) | 2015-12-16 |
| CN102741185A (en) | 2012-10-17 |
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