JPH04160035A - Low-melting point sealing composition - Google Patents
Low-melting point sealing compositionInfo
- Publication number
- JPH04160035A JPH04160035A JP28467390A JP28467390A JPH04160035A JP H04160035 A JPH04160035 A JP H04160035A JP 28467390 A JP28467390 A JP 28467390A JP 28467390 A JP28467390 A JP 28467390A JP H04160035 A JPH04160035 A JP H04160035A
- Authority
- JP
- Japan
- Prior art keywords
- melting point
- pbo
- glass
- powder
- low
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 238000002844 melting Methods 0.000 title claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 28
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006104 solid solution Substances 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 229910052787 antimony Inorganic materials 0.000 claims abstract 2
- 229910052788 barium Inorganic materials 0.000 claims abstract 2
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- 229910052802 copper Inorganic materials 0.000 claims abstract 2
- 229910052742 iron Inorganic materials 0.000 claims abstract 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- 229910052748 manganese Inorganic materials 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 229910052759 nickel Inorganic materials 0.000 claims abstract 2
- 229910052758 niobium Inorganic materials 0.000 claims abstract 2
- 229910052715 tantalum Inorganic materials 0.000 claims abstract 2
- 229910052725 zinc Inorganic materials 0.000 claims abstract 2
- 230000008018 melting Effects 0.000 claims description 9
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910003069 TeO2 Inorganic materials 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229910052844 willemite Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 229910000174 eucryptite Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- -1 That is Substances 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—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
Landscapes
- 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)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は低融点封着用組成物に関し、特にセラミックパ
ッケージや表示デバイス等の気密封着に好適な低融点封
着用組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a low-melting point sealing composition, and particularly to a low-melting point sealing composition suitable for hermetically sealing ceramic packages, display devices, and the like.
［従来の技術］
従来より、セラミックパッケージや表示デバイス等の気
密封着材として、ＰｂＯ−Ｂ２Ｏ，系、ＰｂＯ−Ｚｎ０
−Ｂ、０３系、ＺｎＯ−Ｂ２Ｏ３−５１０□系の低融点
ガラスにウイレマイト、コージェライト、ジルコン、酸
化すず、β−ユークリプタイト等の低膨張耐火フィラー
を混合した封着材が広く用いられている。[Prior Art] Conventionally, PbO-B2O, PbO-Zn0, etc. have been used as hermetic sealing materials for ceramic packages, display devices, etc.
-B, 03 series, ZnO-B2O3-510□ series low melting point glasses mixed with low expansion refractory fillers such as willemite, cordierite, zircon, tin oxide, and β-eucryptite are widely used. There is.
しかしながら、これらの封着材においては封着温度を４
００℃以下にすることが困難であり、熱に敏感な素子、
例えば集積度の高いＩＣや特殊な水晶振動子を搭載した
セラミックパッケージの封着には使用することができな
い。このためより低温で封着できる封着材が求められて
いるが、従来の低融点ガラスを用いたものではこの要求
に応えることが困難である。However, in these sealing materials, the sealing temperature is 4
Heat-sensitive elements that are difficult to maintain at temperatures below 00°C;
For example, it cannot be used to seal ceramic packages equipped with highly integrated ICs or special crystal resonators. For this reason, there is a need for a sealing material that can seal at lower temperatures, but it is difficult to meet this demand with conventional materials using low melting point glass.
近年、このような事情から４００℃以下で封着を行うこ
とが可能なガラスとしてＰｂＯ−Ｖ２Ｏ３−ＴｅＯ２系
ガラスが開発されている。In recent years, under these circumstances, PbO--V2O3-TeO2-based glass has been developed as a glass that can be sealed at 400 DEG C. or lower.
［発明が解決しようとする問題点コ
先記したようにＰｂＯ４２０ａ−ＴｅＯ□系のガラスは
従来のガラスに比べてより低融点のガラスであるが、熱
膨張係数が１００−１４０ Ｘｌ０−’／”Ｃとアルミ
ナのそれ（）ＯＸ １０−７／ ’Ｃ）や窓板ガラスの
それ（８５×１０−’／ ”Ｃ）に比べて高いため、セ
ラミックパッケージや表示デバイスの封着に使用する場
合は、低膨張耐火フィラーを用いて熱膨張係数を調整す
る必要がある。しかしながら通常用いられるフィラー、
即ちウイレマイト、コージェライト、ジルコン、酸化す
ず、β−ユークリプタイト等のセラミック粉末はＰｂＯ
−Ｖ、０５−ＴｅＯ□系ガラスとの相性が悪く、それゆ
えこれらを混合すると熱膨張係数は低下するが、材料の
流動性が著しく損なわれ、封着が困難になるという問題
が生じる。[Problems to be solved by the invention: As mentioned earlier, PbO420a-TeO□-based glass has a lower melting point than conventional glasses, but its thermal expansion coefficient is 100-140 Xl0-'/'' When used for sealing ceramic packages and display devices, the It is necessary to adjust the coefficient of thermal expansion using a low expansion refractory filler. However, commonly used fillers,
That is, ceramic powders such as willemite, cordierite, zircon, tin oxide, and β-eucryptite are PbO
It has poor compatibility with -V, 05-TeO□-based glasses, and therefore, when these are mixed, the coefficient of thermal expansion decreases, but the fluidity of the material is significantly impaired, causing problems in that sealing becomes difficult.
本発明の目的は、ＰｂＯ−ＴｅＯ８−ＴｅＯｚ系ガラス
と、この系のガラスに対して相性の良いフィラーを混合
してなり、熱膨張係数がアルミナや窓板ガラスのそれと
近似するとともに、良好な流動性を示し、４００℃以下
の温度で封着できる低融点封着用組成物を提供すること
である。The object of the present invention is to mix PbO-TeO8-TeOz glass with a filler that is compatible with this type of glass, so that the coefficient of thermal expansion is close to that of alumina or window glass, and it has good fluidity. It is an object of the present invention to provide a low melting point sealing composition which exhibits the following properties and can be sealed at a temperature of 400°C or lower.
［問題点を解決するための手段］
本発明者は上記目的を達成するために種々の研究を行っ
た結果、チタン酸鉛（ＰｂＴ１０３）の一部を他の成分
で置換したチタン酸鉛固溶体がｐｂｏ−ｖ２ｏ。[Means for Solving the Problems] In order to achieve the above object, the present inventor conducted various studies and found that a lead titanate solid solution in which a part of lead titanate (PbT103) was replaced with other components was developed. pbo-v2o.
−ＴｅＯ□系ガラスと相性がよく、良好な流動性を示す
ことを見いだし、本発明として提案するものである。It has been found that it is compatible with -TeO□-based glass and exhibits good fluidity, and is proposed as the present invention.
即ち、本発明の低融点封着用組成物は、重量百分率でＰ
ｂＯ２０〜５５％、Ｖ２Ｏ５２０〜５５％、ＴｅＯ□５
〜４０％、１１□０３０〜８％、ＺｎＯＯ〜１０％、Ｗ
ｂ、０５０−１０％の組成を有するガラス粉末と、チタ
ン酸鉛固溶体粉末とからなり、チタン酸鉛固溶体粉末は
、ＰｂＴ１０３のＰｂの５〜４０原子％がＣａ、 Ｓｒ
、 Ｂａの群から選ばれる１種または２種以上により置
換され、及び／または、Ｔ１の５〜３０原子％がＺｒｓ
Ｓｎ、 Ｍｇ１Ｃｏ１Ｚｎ、旧、Ｍｎ、 Ｃｕ１Ｆｅ
１ムＩ、 Ｂｌ、Ｎｂ１Ｔａ１ＳｂｔＴｅ１Ｖ 、Ｍｏ
、Ｗの群から選ばれる１種または２種以上により置換さ
れたものであることを特徴とする。That is, the low melting point sealing composition of the present invention has a weight percentage of P.
bO20-55%, V2O520-55%, TeO□5
~40%, 11□030~8%, ZnOO~10%, W
b, consisting of a glass powder having a composition of 050-10% and a lead titanate solid solution powder, in which 5 to 40 at% of the Pb of PbT103 is Ca, Sr.
, substituted with one or more selected from the group of Ba, and/or 5 to 30 atomic % of T1 is Zrs
Sn, Mg1Co1Zn, old, Mn, Cu1Fe
1muI, Bl, Nb1Ta1SbtTe1V, Mo
, W is substituted with one or more members selected from the group.
［作用コ
本発明で用いるチタン酸鉛固溶体は、ペロブスカイト構
造を有するチタン酸鉛のＰｂまたはＴ１の一部、若しく
は両者の一部を他の成分で置換したものであり、チタン
酸鉛と同様に熱膨張係数が低く、しかもＷｈｏ−Ｖ２Ｏ
５−ＴｅＯ２系ガラスに対して良好な流動性を示すもの
である。[Function] The lead titanate solid solution used in the present invention is a lead titanate having a perovskite structure in which part of Pb or T1, or part of both, is replaced with other components, and it has the same properties as lead titanate. Low coefficient of thermal expansion and Who-V2O
It shows good fluidity with respect to 5-TeO2 glass.
次に、Ｐｂ及びＴｉの置換量を上記のように限定した理
由を以下に述べる。Next, the reason why the amounts of Pb and Ti substituted are limited as described above will be described below.
Ｐｂは、Ｃａ、 ５ｒ１Ｈａの群から選ばれる１種また
は２種以上によって置換され、その置換量は５〜４０原
子％である。Ｐｂの置換量が５原子％より少ないとその
効果がなく、４０原子％より多いと熱膨張係数が大きく
なる。Pb is substituted with one or more selected from the group of Ca and 5r1Ha, and the amount of substitution is 5 to 40 atomic %. If the substitution amount of Pb is less than 5 at %, there is no effect, and if it is more than 40 at %, the coefficient of thermal expansion becomes large.
Ｔｉは、 Ｚｒ、 Ｓｎ、 Ｍｇ１Ｃｏ、 Ｚｎ１旧、
Ｎｎｘ Ｃｕ１Ｆｅ。Ti is Zr, Sn, Mg1Co, Zn1 old,
NnxCu1Fe.
ムｌ、Ｂｌ、１１ｂ１Ｔａ１Ｓｂ１Ｔｅ１Ｖ 、Ｍｏ、
Ｗの群から選ばれる１種または２種以上によって置換さ
れ、その置換量は５〜９０原子％である。Ｔｉの置換量
が５原子％より少ないとその効果がなく、３０原子％よ
り多いと熱膨張係数が大きくなる。なお、Ｔｌの置換を
原子価が４以外の原子で行う場合は、例えばＣＺｎ”５
ｙ３ｖ Ｗｂ”２７３＞、（Ｆｅ”ｗ＊＋ Ｔａ”ｔｚ
２）、（Ｍｇ””１／２１ Ｗ”ｔｚ２） 、（Ｆｅ”
２／３ｔ Ｗ”１／３）のように、いくつかの元素を組
み合わせることにより平均原子価が４になるようにする
。Mul, Bl, 11b1Ta1Sb1Te1V, Mo,
It is substituted with one or more selected from the group of W, and the amount of substitution is 5 to 90 atom %. If the amount of Ti substitution is less than 5 atom %, there is no effect, and if it is more than 30 atom %, the coefficient of thermal expansion becomes large. In addition, when replacing Tl with an atom having a valence other than 4, for example, CZn''5
y3v Wb”273>, (Fe”w*+ Ta”tz
2), (Mg””1/21 W”tz2), (Fe”
By combining several elements, the average valence becomes 4, such as 2/3t W"1/3).
また、本発明で使用するＰｂＯ−Ｖ２Ｏ５−ＴｅＯ□系
ガラスの組成を先記のように限定した理由を以下に述べ
る。Further, the reason why the composition of the PbO-V2O5-TeO□ glass used in the present invention is limited as described above will be described below.
ＰｂＯが２０％より少ないと４００℃以下の温度でガラ
スが十分に流動しなくなり、５５％より多いと封着時に
結晶化を起こし、流動しなくなる。If PbO is less than 20%, the glass will not flow sufficiently at temperatures below 400° C., and if it is more than 55%, crystallization will occur during sealing and the glass will not flow.
Ｖ２Ｏ５が２０％より少ないとガラス化が困難になり、
５５％より多いと封着時に結晶化を起こし、流動しなく
なる。When V2O5 is less than 20%, vitrification becomes difficult,
If it exceeds 55%, crystallization will occur during sealing, resulting in no flow.
ＴｅＯ、が５％より少ないと封着時に結晶化を起こして
流動しなくなり、４０％より多いと溶融ガラスの成形時
に失透する。If TeO is less than 5%, crystallization will occur during sealing and the glass will not flow, and if it is more than 40%, devitrification will occur during molding of the molten glass.
ム１□０３は、失透防止の効果があるが、８％より多い
とガラスの粘度が高くなり、４００℃以下の温度で十分
に流動しなくなる。Mu1□03 has the effect of preventing devitrification, but if it exceeds 8%, the viscosity of the glass increases and it does not flow sufficiently at temperatures below 400°C.
ＺｎＯが１０％より多いとガラスの粘性が高くなる。When ZnO is more than 10%, the viscosity of the glass becomes high.
Ｎｂ２Ｏ５が１０％より多いとガラスの粘性が高くなる
。If Nb2O5 is more than 10%, the viscosity of the glass becomes high.
また、上記成分以外にも例えば１０％以下のＢ１２Ｏ３
、Ｐ２Ｏ５や５％以下のＣｕ２Ｏ、ＷＯ３、Ｂ２Ｏ３、
Ｓｉｎ□、［０２０３、Ｆｅ２Ｏ３、ＺｒＯ２、ＳｒＯ
、ＢａＯを含有させることが可能である。In addition to the above components, for example, 10% or less of B12O3
, P2O5, 5% or less Cu2O, WO3, B2O3,
Sin□, [0203, Fe2O3, ZrO2, SrO
, BaO can be contained.
なお、本発明において、ＰｂＯ−Ｖ２Ｏ３−ＴｅＩＯ２
系ガラス粉末とチタン酸鉛固溶体粉末の混合比は適当な
割合に設定されるが、各々５０〜８０体積％、２０〜５
０体積％の範囲がより好ましい。In addition, in the present invention, PbO-V2O3-TeIO2
The mixing ratio of the glass powder and lead titanate solid solution powder is set at an appropriate ratio, 50 to 80% by volume and 20 to 5% by volume, respectively.
A range of 0% by volume is more preferred.
［実施例コ 以下、本発明を実施例に基づいて説明する。[Example code] Hereinafter, the present invention will be explained based on examples.
表１は本発明におけるＰｂＯ−Ｖ２Ｏ３−ＴｅＯ２系ガ
ラス粉末の実施例を示すものである。Table 1 shows examples of PbO-V2O3-TeO2 glass powders in the present invention.
以下余白
表 １
（重量％）
表１に示したガラス粉末は、鉛丹、五酸化バナジウム、
二酸化テルル、アルミナ、亜鉛華、五酸化ニオブを表記
の組成になるように調合し、白金坩堝に入れ、電気炉に
おいて８００℃で１時間溶融した後、薄板状に成形し、
ついでこの成形物をボールミルで粉砕し、２００メツシ
ユ篩を通過させることによって作製した。Margin Table 1 (% by weight) The glass powder shown in Table 1 contains red lead, vanadium pentoxide,
Tellurium dioxide, alumina, zinc white, and niobium pentoxide are mixed to have the composition shown, placed in a platinum crucible, melted at 800°C for 1 hour in an electric furnace, and then formed into a thin plate.
This molded product was then ground in a ball mill and passed through a 200 mesh sieve.
表２は本発明におけるチタン酸鉛固溶体粉末を示すもの
である。Table 2 shows the lead titanate solid solution powder in the present invention.
表２（その１）
表２（その２）
表２の各試料は、原料として炭酸バリウム、リサージ、
酸化チタン、炭酸ストロンチウム、ジルコニア、酸化す
ず、亜鉛華、五酸化ニオブ、酸化コバルト、マグネシア
、酸化ニッケル、二酸化マンガン、酸化鋼、酸化第二鉄
、五酸化アンチモン、五酸化タンタル、五酸化バナジウ
ム、二酸化テルル、二酸化モリブデン、炭酸カルシウム
、アルミナ、酸化ビスマス、三酸化タングステンを表記
組成になるように調合し、湿式混合した後、乾燥させ、
１１００ ＃１３５０℃で５時間焼成し、次いでこれを
粉砕し、３５Ｇメツシユの篩を通過させて平均粒径を約
５ミクロンとしたものである。Table 2 (Part 1) Table 2 (Part 2) Each sample in Table 2 uses barium carbonate, litharge,
Titanium oxide, strontium carbonate, zirconia, tin oxide, zinc white, niobium pentoxide, cobalt oxide, magnesia, nickel oxide, manganese dioxide, steel oxide, ferric oxide, antimony pentoxide, tantalum pentoxide, vanadium pentoxide, dioxide Tellurium, molybdenum dioxide, calcium carbonate, alumina, bismuth oxide, and tungsten trioxide are mixed to the indicated composition, mixed wet, and then dried.
1100 #13 Calcined at 50°C for 5 hours, then crushed and passed through a 35G mesh sieve to give an average particle size of about 5 microns.
表３は、表１のＰｂＯ−Ｖ２Ｏ３−ＴｅＯ２系ガラス粉
末に表２のチタン酸鉛固溶体粉末を混合してなる本発明
の実施例（試料Ｎｌｌ〜２１）、及びチタン酸鉛固溶体
粉末の代わりにウイレマイト粉末を混合してなる比較例
（試料Ｎｌ１２２）を示している。Table 3 shows examples of the present invention (samples Nll to 21) in which the PbO-V2O3-TeO2-based glass powder in Table 1 is mixed with the lead titanate solid solution powder in Table 2, and in place of the lead titanate solid solution powder. A comparative example (sample Nl122) in which willemite powder is mixed is shown.
以下余白
表３の低融点封着用組成物は、ＰｂＯ−Ｖ２Ｏ３−Ｔｅ
Ｏ３系ガラス粉末に、フィラーとしてチタン酸鉛固溶体
粉末あるいはウイレマイト粉末を表に示す割合に混合し
たものであり、表中の熱膨張係数は、各試料の焼結体を
直径４■、長さ５０ａｍの円柱状に成形し、デイラドメ
ーター（Ｄ ｉ ｌａｔｏｍｅｔｅｒ ）によって測定
したものである。また封着温度は、各試料から外径２０
ＩＩｌ１１高さ５ｍ＋＋のボタンを作製後、板ガラス上
でこのボタンを加熱して流動させ、その外径が２２ｍｍ
になった温度を示したものである。The low melting point sealing composition in Table 3 below is PbO-V2O3-Te.
It is a mixture of O3-based glass powder and lead titanate solid solution powder or willemite powder as a filler in the proportions shown in the table.The thermal expansion coefficients in the table are as follows: It was molded into a cylindrical shape and measured using a dilatometer. In addition, the sealing temperature was determined by the outer diameter 20 mm from each sample.
IIl11 After making a button with a height of 5 m++, the button was heated on a plate glass to make it flow, and its outer diameter was 22 mm.
This shows the temperature reached.
表３から明らかなように実施例である試料点１〜２１は
、熱膨張係数が７０〜８５Ｘ １０−’／ ”Ｃであり
、封着温度が３５０〜３７０℃であった。これに対して
比較例である試料Ｎα２２は、熱膨張係数は８５Ｘ １
０−’／℃と低い値を示したものの、封着温度について
は加熱してもボタンが殆ど流動せず、測定が不可能であ
った。As is clear from Table 3, sample points 1 to 21, which are examples, had a thermal expansion coefficient of 70 to 85X 10-'/''C and a sealing temperature of 350 to 370C. Sample Nα22, which is a comparative example, has a thermal expansion coefficient of 85X 1
Although it showed a low value of 0-'/°C, the button hardly flowed even when heated, making it impossible to measure the sealing temperature.
これらの事実は、本発明の低融点封着用組成物が、アル
ミナや窓板ガラスの熱膨張係数（それぞれ７０Ｘ １０
−７／’Ｃ１８５Ｘ１０〜７／℃）に近似した低い熱膨
張係数を示し、しかも流動性が良好であり、低い温度で
封着できることを示している。These facts indicate that the low melting point sealing composition of the present invention has a thermal expansion coefficient of 70×10
-7/' C185
なお、比較例でチタン酸鉛固溶体粉末の代わりに用いた
ウイレマイト粉末は、亜鉛華、光学ガラス用石粉を２Ｚ
ｎＯ・５ｉＯ７の組成になるように調合、混合し、１４
００℃で１６時間焼成したものを粉砕して２５０メツシ
ユの篩を通過させたものである。In addition, the willemite powder used in place of the lead titanate solid solution powder in the comparative example was zinc white, stone powder for optical glass, and 2Z.
Blend and mix to have a composition of nO・5iO7, 14
It was baked at 00°C for 16 hours, pulverized, and passed through a 250-mesh sieve.
［効果］
以上説明したように、本発明の低融点封着用組成物は、
ＰｂＯ−Ｖ２Ｏ３−ＴｅＯ□系ガラメガラス粉末の系の
ガラスと相性の良いチタン酸鉛固溶体粉末からなり、熱
膨張係数がアルミナや窓板ガラスに近似した低い値を示
すとともに、良好な流動性を有するために、セラミック
パッケージや表示デバイスを４００℃以下の温度で封着
することが可能である。[Effect] As explained above, the low melting point sealing composition of the present invention has the following effects:
It is made of lead titanate solid solution powder that is compatible with glass of the PbO-V2O3-TeO□ type glass powder system, and has a low coefficient of thermal expansion similar to that of alumina and window glass, and has good fluidity. , it is possible to seal ceramic packages and display devices at temperatures below 400°C.
特許出願人 日本電気硝子株式会社 代表者 岸 １）清 作Patent applicant: Nippon Electric Glass Co., Ltd. Representative: Kishi 1) Saku Kiyoshi
Claims (1)
２０〜５５％、ＴｅＯ＿２５〜４０％、Ａｌ＿２Ｏ＿３
０〜８％、ＺｎＯ０〜１０％、Ｎｂ＿２Ｏ＿５０〜１０
％の組成を有するＰｂＯ−Ｖ＿２Ｏ＿５−ＴｅＯ＿２系
ガラス粉末と、チタン酸鉛固溶体粉末とからなり、チタ
ン酸鉛固溶体粉末は、ＰｂＴｉＯ＿３のＰｂの５〜４０
原子％がＣａ、Ｓｒ、Ｂａの群から選ばれる１種または
２種以上により置換され、及び／または、Ｔｉの５〜９
０原子％がＺｒ、Ｓｎ、Ｍｇ、Ｃｏ、Ｚｎ、Ｎｉ、Ｍｎ
、Ｃｕ、Ｆｅ、Ａｌ、Ｂｉ、Ｎｂ、Ｔａ、Ｓｂ、Ｔｅ、
Ｖ、Ｍｏ、Ｗの群から選ばれる１種または２種以上によ
り置換されたものであることを特徴とする低融点封着用
組成物。(1) PbO20-55% by weight percentage, V_2O_5
20-55%, TeO_25-40%, Al_2O_3
0~8%, ZnO0~10%, Nb_2O_50~10
% of PbO-V_2O_5-TeO_2-based glass powder and lead titanate solid solution powder.
Atomic % is substituted with one or more selected from the group of Ca, Sr, and Ba, and/or 5 to 9 of Ti
0 atomic % is Zr, Sn, Mg, Co, Zn, Ni, Mn
, Cu, Fe, Al, Bi, Nb, Ta, Sb, Te,
1. A low melting point sealing composition characterized in that it is substituted with one or more selected from the group of V, Mo, and W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28467390A JPH04160035A (en) | 1990-10-22 | 1990-10-22 | Low-melting point sealing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28467390A JPH04160035A (en) | 1990-10-22 | 1990-10-22 | Low-melting point sealing composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04160035A true JPH04160035A (en) | 1992-06-03 |
Family
ID=17681501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28467390A Pending JPH04160035A (en) | 1990-10-22 | 1990-10-22 | Low-melting point sealing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04160035A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256040A (en) * | 1993-03-03 | 1994-09-13 | Futaba Corp | Sealing glass |
| DE19833252A1 (en) * | 1998-07-23 | 2000-02-10 | Schott Glas | Composite solder glass with a low melting temperature, a filler therefor, and its use |
| US6802987B1 (en) * | 1998-10-22 | 2004-10-12 | Texas Instruments Incorporated | Integrated circuit ferroelectric infrared detector and method |
| WO2016006338A1 (en) * | 2014-07-11 | 2016-01-14 | 株式会社村田製作所 | Composite and cooling device |
-
1990
- 1990-10-22 JP JP28467390A patent/JPH04160035A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256040A (en) * | 1993-03-03 | 1994-09-13 | Futaba Corp | Sealing glass |
| DE19833252A1 (en) * | 1998-07-23 | 2000-02-10 | Schott Glas | Composite solder glass with a low melting temperature, a filler therefor, and its use |
| US6251810B1 (en) | 1998-07-23 | 2001-06-26 | Schott Glas | Composite solder glass, filling material for same and methods of using same |
| DE19833252C2 (en) * | 1998-07-23 | 2002-01-31 | Schott Glas | Composite solder glass with a low melting temperature, a filler therefor, a process for its production and its use |
| US6802987B1 (en) * | 1998-10-22 | 2004-10-12 | Texas Instruments Incorporated | Integrated circuit ferroelectric infrared detector and method |
| WO2016006338A1 (en) * | 2014-07-11 | 2016-01-14 | 株式会社村田製作所 | Composite and cooling device |
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