WO2014103936A1 - Glass for encapsulating semiconductor and sheath tube for encapsulating semiconductor - Google Patents

Glass for encapsulating semiconductor and sheath tube for encapsulating semiconductor Download PDF

Info

Publication number
WO2014103936A1
WO2014103936A1 PCT/JP2013/084263 JP2013084263W WO2014103936A1 WO 2014103936 A1 WO2014103936 A1 WO 2014103936A1 JP 2013084263 W JP2013084263 W JP 2013084263W WO 2014103936 A1 WO2014103936 A1 WO 2014103936A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
semiconductor
temperature
content
sio
Prior art date
Application number
PCT/JP2013/084263
Other languages
French (fr)
Japanese (ja)
Inventor
籔内　浩一
Original Assignee
日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2014103936A1 publication Critical patent/WO2014103936A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
    • 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
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
    • 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
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/108—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing boron
    • 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
    • C03C8/24—Fusion 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a glass for semiconductor encapsulation, that is, a glass for sealing an element such as a silicon diode, a light emitting diode, and a thermistor and an electrode material such as a jumet wire electrically connected thereto, and a sheath tube for semiconductor encapsulation.
  • an electrode material such as a semiconductor element and a dumet wire is inserted and held in a glass sheath tube in a state where the semiconductor element is sandwiched between the electrode materials from both sides.
  • the semiconductor element is hermetically sealed in the glass tube by heating in this state to soften and deform the glass tube.
  • the temperature at which the glass tube is heated is generally the temperature at which the viscosity of the glass is 10 6 dPa ⁇ s, and is called the sealing temperature.
  • the condition required for the encapsulation temperature of the glass is that the electrical characteristics of the semiconductor are not higher than the heat resistance temperature of the semiconductor to be encapsulated so as not to be lost at the encapsulation temperature.
  • the heat resistance temperature of semiconductors varies widely depending on the type and design, since the heat resistance of semiconductors with high versatility is about 650 ° C., it is important that the sealing temperature is 650 ° C. or lower.
  • the thermal expansion coefficient is consistent with the coefficient of thermal expansion of the most commonly used jumet wire as an electrode material, specifically within the range of 85 to 100 ⁇ 10 ⁇ 7 / ° C. (between 30 and 380 ° C.). The thermal expansion coefficient is required.
  • the metal wire exposed outside the glass tube is subjected to an acid treatment or a plating treatment for the purpose of removing the oxide film.
  • an acid treatment or a plating treatment for the purpose of removing the oxide film.
  • a part of the glass tube (leaded type) or the entire surface (surface mount type) is immersed in these chemicals and processed. For this reason, the glass is required to have sufficient chemical resistance, particularly acid resistance.
  • a lead silicate glass containing PbO in a large amount of 45 to 75% by mass has been used as a glass for semiconductor encapsulation that satisfies such conditions (for example, Patent Document 1).
  • the reason why lead silicate glass is widely used includes, for example, the following advantages.
  • PbO has a large effect of reducing the viscosity of glass in silicate glass, and can enclose a semiconductor element at a low temperature.
  • the thermal expansion coefficient can be adjusted by adjusting the amount of PbO, it is easy to match the thermal expansion coefficient of various commonly used jumet wires.
  • the present invention has been made in order to solve the above-mentioned problems.
  • the conditions necessary for glass for semiconductor encapsulation that is, an encapsulation temperature of 650 ° C. or lower, 30
  • an encapsulation temperature of 650 ° C. or lower
  • 30 To provide a glass for semiconductor encapsulation and an outer tube for semiconductor encapsulation, which satisfy a linear expansion coefficient of 85 to 100 ⁇ 10 ⁇ 7 / ° C. in a temperature range of ⁇ 380 ° C. and excellent in acid resistance.
  • the alkali metal oxides R ′ 2 O Li 2 O, Na 2 O, K, etc. are maintained while maintaining the content of SiO 2 and the like. It has been found that by increasing the amount of 2 O), it is possible to obtain a glass that can achieve both a reduction in the sealing temperature and prevention of a decrease in acid resistance.
  • a glass not containing PbO has also been proposed, but this type of glass is difficult to seal at a low temperature equivalent to a glass containing PbO.
  • the glass for semiconductor encapsulation of the present invention is characterized by containing, as a glass composition, PbO 5 to 35%, SiO 2 40 to 55%, Li 2 O + Na 2 O + K 2 O 5 to 20% by mass.
  • Li 2 O + Na 2 O + K 2 O refers to the total content of Li 2 O, Na 2 O and K 2 O.
  • the encapsulation temperature is 650 ° C. or less
  • the linear expansion coefficient in the temperature range of 30 to 380 ° C. satisfies 85 to 100 ⁇ 10 ⁇ 7 / ° C.
  • the semiconductor encapsulation sheath has excellent acid resistance. Tubes can be made.
  • a glass composition PbO 5 to 35%, SiO 2 40 to 55%, Al 2 O 3 0 to 5%, B 2 O 3 0 to 15%, MgO 0 to 5% by mass%.
  • CaO 0-5%, BaO 0-5%, SrO 0-5%, ZnO 0-10%, Li 2 O 1-5%, Na 2 O 0-10%, K 2 O 0-10%, Li 2 O + Na 2 O + K 2 O 5 to 20%, TiO 2 0 to 10%, ZrO 2 0 to 3% are preferably contained.
  • the encapsulation temperature is 650 ° C. or less
  • the linear expansion coefficient in the temperature range of 30 to 380 ° C. satisfies 85 to 100 ⁇ 10 ⁇ 7 / ° C.
  • the semiconductor encapsulation sheath has excellent acid resistance. Tubes can be made easily.
  • the mass% is SiO 2 + TiO 2 45 to 60%.
  • SiO 2 + TiO 2 refers to the total content of SiO 2 and TiO 2 .
  • the temperature corresponding to a viscosity of 10 6 dPa ⁇ s is preferably 650 ° C. or lower.
  • “temperature corresponding to a viscosity of 10 6 dPa ⁇ s” means a temperature determined as follows. First, the softening point of glass is measured by a fiber method conforming to ASTM C338. Next, a temperature corresponding to the viscosity of the working point region is obtained by a platinum ball pulling method. Finally, these viscosities and temperatures are applied to the Fulcher equation to calculate the temperature at 10 6 dPa ⁇ s.
  • the outer tube for semiconductor encapsulation of the present invention is made of the above glass.
  • the glass for semiconductor encapsulation of the present invention can encapsulate a semiconductor element at a low temperature. Moreover, since it is excellent in acid resistance, even if an acid treatment or a plating treatment is performed after the element is encapsulated, a crack is not generated on the surface, so that a highly reliable semiconductor encapsulated part can be produced. In addition, since it is difficult for crystals to precipitate during glass tube forming, it is possible to stably produce a large amount of outer tube.
  • the glass composition range is limited as described above in the lead-free glass for semiconductor encapsulation of the present invention.
  • the following% display indicates mass%, and the numerical range expressed using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • PbO is an important component for lowering the sealing temperature and adjusting to a desired thermal expansion coefficient.
  • the content of PbO is 5 to 35%, preferably 10 to 35%, more preferably 10 to 30%.
  • the glass surface will deteriorate easily by acid treatment, and as a result, the sealing property of a product will fall.
  • SiO 2 is a main component and an important component for stabilizing the glass. It also has a great effect on improving acid resistance. On the other hand, SiO 2 is also a component that raises the sealing temperature.
  • the content of SiO 2 is 40 to 55%, preferably 40 to 52%, more preferably 43 to 52%. When the content of SiO 2 is too small it becomes difficult to enjoy the effects described above. On the other hand, if the SiO 2 content is too large, low-temperature encapsulation becomes difficult.
  • Al 2 O 3 is a component that suppresses precipitation of crystals containing Si and increases water resistance and acid resistance.
  • Al 2 O 3 is also a component that increases the viscosity of the glass.
  • the content of Al 2 O 3 is preferably 0 to 5%, particularly preferably 0.5 to 4.5%. When the content of Al 2 O 3 is too large tends to decrease. Viscosity becomes too high formability of the glass, it is difficult to cold sealed. Further, the composition balance is lost, and crystals containing Li are likely to precipitate.
  • B 2 O 3 is a component that stabilizes the glass and lowers the viscosity of the glass.
  • B 2 O 3 is also a component that lowers chemical resistance.
  • the content of B 2 O 3 is preferably 0 to 15%, 3 to 11%, particularly 5 to 10%. If the content of B 2 O 3 is small, it may be difficult to enjoy the above-described effects. On the other hand, if the content of B 2 O 3 is too large, the chemical resistance is deteriorated.
  • Alkaline earth metal oxides RO (MgO, CaO, SrO, BaO) have a high effect of stabilizing the glass.
  • RO Alkaline earth metal oxides
  • the content of RO is small, and the content is preferably 0 to 5%, particularly preferably 0 to 3%. Further, the total amount of these components is desirably 10% or less, particularly 7% or less.
  • ZnO is a component that can reduce the viscosity of glass without increasing the expansion and without deteriorating acid resistance as compared with alkali metal oxides.
  • the content of ZnO is preferably 0 to 10%, 0.5 to 8%, particularly 3 to 7%. If the amount of ZnO is small, the above-mentioned effects may not be enjoyed. Conversely, if it is excessive, crystals are likely to precipitate.
  • Alkali metal oxide R ′ 2 O (Li 2 O, Na 2 O, K 2 O) has an effect of lowering the viscosity of glass or increasing the expansion.
  • Li 2 O is preferably used as an essential component in the glass having the above composition because it has a great effect of reducing the viscosity of the glass.
  • R ′ 2 O becomes excessive, expansion becomes too high and cracks are generated between the metal wires such as dumet. Therefore, the total amount of R ′ 2 O (Li 2 O, Na 2 O, K 2 O) is 5 to 20%, preferably 6 to 15%, more preferably 9 to 13%.
  • Each alkali metal oxide component will be described below.
  • Li 2 O has a large effect of reducing the viscosity of the glass as described above.
  • the content of Li 2 O increases, crystals containing Li tend to be generated. Therefore, the content of Li 2 O is desirably 1 to 5%, 1.5 to 4.5%, particularly 2.5 to 4.0%.
  • the content of Li 2 O is too large, devitrification tends to occur, and crystals of Li 2 O—ZnO—SiO 2 or Li 2 O—TiO 2 —SiO 2 tend to precipitate.
  • acid resistance tends to deteriorate.
  • Na 2 O has the effect of stabilizing the glass and preventing devitrification in addition to the effects common to the alkali metals described above.
  • Na 2 O deteriorates the acid resistance of the glass.
  • the content of Na 2 O is preferably 0 to 10%, 2 to 7%, particularly 3 to 6%.
  • the Na 2 O content is too small it may be difficult to enjoy the effects described above.
  • the content of Na 2 O is too large, easily devitrified.
  • K 2 O has the effect of stabilizing the glass and preventing devitrification in addition to the effects common to the alkali metals described above. On the other hand, K 2 O worsens the acid resistance of the glass.
  • the content of K 2 O is preferably 0 to 10%, 2 to 7%, particularly 3 to 6%. When the content of K 2 O is too large easily devitrified.
  • TiO 2 is a component added to increase acid resistance. On the other hand, TiO 2 tends to induce crystals and tends to deteriorate the devitrification resistance of the glass. For this reason, if TiO 2 is contained excessively, the glass is easily devitrified by contact with a metal or a refractory, and there is a possibility that the dimensional accuracy of the glass obtained due to the influence of the devitrified material is lowered.
  • the content of TiO 2 is preferably 0 to 10%, 0.5 to 6%, particularly 1.5 to 4%.
  • ZrO 2 is a component that improves chemical resistance.
  • the content of ZrO 2 is preferably 0 to 3%, particularly preferably 0 to 2%.
  • the glass of the present invention by strictly controlling the SiO 2 and the total amount of TiO 2, it is easy to achieve both acid resistance and low temperature (sealing temperature). By increasing the total amount of SiO 2 and TiO 2 , it is possible to efficiently improve acid resistance.
  • the total content of SiO 2 and TiO 2 is preferably 45 to 60%, particularly 47 to 52%. If the total amount of SiO 2 and TiO 2 is 45% or more, the acid resistance is further improved, which is preferable. If the total amount of SiO 2 and TiO 2 is 60% or less, the glass is hard to be hardened, and encapsulation at a low temperature becomes easier.
  • the glass for semiconductor encapsulation of the present invention can contain various components in addition to the above components as long as the properties of the glass are not impaired.
  • F can be added to 0.5%
  • Sb 2 O 3 can be added to 0.5% as a fining agent.
  • environmentally undesirable components such as As 2 O 3 should not be added.
  • the content of As 2 O 3 is limited to 0.1% or less.
  • the temperature corresponding to a viscosity of 10 6 dPa ⁇ s is preferably 650 ° C. or less, more preferably 620 to 640 ° C., and further preferably 620 to 635 ° C.
  • the viscosity temperature of 10 6 dPa ⁇ s generally corresponds to the sealing temperature of the semiconductor element. Therefore, the glass of the present invention can encapsulate a semiconductor element at 650 ° C. or lower.
  • the glass for semiconductor encapsulation of the present invention preferably has a thermal expansion coefficient in the range of 30 ° C. to 380 ° C. of the glass, preferably 85 to 100 ⁇ 10 ⁇ 7 / ° C., and more preferably 85 to 95 ⁇ , for sealing with dumet. 10 ⁇ 7 / ° C., more preferably 90 to 95 ⁇ 10 ⁇ 7 / ° C.
  • the glass for semiconductor encapsulation of the present invention preferably has a weight loss rate of 500 ppm or less, more preferably 400 ppm or less, and even more preferably 300 ppm or less when immersed in a 5% by weight solution (30 ° C.) of 36N sulfuric acid for 60 minutes. is there.
  • a smaller weight reduction rate is preferable because cracks and the like are less likely to occur on the glass surface in the plating process.
  • the glass for semiconductor encapsulation of the present invention has as high a volume resistance as possible.
  • the volume resistance value at 150 ° C. is preferably 7 or more, particularly 9 or more, and more preferably 11 or more in Log ⁇ ( ⁇ ⁇ cm). If the volume resistance of glass is low, for example, in the case of a diode, a slight amount of electricity flows between the electrodes, resulting in a circuit as if a resistor was installed in parallel with the diode.
  • a mixing and mixing step of measuring and mixing minerals and refined crystal powder containing components constituting glass and preparing raw materials to be introduced into a furnace, and raw materials A melting step of forming a molten glass, a forming step of forming the molten glass into a tube shape, and a processing step of cutting the tube into predetermined dimensions.
  • glass raw materials are prepared and mixed so that the above composition range is obtained.
  • the raw materials are composed of minerals and impurities composed of a plurality of components such as oxides and carbonates, and may be prepared in consideration of the analytical values, and the raw materials are not limited. These are measured in terms of weight and mixed with an appropriate mixer according to the scale, such as a V mixer, a rocking mixer, or a mixer equipped with stirring blades, to obtain an input raw material.
  • the melting furnace is for melting the glass raw material into a vitrification tank, a clarification tank for raising and removing bubbles in the glass, and lowering the clarified glass to an appropriate viscosity for molding and leading it to a molding apparatus. It is common to have a passage (feeder).
  • a refractory material or a furnace covered with platinum is used, and it is heated by heating with a burner or electric current to glass.
  • the charged raw materials are usually vitrified in a melting tank at 1100 ° C. to 1400 ° C., and further enter a clarification tank at 1200 ° C. to 1500 ° C.
  • bubbles in the glass are lifted to remove the bubbles.
  • the glass that comes out of the Kiyosumi pass is cooled to a viscosity of 10 3.5 to 10 6 dPa ⁇ s suitable for glass molding as it moves to the molding device through the feeder.
  • the glass is formed into a tubular shape with a forming apparatus.
  • a forming method a Danner method, a tongue method, a downdraw method, and an updraw method can be applied.
  • the outer tube for semiconductor encapsulation of the present invention can be obtained by cutting the glass tube into a predetermined dimension.
  • the glass tube can be cut one by one with a diamond cutter.
  • a large number of tube glasses are bound together and then cut with a diamond wheel cutter. A method of cutting a large number of tube glasses at a time is generally used.
  • the lead-free glass for encapsulating a semiconductor of the present invention is not only molded into a glass tube and used as a mantle tube, but also encapsulates a semiconductor element by, for example, forming a powder into a paste, winding it around a semiconductor element and firing it. You can also.
  • a jig is used to set an electrode material such as a dumet wire in the outer tube so that the semiconductor element is sandwiched from both sides. Thereafter, the whole is heated to a temperature of 650 ° C. or lower, the outer tube is softened and deformed, and the semiconductor element is hermetically sealed.
  • a small electronic component such as a silicon diode, a light emitting diode, or a thermistor can be manufactured.
  • Table 1 shows examples of the present invention (sample Nos. 1 to 11) and comparative examples (samples No. 12 and 13).
  • No. No. 12 is a glass described in Patent Document 1
  • No. 12; 13 is a general lead silicate glass conventionally used as a glass for semiconductor encapsulation.
  • glass raw materials were prepared so as to have the glass composition described in the table, melted at 1300 ° C. for 3 hours using a platinum pot, molded, and subjected to various evaluations.
  • silica powder, aluminum oxide, boric acid, calcium carbonate, barium carbonate, zinc oxide, lithium carbonate, sodium nitrate, potassium carbonate, titanium oxide and the like were used as the glass raw material.
  • sample No. which is an example of the present invention.
  • Nos. 1 to 11 had a temperature at 10 6 dPa ⁇ s of 647 ° C. or lower and could be sealed at a low temperature.
  • the coefficient of thermal expansion was 86.2 to 99.3 ⁇ 10 ⁇ 7 / ° C., indicating a coefficient of thermal expansion consistent with the Jumet line.
  • the volume reduction rate was 420 ppm or less, no crack was generated, and the acid resistance was good. Furthermore, it was confirmed that the crystal precipitation viscosity is high and devitrification hardly occurs.
  • the thermal expansion coefficient is a value obtained by measuring an average linear thermal expansion coefficient in a temperature range of 30 to 380 ° C. with a self-recording differential thermal dilatometer using a cylindrical measurement sample having a diameter of about 5 mm and a length of about 20 mm.
  • the enclosure temperature was determined as follows. First, the softening point was measured by a fiber method conforming to ASTM C338. Next, a temperature corresponding to the viscosity of the working point region was determined by a platinum ball pulling method. Finally, these viscosities and temperatures were applied to the Fulcher equation to calculate the temperature at 10 6 dPa ⁇ s, which was used as the sealing temperature.
  • Acid resistance was determined as follows. A 30 ⁇ 30 ⁇ 5 mm glass plate is prepared, mirror-polished, washed with water and dried to measure the original weight. Then, after dipping in a 5% by mass solution of 36N sulfuric acid (30 ° C) for 60 minutes, washed with pure water for 90 seconds, dried at 100 ° C for 30 minutes or more, measured the weight after treatment, (initial weight-after treatment) The weight reduction rate was calculated by (weight) / (initial weight) ⁇ 100. The unit is expressed in ppm. In addition, the presence or absence of cracks was observed on the treated glass surface with an episcopic microscope.
  • the volume resistivity at 150 ° C. is a value measured by a method based on ASTM C-657.
  • the crystal precipitation viscosity is determined by pulverizing the sample and aligning the particle size with a sieve. Read this, convert this temperature into viscosity, and set it as crystal precipitation viscosity
  • the glass for semiconductor encapsulation of the present invention is suitable as a glass envelope material used for encapsulation of semiconductor elements such as silicon diodes, light emitting diodes, and thermistors.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

Provided are a glass for encapsulating a semiconductor and a sheath tube for encapsulating a semiconductor. The glass exhibits excellent acid resistance and satisfies the requirements necessary as a semiconductor-encapsulating glass, namely, an encapsulation temperature of 650ºC or lower and a linear expansion coefficient of 85 to 100 × 10-7/ºC in a temperature range of 30 to 380ºC, though the glass has a low lead content. The glass for encapsulating a semiconductor comprises, as a glass composition and in mass%, 5 to 35% of PbO, 40 to 55% of SiO2, and 5 to 20% of Li2O+Na2O+K2O.

Description

半導体封入用ガラス及び半導体封入用外套管Glass for semiconductor encapsulation and outer tube for semiconductor encapsulation
　本発明は半導体封入用のガラス、すなわち、シリコンダイオード、発光ダイオード、サーミスタ等の素子と、それに電気的に接続するジュメット線等の電極材料を気密封入するガラス及び半導体封入用外套管に関する。 The present invention relates to a glass for semiconductor encapsulation, that is, a glass for sealing an element such as a silicon diode, a light emitting diode, and a thermistor and an electrode material such as a jumet wire electrically connected thereto, and a sheath tube for semiconductor encapsulation.
　ダイオード、ＬＥＤ、サーミスタ等といった小型の電子部品の製造には以下の方法が広く採用されている。まず半導体素子とジュメット線等の電極材料を、半導体素子が電極材料で両側から挟まれた状態でガラス外套管内に挿入し、保持する。続いて、この状態で加熱してガラス管を軟化変形させることにより、半導体素子をガラス管内に気密封入する。ガラス管を加熱する温度は、一般的にはガラスの粘度が１０６ｄＰａ・ｓとなる温度であり、封入温度と呼ばれる。ここで、ガラスの封入温度に求められる条件は、半導体の電気特性が封入温度で失われないように、封入する半導体の耐熱温度以下であることである。半導体の耐熱温度はその種類や設計に応じて多岐に渡るが、汎用性の高い半導体の耐熱性は６５０℃程度なので、封入温度は６５０℃以下であることが重要になる。また、ガラスに求められる特性として、熱膨張係数がある。これは、電極材料として最も一般的に用いられているジュメット線の熱膨張係数に整合することであり、具体的には８５～１００×１０－７／℃（３０～３８０℃間）の範囲内の熱膨張係数が必要である。さらに、半導体素子の加熱封入後、ガラス管外に露出した金属線は、酸化膜を除去する目的で酸処理やメッキ処理等が行われる。この際、部品の仕様によっては、ガラス管の一部（リード付タイプ）、もしくは全面（表面実装タイプ）をこれら薬液に浸漬し、処理する。このため、ガラスには十分な耐薬品性、特に耐酸性が要求される。 The following methods are widely used for manufacturing small electronic components such as diodes, LEDs, thermistors, and the like. First, an electrode material such as a semiconductor element and a dumet wire is inserted and held in a glass sheath tube in a state where the semiconductor element is sandwiched between the electrode materials from both sides. Subsequently, the semiconductor element is hermetically sealed in the glass tube by heating in this state to soften and deform the glass tube. The temperature at which the glass tube is heated is generally the temperature at which the viscosity of the glass is 10 6 dPa · s, and is called the sealing temperature. Here, the condition required for the encapsulation temperature of the glass is that the electrical characteristics of the semiconductor are not higher than the heat resistance temperature of the semiconductor to be encapsulated so as not to be lost at the encapsulation temperature. Although the heat resistance temperature of semiconductors varies widely depending on the type and design, since the heat resistance of semiconductors with high versatility is about 650 ° C., it is important that the sealing temperature is 650 ° C. or lower. Further, as a characteristic required for glass, there is a thermal expansion coefficient. This is consistent with the coefficient of thermal expansion of the most commonly used jumet wire as an electrode material, specifically within the range of 85 to 100 × 10 −7 / ° C. (between 30 and 380 ° C.). The thermal expansion coefficient is required. Furthermore, after heat sealing the semiconductor element, the metal wire exposed outside the glass tube is subjected to an acid treatment or a plating treatment for the purpose of removing the oxide film. At this time, depending on the specifications of the parts, a part of the glass tube (leaded type) or the entire surface (surface mount type) is immersed in these chemicals and processed. For this reason, the glass is required to have sufficient chemical resistance, particularly acid resistance.
　従来、このような条件を満たす半導体封入用ガラスには、ＰｂＯを４５～７５質量％と多量に含有する鉛ケイ酸塩ガラスが使われている（例えば特許文献１）。鉛ケイ酸塩ガラスが広く採用されている理由として、例えば以下の利点が挙げられる。ＰｂＯはケイ酸塩ガラスにおいて、ガラスの粘度を下げる作用が大きく、低温で半導体素子を封入できる。またＰｂＯ量の調整によって熱膨張係数を調節することが可能であることから、一般的に用いられている種々のジュメット線の熱膨張係数に整合させることが容易である。 Conventionally, a lead silicate glass containing PbO in a large amount of 45 to 75% by mass has been used as a glass for semiconductor encapsulation that satisfies such conditions (for example, Patent Document 1). The reason why lead silicate glass is widely used includes, for example, the following advantages. PbO has a large effect of reducing the viscosity of glass in silicate glass, and can enclose a semiconductor element at a low temperature. In addition, since the thermal expansion coefficient can be adjusted by adjusting the amount of PbO, it is easy to match the thermal expansion coefficient of various commonly used jumet wires.
日本国特開平０８－０６７５３４号公報Japanese Unexamined Patent Publication No. 08-067534 日本国特開２００２－３７６４１号公報Japanese Unexamined Patent Publication No. 2002-37641
　近年、鉛やカドミニウム、砒素などの有害成分による環境汚染が問題視され、工業製品にそれらの有害成分を低減することが要求されている。電子部品においても、先ず半田の鉛低減化が積極的に取り組まれており、次いで、半導体封入用ガラスにもＰｂＯの含有量低減が望まれている。 In recent years, environmental pollution due to harmful components such as lead, cadmium and arsenic is regarded as a problem, and industrial products are required to reduce these harmful components. Also in electronic parts, first, lead reduction of solder has been actively pursued, and then the PbO content reduction is also desired in the glass for semiconductor encapsulation.
　ところで半導体素子の封入の際の温度が高いと、素子が劣化したり、金属の降伏点を越えて弾性を失うことによる金属線の接触不良が生じたりする。これを改善するためにはガラスの封入温度を下げることが望ましい。従来の鉛ケイ酸塩ガラスにおいて、多量にＰｂＯが含有されている理由は封入温度を下げるためといえる。しかし、ＰｂＯは酸溶液に溶出しやすい性質があり、多量にＰｂＯを含有するほど、溶出量が多くなり、封止性が低下することがある。 By the way, when the temperature at the time of encapsulating the semiconductor element is high, the element deteriorates or a metal wire contact failure occurs due to loss of elasticity beyond the yield point of the metal. In order to improve this, it is desirable to lower the glass sealing temperature. In the conventional lead silicate glass, it can be said that the reason why PbO is contained in a large amount is to lower the sealing temperature. However, PbO has a property of being easily eluted in an acid solution, and the more PbO is contained, the greater the amount of elution and the lowering of sealing properties.
　また、耐酸性が十分でないと、ガラス表面の劣化による細かいクラックが生じ、様々な汚れや水分が付着しやすくなり、素子の表面抵抗が下がり、電気製品に不具合を生じることがある。 In addition, if the acid resistance is not sufficient, fine cracks due to deterioration of the glass surface occur, and various stains and moisture are likely to adhere, resulting in a decrease in the surface resistance of the device, which may cause problems in electrical products.
　本発明は、上記課題の解決の為になされたものであり、鉛の含有量の少ないガラスであるにも関わらず、半導体封入用ガラスとして必要な条件、すなわち、封入温度が６５０℃以下、３０～３８０℃の温度範囲における線膨張係数が８５～１００×１０－７／℃を満足しており、しかも耐酸性に優れた半導体封入用ガラス及び半導体封入用外套管を提供することである。 The present invention has been made in order to solve the above-mentioned problems. Despite being a glass having a low content of lead, the conditions necessary for glass for semiconductor encapsulation, that is, an encapsulation temperature of 650 ° C. or lower, 30 To provide a glass for semiconductor encapsulation and an outer tube for semiconductor encapsulation, which satisfy a linear expansion coefficient of 85 to 100 × 10 −7 / ° C. in a temperature range of ˜380 ° C. and excellent in acid resistance.
　本発明者等は、ＰｂＯ含有量を５～３５質量％に低減しても、ＳｉＯ２等の含有量を維持しながら、アルカリ金属酸化物Ｒ’２Ｏ（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）量を増やすことにより、封入温度の低温化の達成と耐酸性の低下防止を両立できるガラスが得られることを見出した。なお、例えば特許文献２のように、ＰｂＯを含まないガラスも提案されているが、この種のガラスは、ＰｂＯを含有するガラスと同等の低い温度で封止することが難しい。 Even if the inventors reduce the PbO content to 5-35% by mass, the alkali metal oxides R ′ 2 O (Li 2 O, Na 2 O, K, etc. are maintained while maintaining the content of SiO 2 and the like. It has been found that by increasing the amount of 2 O), it is possible to obtain a glass that can achieve both a reduction in the sealing temperature and prevention of a decrease in acid resistance. For example, as in Patent Document 2, a glass not containing PbO has also been proposed, but this type of glass is difficult to seal at a low temperature equivalent to a glass containing PbO.
　即ち、本発明の半導体封入用ガラスは、ガラス組成として、質量％で、ＰｂＯ　５～３５％、ＳｉＯ２　４０～５５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　５～２０％含有することを特徴とする。ここで「Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」とは、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの含有量の合量を指す。
　上記構成によれば、封入温度が６５０℃以下、３０～３８０℃の温度範囲における線膨張係数が８５～１００×１０－７／℃を満足しており、しかも耐酸性に優れた半導体封入用外套管を作製することが可能になる。 That is, the glass for semiconductor encapsulation of the present invention is characterized by containing, as a glass composition, PbO 5 to 35%, SiO 2 40 to 55%, Li 2 O + Na 2 O + K 2 O 5 to 20% by mass. . Here, “Li 2 O + Na 2 O + K 2 O” refers to the total content of Li 2 O, Na 2 O and K 2 O.
According to the above configuration, the encapsulation temperature is 650 ° C. or less, the linear expansion coefficient in the temperature range of 30 to 380 ° C. satisfies 85 to 100 × 10 −7 / ° C., and the semiconductor encapsulation sheath has excellent acid resistance. Tubes can be made.
　本発明においては、ガラス組成として、質量％で、ＰｂＯ　５～３５％、ＳｉＯ２　４０～５５％、Ａｌ２Ｏ３　０～５％、Ｂ２Ｏ３　０～１５％、ＭｇＯ　０～５％、ＣａＯ　０～５％、ＢａＯ　０～５％、ＳｒＯ　０～５％、ＺｎＯ　０～１０％、Ｌｉ２Ｏ　１～５％、Ｎａ２Ｏ　０～１０％、Ｋ２Ｏ　０～１０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　５～２０％、ＴｉＯ２　０～１０％、ＺｒＯ２　０～３％含有することが好ましい。 In the present invention, as a glass composition, PbO 5 to 35%, SiO 2 40 to 55%, Al 2 O 3 0 to 5%, B 2 O 3 0 to 15%, MgO 0 to 5% by mass%. CaO 0-5%, BaO 0-5%, SrO 0-5%, ZnO 0-10%, Li 2 O 1-5%, Na 2 O 0-10%, K 2 O 0-10%, Li 2 O + Na 2 O + K 2 O 5 to 20%, TiO 2 0 to 10%, ZrO 2 0 to 3% are preferably contained.
　上記構成によれば、封入温度が６５０℃以下、３０～３８０℃の温度範囲における線膨張係数が８５～１００×１０－７／℃を満足しており、しかも耐酸性に優れた半導体封入用外套管を容易に作製することができる。 According to the above configuration, the encapsulation temperature is 650 ° C. or less, the linear expansion coefficient in the temperature range of 30 to 380 ° C. satisfies 85 to 100 × 10 −7 / ° C., and the semiconductor encapsulation sheath has excellent acid resistance. Tubes can be made easily.
　本発明においては、質量％で、ＳｉＯ２＋ＴｉＯ２　４５～６０％であることが好ましい。ここで「ＳｉＯ２＋ＴｉＯ２」とは、ＳｉＯ２及びＴｉＯ２の含有量の合量を指す。 In the present invention, it is preferable that the mass% is SiO 2 + TiO 2 45 to 60%. Here, “SiO 2 + TiO 2 ” refers to the total content of SiO 2 and TiO 2 .
　上記構成によれば、より耐酸性に優れたガラスを得ることができる。 According to the above configuration, a glass with better acid resistance can be obtained.
　本発明においては、１０６ｄＰａ・ｓの粘度に相当する温度が６５０℃以下であることが好ましい。本発明において、「１０６ｄＰａ・ｓの粘度に相当する温度」は、次のようにして求めた温度を意味する。まずＡＳＴＭ　Ｃ３３８に準拠するファイバ法によりガラスの軟化点を測定する。次に白金球引き上げ法により作業点領域の粘度に相当する温度を求める。最後にこれらの粘度と温度をＦｕｌｃｈｅｒの式に当てはめて、１０６ｄＰａ・ｓにおける温度を算出する。 In the present invention, the temperature corresponding to a viscosity of 10 6 dPa · s is preferably 650 ° C. or lower. In the present invention, “temperature corresponding to a viscosity of 10 6 dPa · s” means a temperature determined as follows. First, the softening point of glass is measured by a fiber method conforming to ASTM C338. Next, a temperature corresponding to the viscosity of the working point region is obtained by a platinum ball pulling method. Finally, these viscosities and temperatures are applied to the Fulcher equation to calculate the temperature at 10 6 dPa · s.
　本発明の半導体封入用外套管は、上記ガラスからなることを特徴とする。 The outer tube for semiconductor encapsulation of the present invention is made of the above glass.
　本発明の半導体封入用ガラスは、低温で半導体素子を封入できる。また耐酸性に優れるため、素子封入後に酸処理やメッキ処理を施しても、表面にクラックが生じないことから信頼性の高い半導体封入部品を作製することができる。しかもガラス管成形時に結晶が析出しにくいことから、安定して大量に外套管を生産することができる。 The glass for semiconductor encapsulation of the present invention can encapsulate a semiconductor element at a low temperature. Moreover, since it is excellent in acid resistance, even if an acid treatment or a plating treatment is performed after the element is encapsulated, a crack is not generated on the surface, so that a highly reliable semiconductor encapsulated part can be produced. In addition, since it is difficult for crystals to precipitate during glass tube forming, it is possible to stably produce a large amount of outer tube.
　本発明の半導体封入用無鉛ガラスにおいて、上記のようにガラス組成範囲を限定した理由を以下に説明する。なお、以下の％表示は質量％を指し、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 The reason why the glass composition range is limited as described above in the lead-free glass for semiconductor encapsulation of the present invention will be described below. In addition, the following% display indicates mass%, and the numerical range expressed using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
　ＰｂＯは、封入温度を下げ、また所望の熱膨張係数に調整するために重要な成分である。しかし、ＰｂＯの含有量が多くなると耐酸性が悪化する。このためＰｂＯの含有量は５～３５％、好ましくは１０～３５％、さらに好ましくは１０～３０％である。ＰｂＯの含有量が少なすぎると上記した効果を享受し難くなる。一方、ＰｂＯの含有量が多すぎると酸処理によって、ガラス表面が劣化しやすくなり、結果として製品の封止性が低下する。 PbO is an important component for lowering the sealing temperature and adjusting to a desired thermal expansion coefficient. However, when the PbO content increases, the acid resistance deteriorates. Therefore, the content of PbO is 5 to 35%, preferably 10 to 35%, more preferably 10 to 30%. When there is too little content of PbO, it will become difficult to enjoy the above-mentioned effect. On the other hand, when there is too much content of PbO, the glass surface will deteriorate easily by acid treatment, and as a result, the sealing property of a product will fall.
　ＳｉＯ２は、主成分であり、またガラスの安定化に重要な成分である。また耐酸性の向上に大きな効果がある。一方、ＳｉＯ２は封止温度を上昇させる成分でもある。ＳｉＯ２の含有量は４０～５５％、好ましくは４０～５２％、さらに好ましくは４３～５２％である。ＳｉＯ２の含有量が少なすぎると上記した効果を享受し難くなる。逆にＳｉＯ２の含有量が多すぎると低温封入が困難になる。 SiO 2 is a main component and an important component for stabilizing the glass. It also has a great effect on improving acid resistance. On the other hand, SiO 2 is also a component that raises the sealing temperature. The content of SiO 2 is 40 to 55%, preferably 40 to 52%, more preferably 43 to 52%. When the content of SiO 2 is too small it becomes difficult to enjoy the effects described above. On the other hand, if the SiO 2 content is too large, low-temperature encapsulation becomes difficult.
　Ａｌ２Ｏ３は、Ｓｉを含有する結晶の析出を抑え、また耐水性や耐酸性を高める成分である。一方、Ａｌ２Ｏ３はガラスの粘性を上昇させる成分でもある。Ａｌ２Ｏ３の含有量は０～５％、特に０．５～４．５％であることが好ましい。Ａｌ２Ｏ３の含有量が多すぎるとガラスの粘性が高くなり過ぎて成形性が低下し易くなり、低温封入が困難になる。さらに組成のバランスを欠いて、Ｌｉを含有する結晶が析出しやすくなる。 Al 2 O 3 is a component that suppresses precipitation of crystals containing Si and increases water resistance and acid resistance. On the other hand, Al 2 O 3 is also a component that increases the viscosity of the glass. The content of Al 2 O 3 is preferably 0 to 5%, particularly preferably 0.5 to 4.5%. When the content of Al 2 O 3 is too large tends to decrease. Viscosity becomes too high formability of the glass, it is difficult to cold sealed. Further, the composition balance is lost, and crystals containing Li are likely to precipitate.
　Ｂ２Ｏ３は、ガラスを安定化させる成分であるとともに、ガラスの粘性を低下させる成分である。一方、Ｂ２Ｏ３は耐薬品性を低下させる成分でもある。Ｂ２Ｏ３の含有量は０～１５％、３～１１％、特に５～１０％であることが好ましい。Ｂ２Ｏ３の含有量が少ないと上記した効果を享受し難くいことがある。逆にＢ２Ｏ３の含有量が多すぎると耐薬品性が悪くなる。 B 2 O 3 is a component that stabilizes the glass and lowers the viscosity of the glass. On the other hand, B 2 O 3 is also a component that lowers chemical resistance. The content of B 2 O 3 is preferably 0 to 15%, 3 to 11%, particularly 5 to 10%. If the content of B 2 O 3 is small, it may be difficult to enjoy the above-described effects. On the other hand, if the content of B 2 O 3 is too large, the chemical resistance is deteriorated.
　アルカリ土類金属酸化物ＲＯ（ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ）はガラスを安定化させる効果が高い。その一方で、１０６ｄＰａ・ｓの粘度に相当する温度が６５０℃以下のガラスにおいては、ＲＯによるガラスの低温化効果は期待できず、むしろ封入温度を上昇させるおそれがある。このためＲＯの含有量は少ない方が好ましく、その含有量は各々０～５％、特に各々０～３％であることが好ましい。またこれらの成分は合量で１０％以下、特に７％以下であることが望ましい。 Alkaline earth metal oxides RO (MgO, CaO, SrO, BaO) have a high effect of stabilizing the glass. On the other hand, in a glass whose temperature corresponding to a viscosity of 10 6 dPa · s is 650 ° C. or less, the effect of lowering the glass temperature by RO cannot be expected, but there is a possibility that the encapsulation temperature is raised. For this reason, it is preferable that the content of RO is small, and the content is preferably 0 to 5%, particularly preferably 0 to 3%. Further, the total amount of these components is desirably 10% or less, particularly 7% or less.
　ＺｎＯはアルカリ金属酸化物に比べて膨張を上げずに、また耐酸性を劣化させずにガラスの粘性を低下させることができる成分である。ＺｎＯの含有量は０～１０％、０．５～８％、特に３～７％であることが好ましい。ＺｎＯが少ないと上記した効果を享受できないことがあり、逆に過剰になると結晶が析出し易くなる。 ZnO is a component that can reduce the viscosity of glass without increasing the expansion and without deteriorating acid resistance as compared with alkali metal oxides. The content of ZnO is preferably 0 to 10%, 0.5 to 8%, particularly 3 to 7%. If the amount of ZnO is small, the above-mentioned effects may not be enjoyed. Conversely, if it is excessive, crystals are likely to precipitate.
　アルカリ金属酸化物Ｒ’２Ｏ（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）は、ガラスの粘性を下げたり、膨張を上げたりする効果がある。特にＬｉ２Ｏはガラスの粘性を低下させる効果が大きいことから、上記組成のガラスでは必須成分として使用することが好ましい。一方、Ｒ’２Ｏが過剰になると、膨張が高くなりすぎてジュメット等の金属線との間でクラックを生じる。それゆえＲ’２Ｏは合量（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）で５～２０％、好ましくは６～１５％、さらに好ましくは９～１３％である。なお各アルカリ金属酸化物成分については以下に述べる。 Alkali metal oxide R ′ 2 O (Li 2 O, Na 2 O, K 2 O) has an effect of lowering the viscosity of glass or increasing the expansion. In particular, Li 2 O is preferably used as an essential component in the glass having the above composition because it has a great effect of reducing the viscosity of the glass. On the other hand, when R ′ 2 O becomes excessive, expansion becomes too high and cracks are generated between the metal wires such as dumet. Therefore, the total amount of R ′ 2 O (Li 2 O, Na 2 O, K 2 O) is 5 to 20%, preferably 6 to 15%, more preferably 9 to 13%. Each alkali metal oxide component will be described below.
　Ｌｉ２Ｏは上記したようにガラスの粘性を低下させる効果が大きいが、その含有量が多くなるとＬｉを含有する結晶を生じさせやすい。このためＬｉ２Ｏの含有量は１～５％、１．５～４．５％、特に２．５～４．０％であることが望ましい。一方、Ｌｉ２Ｏの含有量が多すぎると失透し易くなり、Ｌｉ２Ｏ－ＺｎＯ－ＳｉＯ２系やＬｉ２Ｏ－ＴｉＯ２－ＳｉＯ２の結晶が析出しやすくなる。また耐酸性が悪化する傾向にある。 Li 2 O has a large effect of reducing the viscosity of the glass as described above. However, when the content of Li 2 O increases, crystals containing Li tend to be generated. Therefore, the content of Li 2 O is desirably 1 to 5%, 1.5 to 4.5%, particularly 2.5 to 4.0%. On the other hand, when the content of Li 2 O is too large, devitrification tends to occur, and crystals of Li 2 O—ZnO—SiO 2 or Li 2 O—TiO 2 —SiO 2 tend to precipitate. Moreover, acid resistance tends to deteriorate.
　Ｎａ２Ｏは上記したアルカリ金属共通の効果の他にガラスを安定化させて失透を防止する効果がある。その一方でＮａ２Ｏはガラスの耐酸性を悪化させる。本発明においてはガラスの安定化を考慮して導入することが望ましい。Ｎａ２Ｏの含有量は０～１０％、２～７％、特に３～６％であることが好ましい。Ｎａ２Ｏの含有量が少なすぎると上記した効果を享受し難くなることがある。一方、Ｎａ２Ｏの含有量が多すぎると、失透し易くなる。 Na 2 O has the effect of stabilizing the glass and preventing devitrification in addition to the effects common to the alkali metals described above. On the other hand, Na 2 O deteriorates the acid resistance of the glass. In the present invention, it is desirable to introduce in consideration of stabilization of the glass. The content of Na 2 O is preferably 0 to 10%, 2 to 7%, particularly 3 to 6%. When the Na 2 O content is too small it may be difficult to enjoy the effects described above. On the other hand, when the content of Na 2 O is too large, easily devitrified.
　Ｋ２Ｏは上記したアルカリ金属共通の効果の他にガラスを安定化させ失透を防止する効果がある。その一方でＫ２Ｏはガラスの耐酸性を悪化させる。Ｋ２Ｏの含有量は０～１０％、２～７％、特に３～６％であることが好ましい。Ｋ２Ｏの含有量が多すぎると失透し易くなる。 K 2 O has the effect of stabilizing the glass and preventing devitrification in addition to the effects common to the alkali metals described above. On the other hand, K 2 O worsens the acid resistance of the glass. The content of K 2 O is preferably 0 to 10%, 2 to 7%, particularly 3 to 6%. When the content of K 2 O is too large easily devitrified.
　なおガラスを安定化させるためには、Ｎａ２ＯとＫ２Ｏのどちらか一方または両方を含有させることが望ましい。 In addition, in order to stabilize glass, it is desirable to contain either one or both of Na 2 O and K 2 O.
　ＴｉＯ２は耐酸性を高めるために添加する成分である。その一方でＴｉＯ２は結晶を誘発させやすく、ガラスの耐失透性を悪化させやすい。このためＴｉＯ２を過剰に含有させると金属や耐火物との接触によってガラスが容易に失透し、この失透物の影響によって得られるガラスの寸法精度が低下するという問題を引き起こす虞がある。ＴｉＯ２の含有量は０～１０％、０．５～６％、特に１．５～４％であることが好ましい。 TiO 2 is a component added to increase acid resistance. On the other hand, TiO 2 tends to induce crystals and tends to deteriorate the devitrification resistance of the glass. For this reason, if TiO 2 is contained excessively, the glass is easily devitrified by contact with a metal or a refractory, and there is a possibility that the dimensional accuracy of the glass obtained due to the influence of the devitrified material is lowered. The content of TiO 2 is preferably 0 to 10%, 0.5 to 6%, particularly 1.5 to 4%.
　ＺｒＯ２は耐薬品性を向上させる成分である。その一方で、ＺｒＯ２の含有量が多すぎるとガラスの粘性が高くなりすぎ、低温封入が困難になる。ＺｒＯ２の含有量は０～３％、特に０～２％であることが好ましい。 ZrO 2 is a component that improves chemical resistance. On the other hand, when the content of ZrO 2 is too large too high the viscosity of the glass, it is difficult to cold sealed. The content of ZrO 2 is preferably 0 to 3%, particularly preferably 0 to 2%.
　また本発明のガラスにおいては、ＳｉＯ２とＴｉＯ２の合量を厳密にコントロールすることによって、耐酸性と低温化（封着温度）の両立を図ることが容易になる。ＳｉＯ２とＴｉＯ２の合量を高めることで効率的に耐酸性を向上させることが可能となる。ＳｉＯ２とＴｉＯ２の含有量は合量で４５～６０％、特に４７～５２％であることが好ましい。ＳｉＯ２とＴｉＯ２の合量が４５％以上であれば、耐酸性がより向上するため好ましい。ＳｉＯ２とＴｉＯ２の合量が６０％以下であれば、ガラスが固くなり難く、低温での封入がより容易になる。 In the glass of the present invention, by strictly controlling the SiO 2 and the total amount of TiO 2, it is easy to achieve both acid resistance and low temperature (sealing temperature). By increasing the total amount of SiO 2 and TiO 2 , it is possible to efficiently improve acid resistance. The total content of SiO 2 and TiO 2 is preferably 45 to 60%, particularly 47 to 52%. If the total amount of SiO 2 and TiO 2 is 45% or more, the acid resistance is further improved, which is preferable. If the total amount of SiO 2 and TiO 2 is 60% or less, the glass is hard to be hardened, and encapsulation at a low temperature becomes easier.
　本発明の半導体封入用ガラスは、上記成分以外にも、ガラスの特性を損なわない範囲で種々の成分を添加することができる。例えばガラスの粘性を低下させるためにＦを０．５％まで、清澄剤としてＳｂ２Ｏ３を０．５％までそれぞれ添加することができる。ただしＡｓ２Ｏ３等の環境上好ましくない成分は添加すべきでない。具体的にはＡｓ２Ｏ３の含有量は０．１％以下に制限される。 The glass for semiconductor encapsulation of the present invention can contain various components in addition to the above components as long as the properties of the glass are not impaired. For example, in order to reduce the viscosity of glass, F can be added to 0.5%, and Sb 2 O 3 can be added to 0.5% as a fining agent. However, environmentally undesirable components such as As 2 O 3 should not be added. Specifically, the content of As 2 O 3 is limited to 0.1% or less.
　上記組成を有する本発明の半導体封入用ガラスは、１０６ｄＰａ・ｓの粘度に相当する温度が好ましくは６５０℃以下、より好ましくは６２０～６４０℃、更に好ましくは６２０～６３５℃である。１０６ｄＰａ・ｓの粘度の温度は、概ね半導体素子の封入温度に相当する。それゆえ本発明のガラスは、６５０℃以下で半導体素子を封入することができる。 In the glass for semiconductor encapsulation of the present invention having the above composition, the temperature corresponding to a viscosity of 10 6 dPa · s is preferably 650 ° C. or less, more preferably 620 to 640 ° C., and further preferably 620 to 635 ° C. The viscosity temperature of 10 6 dPa · s generally corresponds to the sealing temperature of the semiconductor element. Therefore, the glass of the present invention can encapsulate a semiconductor element at 650 ° C. or lower.
　また本発明の半導体封入用ガラスは、ジュメットとシールするために、ガラスの３０℃～３８０℃の範囲における熱膨張係数が好ましくは８５～１００×１０－７／℃、より好ましくは８５～９５×１０－７／℃、更に好ましくは９０～９５×１０－７／℃である。 The glass for semiconductor encapsulation of the present invention preferably has a thermal expansion coefficient in the range of 30 ° C. to 380 ° C. of the glass, preferably 85 to 100 × 10 −7 / ° C., and more preferably 85 to 95 ×, for sealing with dumet. 10 −7 / ° C., more preferably 90 to 95 × 10 −7 / ° C.
　また本発明の半導体封入用ガラスは、３６Ｎ硫酸の５質量％溶液（３０℃）に６０分間浸漬した場合に、好ましくは重量減少率が５００ｐｐｍ以下、より好ましくは４００ｐｐｍ以下、更に好ましくは３００ｐｐｍ以下である。重量減少率が小さいほど、めっき処理工程においてガラス表面にクラック等が発生し難くなるため好ましい。 The glass for semiconductor encapsulation of the present invention preferably has a weight loss rate of 500 ppm or less, more preferably 400 ppm or less, and even more preferably 300 ppm or less when immersed in a 5% by weight solution (30 ° C.) of 36N sulfuric acid for 60 minutes. is there. A smaller weight reduction rate is preferable because cracks and the like are less likely to occur on the glass surface in the plating process.
　また本発明の半導体封入用ガラスは、体積抵抗が極力高いことが好ましい。具体的には１５０℃における体積抵抗値が、Ｌｏｇρ（Ω・ｃｍ）で７以上、特に９以上、さらには１１以上であることが望ましい。なおガラスの体積抵抗が低いと、例えばダイオードの場合は電極間にわずかに電気が流れるようになり、あたかもダイオードに平行して抵抗体を設置したような回路を生じてしまう。 Moreover, it is preferable that the glass for semiconductor encapsulation of the present invention has as high a volume resistance as possible. Specifically, the volume resistance value at 150 ° C. is preferably 7 or more, particularly 9 or more, and more preferably 11 or more in Logρ (Ω · cm). If the volume resistance of glass is low, for example, in the case of a diode, a slight amount of electricity flows between the electrodes, resulting in a circuit as if a resistor was installed in parallel with the diode.
　次に本発明の半導体封入用ガラスからなる半導体封入用外套管の製造方法を説明する。ただし本発明の半導体封入用外套管を製造する方法は、下記の方法に限られるものではない。 Next, a method for manufacturing a semiconductor encapsulation outer tube made of the semiconductor encapsulation glass of the present invention will be described. However, the method for producing the outer tube for semiconductor encapsulation of the present invention is not limited to the following method.
　工業的規模での半導体封入用外套管の製造方法の一つの態様では、ガラスを構成する成分を含む鉱物や精製結晶粉末を計測混合し、炉に投入する原料を調合する調合混合工程と、原料を溶融ガラス化する溶融工程と、溶融したガラスを管の形に成形する成形工程と、管を所定の寸法に切断する加工工程を含む。 In one aspect of the manufacturing method of the outer tube for semiconductor encapsulation on an industrial scale, a mixing and mixing step of measuring and mixing minerals and refined crystal powder containing components constituting glass and preparing raw materials to be introduced into a furnace, and raw materials A melting step of forming a molten glass, a forming step of forming the molten glass into a tube shape, and a processing step of cutting the tube into predetermined dimensions.
　まず上記組成範囲となるように、ガラス原料を調合混合する。原料は、酸化物や炭酸塩など複数の成分からなる鉱物や不純物からなっており、分析値を考慮して調合すればよく、原料は限定されない。これらを重量換算で計測し、Ｖミキサーやロッキングミキサー、攪拌羽根のついたミキサーなど規模に応じた適当な混合機で混合し、投入原料を得る。 First, glass raw materials are prepared and mixed so that the above composition range is obtained. The raw materials are composed of minerals and impurities composed of a plurality of components such as oxides and carbonates, and may be prepared in consideration of the analytical values, and the raw materials are not limited. These are measured in terms of weight and mixed with an appropriate mixer according to the scale, such as a V mixer, a rocking mixer, or a mixer equipped with stirring blades, to obtain an input raw material.
　次に原料をガラス溶融炉に投入し、ガラス化する。溶融炉は、ガラス原料を溶融しガラス化するための溶融槽と、ガラス中の泡を上昇除去するための清澄槽と、清澄されたガラスを成形に適当な粘度まで下げ、成形装置に導くための通路（フィーダー）とを有するものが一般的である。溶融炉は、耐火物や内部を白金で覆った炉が使用され、バーナーによる加熱やガラスへの電気通電によって加熱される。投入された原料は通常１１００℃～１４００℃の溶解槽でガラス化され、さらに１２００℃～１５００℃の清澄槽に入る。ここでガラス中の泡を浮上させて泡を除去する。清澄糟から出たガラスは、フィーダーを通って成形装置に移動するうちに温度が下がり、ガラスの成形に適した粘度１０３．５～１０６ｄＰａ・ｓになる。 Next, the raw material is put into a glass melting furnace and vitrified. The melting furnace is for melting the glass raw material into a vitrification tank, a clarification tank for raising and removing bubbles in the glass, and lowering the clarified glass to an appropriate viscosity for molding and leading it to a molding apparatus. It is common to have a passage (feeder). As the melting furnace, a refractory material or a furnace covered with platinum is used, and it is heated by heating with a burner or electric current to glass. The charged raw materials are usually vitrified in a melting tank at 1100 ° C. to 1400 ° C., and further enter a clarification tank at 1200 ° C. to 1500 ° C. Here, bubbles in the glass are lifted to remove the bubbles. The glass that comes out of the Kiyosumi pass is cooled to a viscosity of 10 3.5 to 10 6 dPa · s suitable for glass molding as it moves to the molding device through the feeder.
　次いで成形装置にてガラスを管状に成形する。成形法としてはダンナー法、ベロ法、ダウンドロー法、アップドロー法を適用することができる。 Next, the glass is formed into a tubular shape with a forming apparatus. As a forming method, a Danner method, a tongue method, a downdraw method, and an updraw method can be applied.
　その後、ガラス管を所定の寸法に切断することにより、本発明の半導体封入用外套管を得ることができる。ガラス管の切断加工は、管１本ずつをダイヤモンドカッターで切断することも可能であるが、大量生産に適した方法として、多数の管ガラスを１本に結束してからダイヤモンドホイールカッターで切断し、一度に多数の管ガラスを切断する方法が一般的に用いられている。 Then, the outer tube for semiconductor encapsulation of the present invention can be obtained by cutting the glass tube into a predetermined dimension. The glass tube can be cut one by one with a diamond cutter. However, as a method suitable for mass production, a large number of tube glasses are bound together and then cut with a diamond wheel cutter. A method of cutting a large number of tube glasses at a time is generally used.
　また本発明の半導体封入用無鉛ガラスは、ガラス管に成形して外套管として使用する以外にも、例えば、粉末状にしてペースト化し、半導体素子に巻き付けて焼成することで半導体素子を封入することもできる。 The lead-free glass for encapsulating a semiconductor of the present invention is not only molded into a glass tube and used as a mantle tube, but also encapsulates a semiconductor element by, for example, forming a powder into a paste, winding it around a semiconductor element and firing it. You can also.
　次に本発明の半導体封入用外套管を用いた半導体素子の封入方法の一例を述べる。 Next, an example of a method for encapsulating a semiconductor element using the outer tube for semiconductor encapsulation of the present invention will be described.
　まず外套管内でジュメット線などの電極材料が半導体素子を両側から挟み込んだ状態となるように冶具を用いてセットする。その後、全体を６５０℃以下の温度に加熱し、外套管を軟化変形させて半導体素子を気密封入する。このような方法でシリコンダイオード、発光ダイオード、サーミスタなどの小型の電子部品を作製することができる。 First, a jig is used to set an electrode material such as a dumet wire in the outer tube so that the semiconductor element is sandwiched from both sides. Thereafter, the whole is heated to a temperature of 650 ° C. or lower, the outer tube is softened and deformed, and the semiconductor element is hermetically sealed. By such a method, a small electronic component such as a silicon diode, a light emitting diode, or a thermistor can be manufactured.
　以下、実施例に基づいて本発明を説明する。なお本発明は、下記実施例に限定されるものではない。 Hereinafter, the present invention will be described based on examples. In addition, this invention is not limited to the following Example.
　表１は本発明の実施例（試料Ｎｏ．１～１１）、及び比較例（試料Ｎｏ．１２、１３）を示している。なおＮｏ．１２は特許文献１に記載のガラス、Ｎｏ．１３は従来から半導体封入用ガラスとして用いられている一般的な鉛ケイ酸塩ガラスである。 Table 1 shows examples of the present invention (sample Nos. 1 to 11) and comparative examples (samples No. 12 and 13). No. No. 12 is a glass described in Patent Document 1, No. 12; 13 is a general lead silicate glass conventionally used as a glass for semiconductor encapsulation.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　各試料は次のようにして調製した。ます表中に記載のガラス組成となるように、ガラス原料を調合し、白金ポットを用いて１３００℃で３時間溶融し、成形して各種の評価に供した。なおガラス原料としては、珪石粉、酸化アルミニウム、硼酸、炭酸カルシウム、炭酸バリウム、酸化亜鉛、炭酸リチウム、硝酸ソーダ、炭酸カリウム、酸化チタン等を使用した。 Each sample was prepared as follows. First, glass raw materials were prepared so as to have the glass composition described in the table, melted at 1300 ° C. for 3 hours using a platinum pot, molded, and subjected to various evaluations. As the glass raw material, silica powder, aluminum oxide, boric acid, calcium carbonate, barium carbonate, zinc oxide, lithium carbonate, sodium nitrate, potassium carbonate, titanium oxide and the like were used.
　次に得られた試料について、熱膨張係数、１０６ｄＰａ・ｓにおける温度、耐酸性（重量減少率、クラック有無）、体積抵抗、及び結晶析出粘度を評価した。 Next, the thermal expansion coefficient, temperature at 10 6 dPa · s, acid resistance (weight reduction rate, presence or absence of cracks), volume resistance, and crystal precipitation viscosity were evaluated for the obtained samples.
　表１から明らかなように、本発明の実施例である試料Ｎｏ．１～１１は、１０６ｄＰａ・ｓにおける温度が６４７℃以下であり、低温封入可能であった。また熱膨張係数が８６．２～９９．３×１０－７／℃であり、ジュメット線と整合する熱膨張係数を示した。また体積減少率が４２０ｐｐｍ以下であり、クラックの発生もなく、耐酸性が良好であった。さらに結晶析出粘度が高く、失透が生じ難いことが確認された。 As is apparent from Table 1, sample No. which is an example of the present invention. Nos. 1 to 11 had a temperature at 10 6 dPa · s of 647 ° C. or lower and could be sealed at a low temperature. The coefficient of thermal expansion was 86.2 to 99.3 × 10 −7 / ° C., indicating a coefficient of thermal expansion consistent with the Jumet line. Further, the volume reduction rate was 420 ppm or less, no crack was generated, and the acid resistance was good. Furthermore, it was confirmed that the crystal precipitation viscosity is high and devitrification hardly occurs.
　熱膨張係数は、直径約５ｍｍ、長さ約２０ｍｍの円柱状の測定試料を用いて、自記示差熱膨張計により３０～３８０℃の温度範囲における平均線熱膨張係数を測定した値である。 The thermal expansion coefficient is a value obtained by measuring an average linear thermal expansion coefficient in a temperature range of 30 to 380 ° C. with a self-recording differential thermal dilatometer using a cylindrical measurement sample having a diameter of about 5 mm and a length of about 20 mm.
　封入温度は次のようにして求めた。まずＡＳＴＭ　Ｃ３３８に準拠するファイバ法により軟化点を測定した。次に、白金球引き上げ法により作業点領域の粘度に相当する温度を求めた。最後に、これらの粘度と温度をＦｕｌｃｈｅｒの式に当てはめて、１０６ｄＰａ・ｓにおける温度を算出し、これを封入温度とした。 The enclosure temperature was determined as follows. First, the softening point was measured by a fiber method conforming to ASTM C338. Next, a temperature corresponding to the viscosity of the working point region was determined by a platinum ball pulling method. Finally, these viscosities and temperatures were applied to the Fulcher equation to calculate the temperature at 10 6 dPa · s, which was used as the sealing temperature.
　耐酸性は次のようにして求めた。３０×３０×５ｍｍのガラス板を作製し、鏡面研磨後、水洗い乾燥して元の重量を計測する。その後、３６Ｎ硫酸の５質量％溶液（３０℃）に６０分間浸漬したのち、９０秒間純水で洗い、１００℃で３０分以上乾燥後、処理後の重量を計測し、（初期重量―処理後重量）／（初期重量）×１００により重量減少率を算出した。単位はｐｐｍで表記した。またクラックの有無は処理後のガラス表面を落射顕微鏡で観察した。 Acid resistance was determined as follows. A 30 × 30 × 5 mm glass plate is prepared, mirror-polished, washed with water and dried to measure the original weight. Then, after dipping in a 5% by mass solution of 36N sulfuric acid (30 ° C) for 60 minutes, washed with pure water for 90 seconds, dried at 100 ° C for 30 minutes or more, measured the weight after treatment, (initial weight-after treatment) The weight reduction rate was calculated by (weight) / (initial weight) × 100. The unit is expressed in ppm. In addition, the presence or absence of cracks was observed on the treated glass surface with an episcopic microscope.
　１５０℃における体積抵抗率は、ＡＳＴＭ　Ｃ－６５７に準拠した方法で測定した値である。 The volume resistivity at 150 ° C. is a value measured by a method based on ASTM C-657.
　結晶析出粘度は、試料を粉砕し、ふるいで粒度をそろえた後、白金製ボートに移し、温度傾斜のある炉で３時間処理して取り出し、偏光顕微鏡を用い、結晶の析出した最も高い温度を読み取り、この温度を粘度に換算し、結晶析出粘度とした The crystal precipitation viscosity is determined by pulverizing the sample and aligning the particle size with a sieve. Read this, convert this temperature into viscosity, and set it as crystal precipitation viscosity
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１２年１２月２５日出願の日本国特許出願（特願２０１２－２８０６３８）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on December 25, 2012 (Japanese Patent Application No. 2012-280638), the contents of which are incorporated herein by reference.
　本発明の半導体封入用ガラスは、シリコンダイオード、発光ダイオード、サーミスタ等の半導体素子の封入に用いられるガラス外套管材料として好適である。
  The glass for semiconductor encapsulation of the present invention is suitable as a glass envelope material used for encapsulation of semiconductor elements such as silicon diodes, light emitting diodes, and thermistors.

Claims (5)

  1. 　ガラス組成として、質量％で、ＰｂＯ　５～３５％、ＳｉＯ２　４０～５５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　５～２０％含有する半導体封入用ガラス。 A glass for encapsulating a semiconductor containing 5 to 35% of PbO, 40 to 55% of SiO 2 , and 5 to 20% of Li 2 O + Na 2 O + K 2 O as a glass composition.
  2. 　ガラス組成として、質量％で、ＰｂＯ　５～３５％、ＳｉＯ２　４０～５５％、Ａｌ２Ｏ３　０～５％、Ｂ２Ｏ３　０～１５％、ＭｇＯ　０～５％、ＣａＯ　０～５％、ＢａＯ　０～５％、ＳｒＯ　０～５％、ＺｎＯ　０～１０％、Ｌｉ２Ｏ　１～５％、Ｎａ２Ｏ　０～１０％、Ｋ２Ｏ　０～１０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　５～２０％、ＴｉＯ２　０～１０％、ＺｒＯ２　０～３％含有する請求項１に記載の半導体封入用ガラス。 As a glass composition, PbO 5 to 35%, SiO 2 40 to 55%, Al 2 O 3 0 to 5%, B 2 O 3 0 to 15%, MgO 0 to 5%, CaO 0 to 5% by mass%. BaO 0-5%, SrO 0-5%, ZnO 0-10%, Li 2 O 1-5%, Na 2 O 0-10%, K 2 O 0-10%, Li 2 O + Na 2 O + K 2 O The glass for semiconductor encapsulation according to claim 1, containing 5 to 20%, TiO 2 0 to 10%, ZrO 2 0 to 3%.
  3. 　質量％で、ＳｉＯ２＋ＴｉＯ２が４５～６０％である請求項１又は２に記載の半導体封入用ガラス。 The glass for semiconductor encapsulation according to claim 1, wherein SiO 2 + TiO 2 is 45% to 60% by mass.
  4. 　１０６ｄＰａ・ｓの粘度に相当する温度が６５０℃以下である請求項１～３の何れかに記載の半導体封入用ガラス。 The glass for semiconductor encapsulation according to any one of claims 1 to 3, wherein a temperature corresponding to a viscosity of 10 6 dPa · s is 650 ° C or lower.
  5. 　請求項１～４の何れかに記載のガラスからなる半導体封入用外套管。 An outer tube for semiconductor encapsulation made of the glass according to any one of claims 1 to 4.
PCT/JP2013/084263 2012-12-25 2013-12-20 Glass for encapsulating semiconductor and sheath tube for encapsulating semiconductor WO2014103936A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-280638 2012-12-25
JP2012280638 2012-12-25

Publications (1)

Publication Number Publication Date
WO2014103936A1 true WO2014103936A1 (en) 2014-07-03

Family

ID=51021020

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/084263 WO2014103936A1 (en) 2012-12-25 2013-12-20 Glass for encapsulating semiconductor and sheath tube for encapsulating semiconductor

Country Status (3)

Country Link
JP (1) JP2014141397A (en)
TW (1) TW201429912A (en)
WO (1) WO2014103936A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109153595A (en) * 2016-04-28 2019-01-04 日本电气硝子株式会社 Metal sealing glass tube and metal sealing glass

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7257350B2 (en) 2020-03-16 2023-04-13 三菱重工業株式会社 gas turbine combustor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01308843A (en) * 1988-02-26 1989-12-13 Ohara Inc Optical glass
JPH0350138A (en) * 1989-07-18 1991-03-04 Canon Inc Optical glass
JP2000143286A (en) * 1998-09-04 2000-05-23 Nippon Electric Glass Co Ltd Tube glass less liable to leach lead
JP2002211948A (en) * 2001-01-12 2002-07-31 Nippon Electric Glass Co Ltd Funnel glass for cathode-ray tube

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01308843A (en) * 1988-02-26 1989-12-13 Ohara Inc Optical glass
JPH0350138A (en) * 1989-07-18 1991-03-04 Canon Inc Optical glass
JP2000143286A (en) * 1998-09-04 2000-05-23 Nippon Electric Glass Co Ltd Tube glass less liable to leach lead
JP2002211948A (en) * 2001-01-12 2002-07-31 Nippon Electric Glass Co Ltd Funnel glass for cathode-ray tube

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109153595A (en) * 2016-04-28 2019-01-04 日本电气硝子株式会社 Metal sealing glass tube and metal sealing glass
CN109153595B (en) * 2016-04-28 2022-08-09 日本电气硝子株式会社 Glass tube for metal sealing and glass for metal sealing

Also Published As

Publication number Publication date
TW201429912A (en) 2014-08-01
JP2014141397A (en) 2014-08-07

Similar Documents

Publication Publication Date Title
US6534346B2 (en) Glass and glass tube for encapsulating semiconductors
JP5029014B2 (en) Semiconductor sealing glass, semiconductor sealing outer tube, and semiconductor electronic component
JP5354445B2 (en) Glass for metal coating and semiconductor sealing material
US9230872B2 (en) Lead-free glass for semiconductor encapsulation
JP2012116744A (en) Lead-free glass for sealing of semiconductor and overcoat tube for sealing of semiconductor
JP4789052B2 (en) Semiconductor encapsulation glass, semiconductor encapsulation envelope, and semiconductor element encapsulation method
JP5088914B2 (en) Glass for semiconductor encapsulation and outer tube for semiconductor encapsulation
WO2014103936A1 (en) Glass for encapsulating semiconductor and sheath tube for encapsulating semiconductor
WO2012060337A1 (en) Semiconductor encapsulating non-lead glass and semiconductor encapsulating coating tube
JP2020172423A (en) Alkali-free glass plate
JP6041201B2 (en) Lead-free glass for semiconductor encapsulation
EP1219572B1 (en) Glass for encapsulating semiconductor and overcoat tube for encapsulating semiconductor using the same
JP2011116578A (en) Glass for sealing semiconductor, sheath tube for sealing semiconductor, and method for sealing semiconductor element
JP5678410B2 (en) Lead-free low melting point glass
JP2011184216A (en) Glass for sealing semiconductor, mantle tube for sealing semiconductor and semiconductor electronic component
JP2012140259A (en) Method for producing sheath tube for sealing semiconductor and sheath tube for sealing semiconductor
JPH0867534A (en) Semiconductor-encapsulating glass

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13866781

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13866781

Country of ref document: EP

Kind code of ref document: A1