TWI615370B - Semiconductor component coated glass - Google Patents

Semiconductor component coated glass Download PDF

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TWI615370B
TWI615370B TW101130709A TW101130709A TWI615370B TW I615370 B TWI615370 B TW I615370B TW 101130709 A TW101130709 A TW 101130709A TW 101130709 A TW101130709 A TW 101130709A TW I615370 B TWI615370 B TW I615370B
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glass
semiconductor element
coating
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zno
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TW101130709A
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TW201309612A (en
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西川欣克
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日本電氣硝子股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

本發明提供一種對環境之負荷較小,化學耐久性優異,且表面電荷密度較低,尤其是較佳用於被覆低耐壓用之半導體元件的玻璃。其特徵在於:作為玻璃組成,以質量%計含有:52~65%之ZnO、5~20%之B2O3、15~35%之SiO2及3~6%之Al2O3,且實質上不含鉛成分。較佳為進而含有0~5%之Ta2O5、0~5%之MnO2、0~5%之Nb2O5、0~3%之CeO2及Sb2O3作為組成。 The present invention provides a glass that has a small load on the environment, excellent chemical durability, and low surface charge density, and is particularly suitable for coating semiconductor elements with low withstand voltage. It is characterized in that as a glass composition, it contains 52 to 65% of ZnO, 5 to 20% of B 2 O 3 , 15 to 35% of SiO 2 and 3 to 6% of Al 2 O 3 in terms of mass, and It is substantially free of lead. Preferably, it further contains 0 to 5% of Ta 2 O 5 , 0 to 5% of MnO 2 , 0 to 5% of Nb 2 O 5 , 0 to 3% of CeO 2 and Sb 2 O 3 as a composition.

Description

半導體元件被覆用玻璃 Glass for semiconductor device coating

本發明係關於一種用作包含P-N接合之半導體元件之被覆用的玻璃。 The present invention relates to a glass for coating a semiconductor element including a P-N junction.

通常,矽二極體或電晶體等半導體元件就防止由外部空氣所致之污染之觀點而言,藉由玻璃被覆半導體元件之包含P-N接合部之表面。藉此,可謀求半導體元件表面之穩定化,抑制經時之特性劣化。 In general, a semiconductor device such as a silicon diode or a transistor is covered with a surface including a P-N junction portion of the semiconductor device by glass from the viewpoint of preventing contamination due to external air. This makes it possible to stabilize the surface of the semiconductor element and suppress deterioration of characteristics over time.

作為半導體元件被覆用玻璃所要求之特性,可列舉:(1)熱膨脹係數適合於半導體元件之熱膨脹係數,以避免因與半導體元件之熱膨脹係數差而產生龜裂等;(2)可於低溫(例如900℃以下)下被覆,以防止半導體元件之特性劣化;(3)不包含對半導體元件表面產生不良影響之鹼成分等雜質等。 As the characteristics required for the semiconductor element coating glass, (1) the thermal expansion coefficient is suitable for the thermal expansion coefficient of the semiconductor element to avoid cracks due to the difference in thermal expansion coefficient with the semiconductor element, etc .; (2) it can be used at low temperature ( (For example, below 900 ° C) to prevent the characteristics of the semiconductor device from deteriorating; (3) do not include impurities such as alkali components that adversely affect the surface of the semiconductor device.

先前,作為半導體元件被覆用玻璃,已知有ZnO-B2O3-SiO2系等之鋅系玻璃,或PbO-SiO2-Al2O3系或者PbO-SiO2-Al2O3-B2O3系等之鉛系玻璃,但就操作性之觀點而言,PbO-SiO2-Al2O3系及PbO-SiO2-Al2O3-B2O3系等之鉛系玻璃正成為主流(例如參照專利文獻1~4)。 Conventionally, as a glass for coating a semiconductor element, zinc-based glass such as ZnO-B 2 O 3 -SiO 2 system, PbO-SiO 2 -Al 2 O 3 system, or PbO-SiO 2 -Al 2 O 3- Lead-based glass such as B 2 O 3 system, but from the viewpoint of operability, lead-based system such as PbO-SiO 2 -Al 2 O 3 system and PbO-SiO 2 -Al 2 O 3 -B 2 O 3 system Glass is becoming mainstream (see, for example, Patent Documents 1 to 4).

先前技術文獻Prior art literature 專利文獻Patent literature

專利文獻1:日本專利特公平1-49653號公報 Patent Document 1: Japanese Patent Publication No. 1-49653

專利文獻2:日本專利特開昭50-129181號公報 Patent Document 2: Japanese Patent Laid-Open No. 50-129181

專利文獻3:日本專利特開昭48-43275號公報 Patent Document 3: Japanese Patent Laid-Open No. 48-43275

專利文獻4:日本專利特開2008-162881號公報 Patent Document 4: Japanese Patent Laid-Open No. 2008-162881

由於PbO等鉛成分係對環境有害之成分,故而近年來正逐漸禁止於電氣及電子機器中之使用,並推進各種材料之無鉛化。上述ZnO-B2O3-SiO2系等之鋅系玻璃亦有含有少量之鉛成分而就環境方面而言無法使用者。又,鋅系玻璃與鉛系玻璃相比化學耐久性較差,且對玻璃煅燒後之後續步驟中之酸之耐性相對較弱。因此,必需於被覆玻璃表面進而形成保護膜而進行後續步驟。 Since lead components such as PbO are harmful to the environment, in recent years, they have been gradually banned from being used in electrical and electronic equipment, and lead-free materials have been promoted. The above-mentioned zinc-based glass such as ZnO-B 2 O 3 -SiO 2 series also contains a small amount of a lead component, and is not environmentally friendly to users. In addition, zinc-based glass is inferior in chemical durability compared to lead-based glass, and has relatively weak resistance to acids in subsequent steps after the glass is fired. Therefore, it is necessary to cover the surface of the glass and form a protective film to perform the subsequent steps.

再者,若為了提昇化學耐久性而使玻璃組成富SiO2,則半導體元件被覆玻璃層之表面電荷密度增大,半導體元件之逆向耐壓提高,但另一方面,會產生半導體元件之逆向洩漏電流增大之不良狀況。因此,關於用於不那麼需要逆向耐壓之低耐壓用之半導體元件的半導體元件被覆玻璃,為了抑制逆向洩漏電流,必需降低表面電荷密度。 Furthermore, if the glass composition is enriched with SiO 2 in order to improve chemical durability, the surface charge density of the semiconductor element-coated glass layer increases, and the reverse breakdown voltage of the semiconductor element increases. On the other hand, reverse leakage of the semiconductor element occurs Bad current increase. Therefore, regarding a semiconductor element-coated glass used for a semiconductor element for a low withstand voltage that does not require a reverse withstand voltage, in order to suppress the reverse leakage current, it is necessary to reduce the surface charge density.

因此,本發明之目的在於提供一種對環境之負荷較小,化學耐久性優異,且表面電荷密度較低,尤其是較佳用於被覆低耐壓用之半導體元件的玻璃。 Therefore, an object of the present invention is to provide a glass having a small load on the environment, excellent chemical durability, and low surface charge density, and is particularly suitable for coating a semiconductor element for low withstand voltage.

本發明者進行銳意研究,結果發現可藉由具有特定組成之ZnO-B2O3-SiO2系玻璃而解決上述課題,並作為本發明而提出。 As a result of earnest research, the inventors have found that the above-mentioned problems can be solved by a ZnO-B 2 O 3 -SiO 2 -based glass having a specific composition, and have been proposed as the present invention.

即,本發明係關於一種半導體元件被覆用玻璃,其特徵在於:作為玻璃組成,以質量%計含有:52~65%之ZnO、5~20%之B2O3、15~35%之SiO2及3~6%之Al2O3,且實質上不含鉛成分。 That is, the present invention relates to a glass for coating a semiconductor element, which is characterized in that as a glass composition, it contains 52 to 65% of ZnO, 5 to 20% of B 2 O 3 , and 15 to 35% of SiO. 2 and 3 to 6% of Al 2 O 3 and substantially no lead component.

本發明之半導體元件被覆用玻璃係藉由對ZnO-B2O3-SiO2系玻璃嚴格限制各成分之含量而抑制表面電荷密度而尤其是適於低耐壓用半導體元件之被覆者,且具有化學耐久性較高之特徵。又,由於實質上不含鉛成分,故而對環境之負荷較小。 The glass for coating a semiconductor element of the present invention is a ZnO-B 2 O 3 -SiO 2 -based glass with a strict limitation on the content of each component, thereby suppressing the surface charge density, and is particularly suitable for coating a semiconductor element for low withstand voltage. It has the characteristics of high chemical durability. In addition, since it does not substantially contain a lead component, the load on the environment is small.

再者,於本發明中,所謂「實質上不含」,意指未有意添加相關成分作為玻璃成分,並不意指連不可避免地混入之雜質亦完全排除。客觀而言,意指包括雜質之相關成分之含量未達0.1質量%。 Furthermore, in the present invention, the term "substantially free" means that the relevant component is not intentionally added as a glass component, and does not mean that even impurities that are inevitably mixed in are completely excluded. Objectively speaking, it means that the content of related components including impurities is less than 0.1% by mass.

第二,本發明之半導體元件被覆用玻璃較佳為進而含有0~5%之Ta2O5、0~5%之MnO2、0~5%之Nb2O5、0~3%之CeO2及0~3%之Sb2O3作為組成。 Secondly, the glass for coating a semiconductor element of the present invention preferably further contains 0 to 5% of Ta 2 O 5 , 0 to 5% of MnO 2 , 0 to 5% of Nb 2 O 5 , and 0 to 3% of CeO. 2 and 0 ~ 3% of Sb 2 O 3 as a composition.

第三,本發明係關於一種半導體元件被覆用材料,其特徵在於含有包含上述半導體元件被覆用玻璃之玻璃粉末。 Third, the present invention relates to a material for coating a semiconductor element, which is characterized by containing a glass powder including the glass for coating a semiconductor element.

藉由使用該半導體元件被覆用材料,可容易地進行半導體元件表面之被覆。 By using this semiconductor element coating material, the surface of the semiconductor element can be easily covered.

第四,本發明之半導體元件被覆用材料較佳為相對於玻璃粉末100質量份,含有選自TiO2、ZrO2、ZnO、ZnO‧B2O3及2ZnO‧SiO2中之至少一種無機粉末0.01~5質量份而成。 Fourth, the semiconductor element coating material of the present invention preferably contains at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO‧B 2 O 3 and 2ZnO‧SiO 2 with respect to 100 parts by mass of the glass powder. 0.01 to 5 parts by mass.

尤其是於包含Si等之半導體元件與玻璃之接觸面積較大之情形時,理想的是玻璃與Si之熱膨脹係數相近。藉此,可抑制由半導體元件與玻璃之熱膨脹係數差所導致之被覆玻璃表面之龜裂之產生。玻璃之熱膨脹係數可藉由玻璃中所包含之晶體成分而加以調整,但難以適當控制自玻璃中析出之晶體之量。因此,若對半導體元件被覆用玻璃適當添加上述無機粉末,則該等無機粉末發揮成核劑之作用,故而可相對容易地控制析出之晶體量。結果,可容易地調整為所需之熱膨脹係數。 Especially when the contact area between a semiconductor element including Si and glass is large, it is desirable that the thermal expansion coefficients of glass and Si are similar. This can suppress the occurrence of cracks on the surface of the coated glass caused by the difference in thermal expansion coefficient between the semiconductor element and the glass. The thermal expansion coefficient of glass can be adjusted by the crystal components contained in the glass, but it is difficult to properly control the amount of crystals precipitated from the glass. Therefore, if the above-mentioned inorganic powder is appropriately added to the glass for coating a semiconductor element, these inorganic powders function as a nucleating agent, and therefore it is possible to control the amount of crystals precipitated relatively easily. As a result, the desired thermal expansion coefficient can be easily adjusted.

本發明之半導體元件被覆用玻璃由於表面電荷密度較低,故而尤其是適於低耐壓用之半導體元件之被覆,且由於化學耐久性較高,故而可降低經時劣化。又,由於實質上不含鉛成分,故而對於環境之負荷較小。 The glass for coating a semiconductor element of the present invention has a low surface charge density, and is therefore particularly suitable for coating a semiconductor element for low withstand voltage. Further, since the chemical durability is high, deterioration over time can be reduced. In addition, since it does not substantially contain a lead component, the load on the environment is small.

以下,說明於本發明之半導體元件被覆用玻璃中如上述般規定各成分之理由。再者,於以下各成分之含量之說明中,「%」只要未特別說明則意指「質量%」。 Hereinafter, the reason why each component is prescribed | regulated as mentioned above in the glass for coating a semiconductor element of this invention is demonstrated. In addition, in the following description of the content of each component, "%" means "mass%" unless otherwise specified.

ZnO係使玻璃穩定化之成分。ZnO之含量較佳為52~65%,尤佳為55~60%。若ZnO之含量過少,則熔融時之失透性變強,不易獲得均質之玻璃。另一方面,若ZnO之含量過多,則存在耐酸性變弱之傾向。 ZnO is a component that stabilizes glass. The content of ZnO is preferably 52 to 65%, particularly preferably 55 to 60%. If the content of ZnO is too small, the devitrification property at the time of melting becomes strong, and it is difficult to obtain a homogeneous glass. On the other hand, if the content of ZnO is too large, the acid resistance tends to weaken.

B2O3係玻璃之網絡形成成分,且為提高流動性之成分。B2O3之含量較佳為5~20%,尤佳為7~15%。若B2O3之含量 過少,則存在結晶性增強而於被覆時損害流動性,難以均勻地被覆於半導體元件表面之傾向。另一方面,若B2O3之含量過多,則存在熱膨脹係數增大,或化學耐久性降低之傾向。 B 2 O 3 is a component that forms a network of glass and is a component that improves fluidity. The content of B 2 O 3 is preferably 5 to 20%, particularly preferably 7 to 15%. When the content of B 2 O 3 is too small, the crystallinity tends to increase, and the fluidity is impaired during coating, and it is difficult to uniformly coat the surface of the semiconductor element. On the other hand, when the content of B 2 O 3 is too large, the thermal expansion coefficient tends to increase or the chemical durability tends to decrease.

SiO2係玻璃之網絡形成成分,且為提高耐酸性之成分。SiO2之含量較佳為15~35%,尤佳為20~33%。若SiO2之含量過少,則存在化學耐久性較差之傾向。另一方面,若SiO2之含量過多,則熔融時之失透性變強,不易獲得均質之玻璃。 The SiO 2 based glass is a component for forming a network and is a component for improving acid resistance. The content of SiO 2 is preferably 15 to 35%, particularly preferably 20 to 33%. When the content of SiO 2 is too small, the chemical durability tends to be poor. On the other hand, if the content of SiO 2 is too large, the devitrification property at the time of melting becomes strong, making it difficult to obtain a homogeneous glass.

Al2O3係使玻璃穩定化並調整表面電荷密度之成分。Al2O3之含量較佳為3~6%,尤佳為4~5.5%。若Al2O3之含量過少,則容易失透。另一方面,若Al2O3之含量過多,則存在表面電荷密度過於增大之傾向。 Al 2 O 3 is a component that stabilizes glass and adjusts the surface charge density. The content of Al 2 O 3 is preferably 3 to 6%, particularly preferably 4 to 5.5%. If the content of Al 2 O 3 is too small, devitrification tends to occur. On the other hand, if the content of Al 2 O 3 is too large, the surface charge density tends to increase too much.

本發明之半導體元件被覆用玻璃可進而含有Ta2O5、MnO2、Nb2O5、CeO2或Sb2O3作為降低玻璃表面電荷密度而抑制洩漏電流之產生之成分。 The glass for coating a semiconductor element of the present invention may further contain Ta 2 O 5 , MnO 2 , Nb 2 O 5 , CeO 2 or Sb 2 O 3 as a component that reduces the surface charge density of the glass and suppresses the generation of a leakage current.

Ta2O5係上述效果尤其較大之成分。Ta2O5之含量較佳為0~5%,尤佳為0.1~3%。若Ta2O5之含量過多,則存在熔融性降低之傾向。 Ta 2 O 5 is a component having a particularly large effect as described above. The content of Ta 2 O 5 is preferably 0 to 5%, particularly preferably 0.1 to 3%. If the content of Ta 2 O 5 is too large, the meltability tends to decrease.

MnO2之含量較佳為0~5%,尤佳為0.1~3%。若MnO2之含量過多,則存在熔融性降低之傾向。 The content of MnO 2 is preferably 0 to 5%, particularly preferably 0.1 to 3%. If the content of MnO 2 is too large, the meltability tends to decrease.

Nb2O5之含量較佳為0~5%,尤佳為0.1~3%。若Nb2O5之含量過多,則存在熔融性降低之傾向。 The content of Nb 2 O 5 is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of Nb 2 O 5 is too large, the meltability tends to decrease.

CeO2之含量較佳為0~3%,尤佳為0.1~2%。若CeO2之含 量過多,則存在結晶性過於增強而於被覆時降低流動性之傾向。 The content of CeO 2 is preferably 0 to 3%, particularly preferably 0.1 to 2%. If the content of CeO 2 is too large, the crystallinity tends to be too strong and the fluidity tends to decrease during coating.

Sb2O3之含量較佳為0~3%,尤佳為0.1~2%。若Sb2O3之含量過多,則存在熔融性降低之傾向。 The content of Sb 2 O 3 is preferably 0 to 3%, particularly preferably 0.1 to 2%. When the content of Sb 2 O 3 is too large, the meltability tends to decrease.

就環境方面之觀點而言,本發明之半導體元件被覆用玻璃實質上不含鉛成分(PbO等)。又,較佳為實質上亦不含對半導體元件表面產生不良影響之鹼成分(Li2O、Na2O及K2O)。 From the environmental point of view, the glass for coating a semiconductor element of the present invention does not substantially contain a lead component (PbO, etc.). In addition, it is preferable that it does not substantially contain an alkali component (Li 2 O, Na 2 O, and K 2 O) that adversely affects the surface of the semiconductor element.

本發明之半導體元件被覆用玻璃較佳為粉末狀。藉此,例如可使用漿料法或電泳塗佈法等而容易地進行半導體元件表面之被覆。於該情形時,玻璃粉末之平均粒徑D50較佳為25 μm以下,尤佳為15 μm以下。若玻璃粉末之平均粒徑D50過大,則存在難以漿料化之傾向。又,電泳塗佈亦變難。再者,玻璃粉末之平均粒徑D50之下限並無特別限定,但現實而言為0.1 μm以上。 The glass for coating a semiconductor element of the present invention is preferably powdery. This makes it possible to easily coat the surface of the semiconductor element using, for example, a slurry method or an electrophoretic coating method. In this case, the average particle diameter D 50 of the glass powder is preferably 25 μm or less, and particularly preferably 15 μm or less. When the average particle diameter D 50 of the glass powder is too large, it tends to be difficult to make a slurry. Moreover, electrophoretic coating becomes difficult. The lower limit of the average particle diameter D 50 of the glass powder is not particularly limited, but is practically 0.1 μm or more.

本發明之半導體元件被覆用材料係含有包含上述半導體元件被覆用玻璃之玻璃粉末(以下亦稱為「半導體元件被覆用玻璃粉末」)而成者。本發明之半導體元件被覆用材料亦可為對半導體元件被覆用玻璃粉末含有選自TiO2、ZrO2、ZnO、ZnO‧B2O3及2ZnO‧SiO2中之至少一種無機粉末作為成核劑而成者。藉由添加該等無機粉末,可相對容易地控制析出晶體量。結果,可容易地調整為所需之熱膨脹係數。 The semiconductor element coating material of the present invention is a material containing a glass powder (hereinafter also referred to as a "semiconductor element coating glass powder") containing the above-mentioned glass for coating a semiconductor element. The semiconductor element coating material of the present invention may be such that the glass powder for semiconductor element coating contains at least one inorganic powder selected from the group consisting of TiO 2 , ZrO 2 , ZnO, ZnO‧B 2 O 3 and 2ZnO‧SiO 2 as a nucleating agent. Become. By adding these inorganic powders, the amount of precipitated crystals can be controlled relatively easily. As a result, the desired thermal expansion coefficient can be easily adjusted.

該等無機粉末之含量相對於半導體元件被覆用玻璃粉末 100質量份,較佳為0.01~5質量份,尤佳為0.1~3質量份。若無機粉末之含量過少,則存在析出晶體量較少,難以達成所需之熱膨脹係數之傾向。若無機粉末之含量過多,則存在析出晶體量過於增多而於被覆時損害流動性,半導體元件表面之被覆變困難之傾向。 Content of these inorganic powders with respect to glass powder for semiconductor element coating 100 parts by mass, preferably 0.01 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass. When the content of the inorganic powder is too small, the amount of precipitated crystals tends to be small, and it is difficult to achieve a desired thermal expansion coefficient. When the content of the inorganic powder is too large, the amount of precipitated crystals is excessively increased, and fluidity is impaired during coating, and the coating of the surface of the semiconductor element tends to be difficult.

再者,存在上述無機粉末之粒徑越小,則析出晶體之粒徑越小,機械性強度越大之傾向。因此,無機粉末之平均粒徑D50較佳為5 μm以下,尤佳為3 μm以下。無機粉末之平均粒徑D50之下限並無特別限定,但現實而言為0.1 μm以上。 Furthermore, the smaller the particle size of the inorganic powder, the smaller the particle size of the precipitated crystals and the higher the mechanical strength. Therefore, the average particle diameter D 50 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 D 50 of the inorganic powder is not particularly limited, but is practically 0.1 μm or more.

本發明之半導體元件被覆用玻璃之熱膨脹係數(30~300℃)係根據半導體元件之熱膨脹係數,於例如20~60×10-7/℃,進而於30~50×10-7/℃之範圍內適當調整。 The thermal expansion coefficient (30 to 300 ° C) of the glass for coating a semiconductor element of the present invention is in the range of, for example, 20 to 60 × 10 -7 / ° C, and further to 30 to 50 × 10 -7 / ° C, based on the thermal expansion coefficient of the semiconductor element. Adjust appropriately.

例如於對1000 V以下之半導體元件使用之情形時,半導體元件被覆用材料之表面電荷密度較佳為6×1011/cm2以下,尤佳為5×1011/cm2以下。再者,表面電荷密度係指藉由下述實施例所記載之方法而測定之值。 For example, when the semiconductor element is used at a voltage of 1000 V or less, the surface charge density of the semiconductor element coating material is preferably 6 × 10 11 / cm 2 or less, and particularly preferably 5 × 10 11 / cm 2 or less. The surface charge density is a value measured by a method described in the following examples.

本發明之半導體元件被覆用玻璃例如可藉由調合各氧化物成分之原料粉末並分批,於1500℃左右下熔融約1小時並玻璃化後加以成形(其後視需要粉碎、分級)而獲得。 The glass for coating a semiconductor element of the present invention can be obtained, for example, by mixing raw material powders of each oxide component and batch-melting it at about 1500 ° C. for about 1 hour and forming it after vitrification (they are crushed and classified as necessary) .

實施例Examples

以下,基於實施例說明本發明,但本發明並不限定於該等實施例。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

表1表示本發明之實施例1~6及比較例1~3。 Table 1 shows Examples 1 to 6 and Comparative Examples 1 to 3 of the present invention.

Figure TWI615370BD00001
Figure TWI615370BD00001

各試樣係以如下方式製作。首先,以成為表中之玻璃組成之方式調合原料粉末並分批,於1500℃下熔融1小時而玻璃化。繼而,將熔融玻璃成形為膜狀,之後利用球磨機粉碎,並使用350目之篩進行分級,獲得平均粒徑D50為12 μm之玻璃粉末(半導體元件被覆用材料)。再者,關於實施例4,係對所獲得之玻璃粉末添加ZnO粉末而製成半導體元件被覆用材料。 Each sample was produced as follows. First, the raw material powder was prepared so as to have a glass composition in the table, and was batchwise melted at 1500 ° C. for 1 hour to vitrify. Next, the molten glass was formed into a film shape, and then pulverized with a ball mill and classified using a 350-mesh sieve to obtain a glass powder (material for semiconductor element coating) having an average particle diameter D 50 of 12 μm. In addition, regarding Example 4, a ZnO powder was added to the obtained glass powder to prepare a material for coating a semiconductor element.

藉由以下方法測定或評價半導體元件被覆用材料之熱膨脹係數、表面電荷密度及耐酸性。將結果示於表1。 The thermal expansion coefficient, surface charge density, and acid resistance of the semiconductor element coating material were measured or evaluated by the following methods. The results are shown in Table 1.

熱膨脹係數係表示使用膨脹計於30~300℃之溫度範圍內測定之值。 The coefficient of thermal expansion is a value measured using a dilatometer in a temperature range of 30 to 300 ° C.

表面電荷密度係以如下方式測定。首先,將半導體元件被覆用材料分散於有機溶劑中,藉由電泳而以成為一定膜 厚之方式附著於矽基板表面,並進行煅燒而形成燒結層。於燒結層之表面形成鋁電極後,使用C-V計測定燒結層中之電容之變化,算出表面電荷密度。 The surface charge density was measured as follows. First, the semiconductor element coating material is dispersed in an organic solvent, and becomes a fixed film by electrophoresis. It is attached to the surface of the silicon substrate in a thick manner, and is fired to form a sintered layer. After forming an aluminum electrode on the surface of the sintered layer, the change in capacitance in the sintered layer was measured using a C-V meter to calculate the surface charge density.

耐酸性係以如下方式評價。首先,將半導體元件被覆用材料加壓成型為直徑20 mm、厚度4 mm左右之大小,並煅燒而製作顆粒狀試樣,根據將該試樣於25℃下浸漬於30%硝酸中1分鐘後之質量減少而算出每單位面積之質量變化,並作為耐酸性之指標。再者,該質量變化量越小,則耐酸性越優異。 The acid resistance was evaluated as follows. First, the semiconductor element coating material was pressure-molded to a size of 20 mm in diameter and about 4 mm in thickness, and then calcined to prepare a granular sample. The sample was immersed in 30% nitric acid at 25 ° C for 1 minute As the mass decreases, the mass change per unit area is calculated and used as an index of acid resistance. Furthermore, the smaller the amount of mass change, the more excellent the acid resistance.

根據表1可知:實施例1~6之半導體元件被覆用材料之表面電荷密度低至6×1011/cm2以下,且耐酸性試驗所致之質量減少為1.0 mg/cm2以下,耐酸性優異。因此可知:實施例1~6之半導體元件被覆用材料適於低耐壓用半導體元件之被覆,且化學耐久性亦優異。 According to Table 1, it can be known that the surface charge density of the semiconductor element coating materials of Examples 1 to 6 is as low as 6 × 10 11 / cm 2 or less, and the mass reduction caused by the acid resistance test is 1.0 mg / cm 2 or less, and acid resistance Excellent. Therefore, it can be seen that the materials for coating semiconductor devices of Examples 1 to 6 are suitable for coating semiconductor devices for low withstand voltage, and have excellent chemical durability.

另一方面,比較例1及2之試樣雖然表面電荷密度較低為6×1011/cm2以下,但耐酸性試驗所致之質量減少為3.5 mg/cm2以上,耐酸性較差。又,比較例3之試樣雖然耐酸性試驗所致之質量減少較少而為0.4 mg/cm2,但表面電荷密度較大為15×1011/cm2On the other hand, although the samples of Comparative Examples 1 and 2 had a low surface charge density of 6 × 10 11 / cm 2 or less, the mass reduction caused by the acid resistance test was 3.5 mg / cm 2 or more, and the acid resistance was poor. The sample of Comparative Example 3 had a small decrease in mass due to the acid resistance test of 0.4 mg / cm 2 , but had a large surface charge density of 15 × 10 11 / cm 2 .

雖對本發明詳細且參照特定之實施形態進行說明,但業者應知曉可不脫離本發明之精神與範圍而加以各種變更或修正。 Although the present invention has been described in detail and with reference to specific embodiments, those skilled in the art should know that various changes or modifications can be made without departing from the spirit and scope of the present invention.

本申請案係基於2011年8月25日提出申請之日本專利申請案(日本專利特願2011-183703)及2012年6月12日提出申 請之日本專利申請案(日本專利特願2012-132531)者,其內容係作為參照而併入於此。 This application is based on a Japanese patent application filed on August 25, 2011 (Japanese Patent Application No. 2011-183703) and a filed on June 12, 2012 The contents of Japanese Patent Application (Japanese Patent Application No. 2012-132531) are hereby incorporated by reference.

產業上之可利用性Industrial availability

本發明之玻璃對環境之負荷較小,化學耐久性優異,且表面電荷密度較低,尤其是較佳用於低耐壓用之半導體元件之被覆。 The glass of the present invention has a small load on the environment, excellent chemical durability, and low surface charge density, and is particularly preferably used for coating semiconductor devices with low withstand voltage.

Claims (4)

一種半導體元件被覆用玻璃,其特徵在於:作為玻璃組成,以質量%計含有:52~65%之ZnO、5~20%之B2O3、15~35%之SiO2及4~6%之Al2O3,其更含有Ta2O5、MnO2、Nb2O5、CeO2或Sb2O3,且實質上不含鉛成分。 A glass for covering a semiconductor element, which is characterized in that as a glass composition, it contains 52 to 65% of ZnO, 5 to 20% of B 2 O 3 , 15 to 35% of SiO 2 and 4 to 6%. Al 2 O 3 , which further contains Ta 2 O 5 , MnO 2 , Nb 2 O 5 , CeO 2 or Sb 2 O 3 , and substantially contains no lead component. 如請求項1之半導體元件被覆用玻璃,其更含有:0~5%之Ta2O5、0~5%之MnO2、0~5%之Nb2O5、0~3%之CeO2及0~3%之Sb2O3作為組成。 For example, the glass for covering a semiconductor element of claim 1 further contains: 0 to 5% of Ta 2 O 5 , 0 to 5% of MnO 2 , 0 to 5% of Nb 2 O 5 , and 0 to 3% of CeO 2 And 0 ~ 3% of Sb 2 O 3 as a composition. 一種半導體元件被覆用材料,其特徵在於含有包含如請求項1或2之半導體元件被覆用玻璃之玻璃粉末。 A semiconductor element coating material comprising a glass powder containing the glass for coating a semiconductor element as claimed in claim 1 or 2. 如請求項3之半導體元件被覆用材料,其相對於玻璃粉末100質量份,含有選自TiO2、ZrO2、ZnO、ZnO‧B2O3及2ZnO‧SiO2中之至少一種無機粉末0.01~5質量份而成。 For example, the semiconductor element coating material of claim 3 contains at least one inorganic powder selected from TiO 2 , ZrO 2 , ZnO, ZnO‧B 2 O 3, and 2ZnO‧SiO 2 with respect to 100 parts by mass of glass powder. 5 parts by mass.
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