JP4988375B2 - Glass composition - Google Patents
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- JP4988375B2 JP4988375B2 JP2007041922A JP2007041922A JP4988375B2 JP 4988375 B2 JP4988375 B2 JP 4988375B2 JP 2007041922 A JP2007041922 A JP 2007041922A JP 2007041922 A JP2007041922 A JP 2007041922A JP 4988375 B2 JP4988375 B2 JP 4988375B2
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- 239000011521 glass Substances 0.000 title claims description 83
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000010703 silicon Substances 0.000 claims description 47
- 229910052710 silicon Inorganic materials 0.000 claims description 47
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 46
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 19
- 239000005297 pyrex Substances 0.000 description 19
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 239000005388 borosilicate glass Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 239000002419 bulk glass Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910000575 Ir alloy Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Glass Compositions (AREA)
Description
本発明は、熱膨張率が小さく、かつ脱泡・清澄性に優れ、熔融し易いガラス組成物に関する。さらに、熱膨張特性がシリコンのそれに類似し、陽極接合用ガラスとして好適なガラス組成物に関する。 The present invention relates to a glass composition that has a low coefficient of thermal expansion, is excellent in defoaming and clarity, and is easy to melt. Further, the present invention relates to a glass composition having thermal expansion characteristics similar to that of silicon and suitable as an anodic bonding glass.
熱膨張率の小さなガラス、すなわち低膨張ガラスは、温度変化による膨張・収縮率が小さいことから、熱ショックが加わっても割れにくい、食器や理化学容器として、さらに外温が変化しても特性が変化しにくい光学部品など、様々な分野で用いられている。 Glass with a low coefficient of thermal expansion, that is, low expansion glass, has a small expansion / contraction rate due to temperature change, so it is difficult to break even when heat shock is applied. It is used in various fields such as optical components that are difficult to change.
最も汎用性のある安価な低膨張ガラスとして、パイレックス（登録商標）と呼ばれるコーニング社の硼珪酸ガラスが知られている。このガラスは、概略組成が質量百分率でＳｉＯ2 ８１％、Ｂ2Ｏ3 １３％、Ａｌ2Ｏ3 ２％、Ｎａ2Ｏ ４％であり、室温から３５０℃までの平均熱膨張係数は約３３×１０-7Ｋ-1である。 As the most versatile and inexpensive low expansion glass, Corning borosilicate glass called Pyrex (registered trademark) is known. This glass has an approximate composition of SiO 2 81%, B 2 O 3 13%, Al 2 O 3 2%, Na 2 O 4% by mass percentage, and an average coefficient of thermal expansion from room temperature to 350 ° C. is about 33 × 10 -7 K -1
この平均熱膨張係数は、窓ガラスなど一般建材に用いられるソーダライムガラスと比較して半分程度以下であり、パイレックス（登録商標）が産業用および民生用として様々な分野で用いられている大きな理由のひとつである。 This average coefficient of thermal expansion is less than about half that of soda-lime glass used for general building materials such as window glass, and Pyrex (registered trademark) is used in various fields for industrial and consumer purposes. It is one of.
一方、パイレックス（登録商標）を始めとし、低膨張ガラスとして知られる硼珪酸ガラスは、ＳｉＯ2含有率の高いことがひとつの特徴である。前述したように、パイレックス（登録商標）には、質量百分率で８０％ものＳｉＯ2が含まれている。 On the other hand, borosilicate glass known as low expansion glass such as Pyrex (registered trademark) is characterized by high SiO 2 content. As described above, Pyrex (registered trademark) contains as much as 80% SiO 2 by mass.
一般に、ＳｉＯ2含有率を高くすると、低い熱膨張率が得られるほか、耐水性や耐酸性といった、化学的耐久性が向上するなどの利点がある。 In general, when the SiO 2 content is increased, a low coefficient of thermal expansion is obtained, and there are advantages such as improved chemical durability such as water resistance and acid resistance.
一方、このような硼珪酸ガラスの熔融には、非常に高い温度を必要とする。
低膨張ガラスの熔融には、ソーダライムガラスと比較して、概ね数百℃以上の高い温度が必要であって、具体的には、概ね１６００℃程度以上の温度である。高温熔融が必要であるほど、燃料費が上昇するばかりか、熔融炉の維持にもコストがかかり、結果的に製造原価が上昇してしまう。
On the other hand, melting of such borosilicate glass requires a very high temperature.
The melting of the low expansion glass requires a high temperature of about several hundred degrees Celsius or higher as compared with soda lime glass, and specifically, a temperature of about 1600 degrees Celsius or higher. The higher the melting required, the higher the fuel cost, and the higher the cost of maintaining the melting furnace, resulting in an increase in manufacturing costs.
また、高温で原料を熔融するために、高温で安定な白金製の容器が必要である。例えば、純白金製容器の利用可能な温度上限は、実用的に１６５０℃〜１７００℃程度である。さらに高温で原料を熔融する場合には、例えば、白金とイリジウムの合金を用いた、非常に高価な容器を使用しなければならない。 Further, in order to melt the raw material at a high temperature, a platinum container stable at a high temperature is required. For example, the upper limit of the usable temperature of a pure platinum container is practically about 1650 ° C. to 1700 ° C. Further, when melting the raw material at a high temperature, for example, a very expensive container using an alloy of platinum and iridium must be used.
さらに、組成に占めるＳｉＯ2の割合が高ければ、原料の総重量のうち酸化珪素の占める割合が高くなるため、得率、すなわち原料中の酸化物の重量を全原料の総重量で除した値の百分率は高くなってしまう。 Furthermore, if the proportion of SiO 2 in the composition is high, the proportion of silicon oxide in the total weight of the raw material increases, so the yield, that is, the value obtained by dividing the weight of oxide in the raw material by the total weight of all raw materials. The percentage of will be high.
一般に、酸化物原料の割合が高く高得率のバッチは、得率を適度に抑えたバッチと比較して、脱泡や清澄が難しい。得率を抑えたバッチでは、熔融の際に炭酸ガスを発生する炭酸塩等の原料を適度に使用できるので、脱泡や清澄が容易である。
このため、高得率のバッチでは、攪拌を最適化することのほか、長時間熔融する、あるいは清澄剤を添加することなどが必要とされる。高温でしかも長時間の熔融が必要であれば、製造コストが高くなることは自明である。
In general, a batch with a high ratio of oxide raw materials and a high yield is difficult to defoam and clarify as compared with a batch with a moderate yield. In batches with a reduced yield, raw materials such as carbonates that generate carbon dioxide gas during melting can be used in an appropriate manner, so that defoaming and clarification are easy.
For this reason, in addition to optimizing the agitation, it is necessary to melt for a long time or to add a clarifier in a high yield batch. It is self-evident that the manufacturing cost increases if melting at a high temperature is required for a long time.
一方、高温において融液の清澄効果が期待できる添加物としては、例えば亜ヒ酸が挙げられるが、亜ヒ酸は環境問題もあり、可能な限り使用しないことが望ましい。
以上のことから、従来の低熱膨張硼珪酸ガラスと同様の低い熱膨張率を持ち、かつ、原料をより低温で熔融し得るガラスの開発が望まれていた。
On the other hand, an additive that can be expected to have a clarification effect on the melt at high temperatures includes, for example, arsenic acid. However, arsenic acid also has environmental problems, and it is desirable not to use it as much as possible.
From the above, it has been desired to develop a glass having a low thermal expansion coefficient similar to that of conventional low thermal expansion borosilicate glass and capable of melting raw materials at a lower temperature.
ところで、気体や液体の圧力センサ、動体の加速度センサ、光通信光のスイッチングデバイスなどの小型化、低コスト化の実現のために、ＭＥＭＳ（Micro Electro Mechanical System：微小電気機械システム）と呼ばれるデバイスが用いられている。その構成部品のひとつとして、３５×１０-7Ｋ-1程度の熱膨張係数を持つシリコンとできる限り熱膨張特性の近いガラスが必要とされるようになった。 By the way, in order to realize miniaturization and cost reduction of gas and liquid pressure sensors, moving body acceleration sensors, optical communication light switching devices, and the like, there is a device called MEMS (Micro Electro Mechanical System). It is used. As one of the components, silicon having a thermal expansion coefficient of about 35 × 10 −7 K −1 and glass having a thermal expansion characteristic as close as possible have been required.
ＭＥＭＳとは、半導体の微細加工技術を駆使して作られる微小な部品から構成される電気機械システムであり、マイクロマシンとも呼ばれている。ＭＥＭＳを構成する部品のひとつとして、ガラスは、シリコンを支持する台座や、電気的絶縁を取るための基板として用いられている。 MEMS is an electromechanical system composed of minute parts made by making full use of semiconductor microfabrication technology, and is also called a micromachine. As one of the components constituting the MEMS, glass is used as a base for supporting silicon and a substrate for taking electrical insulation.
ガラスとシリコンとは接合して用いられる。この接合には、陽極接合法という接着剤を用いない方法が利用される。この陽極接合時に数百℃程度の加熱が必要であるため、ガラスの熱膨張係数は、シリコンのそれ（３５×１０-7Ｋ-1程度）にできるだけ近いことが望ましい。 Glass and silicon are used by bonding. For this bonding, an anodic bonding method that does not use an adhesive is used. Since heating at about several hundred degrees Celsius is necessary at the time of this anodic bonding, it is desirable that the thermal expansion coefficient of glass be as close as possible to that of silicon (about 35 × 10 −7 K −1 ).
シリコンとの熱膨張係数差が大きいと、陽極接合後の接合境界面での残留歪みが大となり、ＭＥＭＳの強度や特性に悪影響を及ぼす可能性が生じる。さらに、シリコンとの熱膨張係数差が大きすぎると、陽極接合の際の冷却時に、ガラスやシリコンが破損する。
なお、この陽極接合のために、ＭＥＭＳに用いられるガラスの組成には、易移動性陽イオン、実質的にはＬｉ+またはＮａ+が適量含まれていることが必要である。
When the difference in thermal expansion coefficient from silicon is large, the residual strain at the bonding interface after anodic bonding becomes large, which may adversely affect the strength and characteristics of the MEMS. Furthermore, if the difference in thermal expansion coefficient from silicon is too large, glass and silicon are damaged during cooling during anodic bonding.
For this anodic bonding, the composition of the glass used for MEMS needs to contain an appropriate amount of a mobile cation, substantially Li + or Na + .
前述のパイレックス（登録商標）は、組成中にＮａ+を含み、かつシリコンと熱膨張係数が近いことから、シリコンとの陽極接合が可能であり、ＭＥＭＳ用途としては広く用いられている。しかし、パイレックス（登録商標）の平均熱膨張係数は、シリコンのそれに近いものの、熱膨張の温度依存性については、シリコンのそれと完全に一致するわけではない。 The above-mentioned Pyrex (registered trademark) contains Na + in the composition and has a thermal expansion coefficient close to that of silicon, so that anodic bonding with silicon is possible, and it is widely used as a MEMS application. However, although the average thermal expansion coefficient of Pyrex (registered trademark) is close to that of silicon, the temperature dependence of thermal expansion does not completely match that of silicon.
すなわち、熱膨張の温度依存性をシリコンのそれと比較すると、パイレックス（登録商標）は、３００℃程度までの比較的低温の領域ではシリコンよりも熱膨張が大きく、３００℃より高温の領域ではシリコンよりも熱膨張が小さくなるという特性を持っている。その結果、例えば、パイレックス（登録商標）を台座とした圧力センサは、温度変化によってシリコンに歪みが生じ、高精度の測定に支障をきたすという課題があった。 That is, comparing the temperature dependence of thermal expansion with that of silicon, Pyrex (registered trademark) has a larger thermal expansion than silicon in a relatively low temperature region up to about 300 ° C., and higher than that of silicon in a region higher than 300 ° C. Also has a characteristic that thermal expansion is reduced. As a result, for example, a pressure sensor using Pyrex (registered trademark) as a pedestal has a problem in that silicon is distorted by a change in temperature, which hinders high-accuracy measurement.
この課題の解決のため、「陽極接合用ガラス」と呼ばれる陽極接合専用のガラスも開発されている。陽極接合用途のガラス組成物としては、例えば特開平４−８３７３３号公報や、特開平７−５３２３５号公報、特開２００１−７２４３３号公報などが公開されている。
これら公報に示されているガラス組成物は、シリコンの熱膨張曲線と合致するように組成設計されている。このため、パイレックス（登録商標）よりも良好な、すなわち、残留応力の小さい陽極接合を行うことができる。このようなガラス組成物を陽極接合したＭＥＭＳでは、温度変化に対するシリコンの歪みも小さいとされている。 The glass compositions shown in these publications are designed to match the thermal expansion curve of silicon. For this reason, it is possible to perform anodic bonding that is better than Pyrex (registered trademark) , that is, with low residual stress. In MEMS in which such a glass composition is anodically bonded, the strain of silicon with respect to temperature change is also small.
しかしながら、このような陽極接合用ガラスは、組成中にＳｉＯ2を比較的多くの割合で含んでいる。前述したように、このような組成は、熔融可能な温度が高く、熔融温度での融液の粘性も高い。したがって、脱泡、清澄、均質化に時間を要し、品質の良いガラスを製造するためには、コスト高になっていた。 However, such an anodic bonding glass contains SiO 2 in a relatively large proportion in the composition. As described above, such a composition has a high melting temperature and a high viscosity of the melt at the melting temperature. Therefore, it takes time for defoaming, clarification, and homogenization, and it has been expensive to produce a glass of good quality.
そこで本発明の目的は、１６００℃程度以下で、比較的短時間での熔融が可能であり、かつ５０℃〜３５０℃の平均熱膨張係数が５０×１０-7Ｋ-1以下の低い熱膨張係数を有するガラス組成物を提供する。 Accordingly, an object of the present invention is to achieve melting in a relatively short time at about 1600 ° C. or less, and low thermal expansion with an average coefficient of thermal expansion of 50 ° C. to 350 ° C. of 50 × 10 −7 K −1 or less. A glass composition having a modulus is provided.
課題を解決するために研究を重ねた結果、組成中のシリカの含有率が５５ｍｏｌ％以下のアルミノ硼珪酸ガラス系において、１６００℃程度以下で熔融できる低膨張ガラスの組成範囲を見出した。さらに、この組成範囲の中でも、シリコンとの熱膨張の温度依存性が極めて近く、良好な陽極接合を可能とするガラス組成範囲をも見出した。 As a result of repeated studies to solve the problems, the inventors have found a composition range of low expansion glass that can be melted at about 1600 ° C. or less in an aluminoborosilicate glass system having a silica content of 55 mol% or less. Furthermore, among these composition ranges, the temperature dependence of thermal expansion with silicon was extremely close, and a glass composition range that enables good anodic bonding was also found.
本発明によるガラス組成物は、
ｍｏｌ％で表示して、
ＳｉＯ2：２５〜５５％、
Ｂ2Ｏ3：２０〜４５％、
Ａｌ2Ｏ3：１５〜２５％、
ＣａＯ＋ＭｇＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ：３〜１８％、
Ｌｉ2Ｏ＋Ｎａ2Ｏ：１〜３％、
を含んでなり、かつ５０℃〜３５０℃における熱膨張係数が５０×１０-7Ｋ-1以下であることを特徴とする。
The glass composition according to the present invention comprises:
Displayed in mol%,
SiO 2 : 25 to 55%,
B 2 O 3 : 20 to 45%,
Al 2 O 3: 15~25%,
CaO + MgO + SrO + BaO + ZnO: 3 to 18%,
Li 2 O + Na 2 O: 1-3%
And a thermal expansion coefficient at 50 ° C. to 350 ° C. is 50 × 10 −7 K −1 or less.
以下に各ガラス成分の限定の理由について説明する。以下の％は、ｍｏｌ表示である。
（ＳｉＯ2）
ＳｉＯ2は、ガラス網目形成する必須成分である。ガラスの安定性や、所望の熱膨張係数を得るために、その含有率の下限は２５％以上とする。
一方、１６００℃程度以下での熔融を可能とし、脱泡や清澄を容易にするために、含有率の上限を５５％とする。
シリコンと陽極接合するために、その含有率の下限を４５％以上とする。こうすると、室温から３５０℃までの平均線膨張係数を、概ね４０×１０-7Ｋ-1以下にできる。
The reason for limitation of each glass component is demonstrated below. The following% is expressed in mol.
(SiO 2 )
SiO 2 is an essential component for forming a glass network. In order to obtain glass stability and a desired thermal expansion coefficient, the lower limit of the content is set to 25% or more.
On the other hand, in order to enable melting at about 1600 ° C. or less and facilitate defoaming and clarification, the upper limit of the content is set to 55%.
In order to perform anodic bonding with silicon, the lower limit of the content is set to 45% or more. In this way, the average linear expansion coefficient from room temperature to 350 ° C. can be made approximately 40 × 10 −7 K −1 or less.
なお、良好な陽極接合のためには、熱膨張係数がシリコンのそれと近いだけではなく、熱膨張係数の温度特性がシリコンのそれに近いことが望ましい。本発明によるガラス組成物とシリコンとの熱膨張係数差の温度特性については、後で詳述する。 For good anodic bonding, it is desirable that not only the thermal expansion coefficient is close to that of silicon but also the temperature characteristic of the thermal expansion coefficient is close to that of silicon. The temperature characteristics of the difference in thermal expansion coefficient between the glass composition according to the present invention and silicon will be described in detail later.
（Ｂ2Ｏ3）
Ｂ2Ｏ3は、ガラス網目を形成する必須成分であり、ガラス形成能を良くするとともに、高温粘性を低下させて熔融性を向上させる成分である。そのために含有率の下限を２０％以上とする。一方、化学的耐久性の確保や熱膨張係数を抑えるために、含有率の上限を４５％以下とする。シリコンと陽極接合するために、その含有率の上限を３０％以下にするとよい。
(B 2 O 3 )
B 2 O 3 is an essential component that forms a glass network, and is a component that improves glass forming ability and lowers high-temperature viscosity to improve meltability. Therefore, the lower limit of the content rate is set to 20% or more. On the other hand, in order to ensure chemical durability and suppress the thermal expansion coefficient, the upper limit of the content is set to 45% or less. In order to perform anodic bonding with silicon, the upper limit of the content is preferably 30% or less.
（Ａｌ2Ｏ3）
Ａｌ2Ｏ3は、ガラス網目の形成と、ガラス網目を修飾する両方の役割を果たす必須成分である。Ａｌ2Ｏ3は、ガラスの安定性と化学的耐久性を向上させるとともに、熱膨張係数の低下に寄与する。そのために含有率の下限を１５％以上とする。一方、融液の粘性を抑え、１６００℃程度以下での熔融を可能とするために、含有率の上限を２５％以下とし、さらに２０％以下とすることが好ましい。
(Al 2 O 3 )
Al 2 O 3 is an essential component that plays both the role of forming a glass network and modifying the glass network. Al 2 O 3 improves the stability and chemical durability of the glass and contributes to a decrease in the thermal expansion coefficient. Therefore, the lower limit of the content rate is set to 15% or more. On the other hand, in order to suppress the viscosity of the melt and enable melting at about 1600 ° C. or less, the upper limit of the content is preferably 25% or less, and more preferably 20% or less.
（アルカリ土類金属酸化物）
アルカリ土類金属酸化物、すなわち、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯは、ガラス網目修飾酸化物であり、ガラスの熔融性を向上させる成分である。同様の効果を持つＺｎＯと合わせ、本発明のガラス組成物は、これらのうち１種類以上を、合計で少なくとも３％以上含む。一方、ガラス化を可能とし、熱膨張係数が大きくなるのを防ぐために、その合計を１８％以下とする。
(Alkaline earth metal oxide)
Alkaline earth metal oxides, that is, MgO, CaO, SrO, and BaO are glass network-modifying oxides and are components that improve the meltability of glass. Combined with ZnO having the same effect, the glass composition of the present invention contains at least 3% of one or more of these. On the other hand, in order to enable vitrification and prevent the thermal expansion coefficient from increasing, the total is made 18% or less.
特にＭｇＯは、ガラスの耐失透性を確保するために、その含有率を１０％以下とすることが特に好ましい。
また、ＺｎＯは、ガラスの安定性の向上や、熔融性を向上させつつ低熱膨張化を図るに効果が大きいことから、１％以上含有させることが特に好ましい。
シリコンと陽極接合するために、上記アルカリ土類酸化物とＺｎＯとの合計含有率を、１３％以下にするとよい。
In particular, MgO is particularly preferably 10% or less in order to ensure the devitrification resistance of the glass.
In addition, ZnO is particularly preferably contained in an amount of 1% or more because it is highly effective for improving the stability of glass and reducing the thermal expansion while improving the meltability.
In order to perform anodic bonding with silicon, the total content of the alkaline earth oxide and ZnO is preferably 13% or less.
（アルカリ金属酸化物）
アルカリ金属酸化物であるＬｉ2ＯとＮａ2Ｏとは、ガラス網目を修飾する成分であり、ガラスの網目を適度に切断し、熔融温度を下げ、融液の粘性を低く抑える効果がある。このため、Ｌｉ2ＯとＮａ2Ｏとは、合計で少なくとも１％以上を含有させる。
一方、熱膨張係数が大きくなるのを防ぐために、その合計を３％以下にする。なお、Ｌｉ2ＯとＮａ2Ｏの合計量が１〜３％であることは、陽極接合するのに、必要にして十分である。
(Alkali metal oxide)
Li 2 O and Na 2 O, which are alkali metal oxides, are components that modify the glass network, and have the effect of appropriately cutting the glass network, lowering the melting temperature, and keeping the melt viscosity low. For this reason, Li 2 O and Na 2 O contain at least 1% in total.
On the other hand, in order to prevent the thermal expansion coefficient from increasing, the total is made 3% or less. It should be noted that the total amount of Li 2 O and Na 2 O being 1 to 3% is necessary and sufficient for anodic bonding.
また、原料として、炭酸塩（例えば炭酸ナトリウム）、硝酸塩（例えば硝酸ナトリウム）、硫酸塩（例えばボウ硝）など、酸化物以外の原料を用いることができるため、熔融時の脱泡や清澄を促進することもできる。 In addition, raw materials other than oxides, such as carbonates (for example, sodium carbonate), nitrates (for example, sodium nitrate), and sulfates (for example, bow glass) can be used as raw materials, thus promoting defoaming and clarification during melting. You can also
さらに、本発明のガラス組成物は、実質的に、
ｍｏｌ％で表示して、
ＳｉＯ2：２５〜５５％、
Ｂ2Ｏ3：２０〜４５％、
Ａｌ2Ｏ3：１５〜２５％、
ＣａＯ＋ＭｇＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ：３〜１８％、
Ｌｉ2Ｏ＋Ｎａ2Ｏ：１〜３％、
のみから構成されていてもよい。
Furthermore, the glass composition of the present invention substantially comprises
Displayed in mol%,
SiO 2 : 25 to 55%,
B 2 O 3 : 20 to 45%,
Al 2 O 3: 15~25%,
CaO + MgO + SrO + BaO + ZnO: 3 to 18%,
Li 2 O + Na 2 O: 1-3%
It may consist only of.
本発明のガラス組成は、１６００℃程度の温度でも脱泡性、清澄性に優れ、熔融し易いという大きな特長を持つ。しかし、一般に知られている清澄剤、すなわち、塩化物、フッ化物、ＣｅＯ2などを、原料中に少量添加することについて制限するものではない。なお、ガラスの安定化、失透の抑制などの効果を得るため、ＴｉＯ2、ＺｒＯ2あるいはＬａ2Ｏ3を、合計で１％未満まで含有させることができる。 The glass composition of the present invention has a great feature that it is excellent in defoaming and clarifying properties even at a temperature of about 1600 ° C. and is easy to melt. However, there is no limitation on the addition of a generally known fining agent, that is, chloride, fluoride, CeO 2 or the like in a small amount to the raw material. Incidentally, the stabilization of the glass, to obtain the effects such as suppression of devitrification, the TiO 2, ZrO 2 or La 2 O 3, can be contained to less than 1% in total.
本発明のガラス組成物は、上述の組成範囲を有し、さらに５０℃〜３５０℃における熱膨張係数が５０×１０-7Ｋ-1以下である、という低い熱膨張係数である特徴を有している。このため、このガラス組成物は、例えばシリコンと陽極接合しても、熱歪みを小さくできる。 The glass composition of the present invention has the above-described composition range, and further has a low thermal expansion coefficient of 50 × 10 −7 K −1 or less at 50 ° C. to 350 ° C. ing. For this reason, even if this glass composition is anodically bonded to, for example, silicon, thermal strain can be reduced.
また、本発明のガラス組成物は、５０℃〜４５０℃の温度範囲において、前記ガラス組成物の熱膨張係数と、シリコンのそれとの差の最大値が、±２．７×１０-7Ｋ-1以内であることが好ましい。このようなガラス組成物では、低い熱膨張係数であることに加えて、シリコンとの熱膨張係数の差そのものが小さいので、熱歪みをより小さくできる。 Further, in the glass composition of the present invention, in the temperature range of 50 ° C. to 450 ° C., the maximum difference between the thermal expansion coefficient of the glass composition and that of silicon is ± 2.7 × 10 −7 K −. It is preferably within 1 . In such a glass composition, in addition to having a low coefficient of thermal expansion, the difference in the coefficient of thermal expansion from silicon itself is small, so that the thermal strain can be further reduced.
本発明によるガラス組成は、脱泡性や清澄性に優れ、熔融し易いガラス組成物である。さらに、５０〜３５０℃における熱膨張係数が５０×１０-7Ｋ-1以下であり、加えてシリコンとの熱膨張率差の温度依存性が、パイレックス（登録商標）の場合に比べて小さく、陽極接合に好適なガラス組成物である。 The glass composition according to the present invention is a glass composition that is excellent in defoaming properties and clarity and is easy to melt. Furthermore, the thermal expansion coefficient at 50 to 350 ° C. is 50 × 10 −7 K −1 or less, and in addition, the temperature dependence of the difference in thermal expansion coefficient from silicon is smaller than that of Pyrex (registered trademark) , It is a glass composition suitable for anodic bonding.
（低膨張ガラス）
表1に示した所定のガラス組成となるように、ガラス原料である酸化物、炭酸塩、硝酸塩、硫酸塩などを秤量し、混合してバッチとした。なお、Ｅ１〜Ｅ２４は実施例であり、Ｃ１〜Ｃ５は、比較例である。
(Low expansion glass)
Oxides, carbonates, nitrates, sulfates, and the like, which are glass raw materials, were weighed and mixed to obtain a predetermined glass composition shown in Table 1, and a batch was obtained. In addition, E1-E24 is an Example and C1-C5 is a comparative example.
このバッチを白金製るつぼに入れ、１４００℃〜１６００℃の電気炉に投入し、適宜攪拌しながら４〜５時間程度熔融した後、カーボン製あるいはステンレス製の鋳型に流し込み、所定の温度に数時間保持して歪を除去した後、室温まで徐冷することによって、バルクのガラスを得た。 This batch is put into a platinum crucible, put into an electric furnace at 1400 ° C. to 1600 ° C., melted for about 4 to 5 hours with appropriate stirring, poured into a mold made of carbon or stainless steel, and kept at a predetermined temperature for several hours. After holding and removing the strain, bulk glass was obtained by gradually cooling to room temperature.
バルクガラス中のガラスの泡は、目視、あるいは光学顕微鏡によって観察した。作製されたバルクのガラスより、熱膨張係数測定用の試料を切り出し、示差熱膨張計によって熱膨張率を測定し、５０〜３５０℃の平均線膨張係数を計算した。 Glass bubbles in the bulk glass were observed visually or with an optical microscope. A sample for measuring the thermal expansion coefficient was cut out from the produced bulk glass, the coefficient of thermal expansion was measured with a differential thermal dilatometer, and an average linear expansion coefficient of 50 to 350 ° C. was calculated.
表２に、各ガラスにおける、平均線膨張係数（×１０-7Ｋ-1）、熔融が可能な概略温度Ｔｍ（℃）、ガラス転移点Ｔｇ（℃）を示した。表２から明らかなように、比較例２と３を除き、全ての実施例・比較例のガラス組成で、１６００℃以下の温度で熔融可能であった。全ての実施例の平均線膨張係数は５０×１０-7Ｋ-1以下であった。 Table 2 shows the average linear expansion coefficient (× 10 −7 K −1 ), the approximate melting temperature Tm (° C.), and the glass transition point Tg (° C.) in each glass. As is apparent from Table 2, the glass compositions of all Examples and Comparative Examples except for Comparative Examples 2 and 3 were meltable at a temperature of 1600 ° C. or lower. The average linear expansion coefficient of all examples was 50 × 10 −7 K −1 or less.
比較例１（Ｃ１）のガラス組成は、Ｂ2Ｏ3の含有率が多く、またＡｌ2Ｏ3含有率が少ないため、平均線膨張係数が５０×１０-7Ｋ-1を超えていた。 In the glass composition of Comparative Example 1 (C1), the average linear expansion coefficient exceeded 50 × 10 −7 K −1 because the B 2 O 3 content was high and the Al 2 O 3 content was low.
比較例４（Ｃ４）と比較例５（Ｃ５）のガラスは、いずれもＳｉＯ2を６０％含む組成物である。ＳｉＯ2含有率の高い、これら比較例のガラス組成物と、本発明のガラス組成物（実施例１７）との泡品質を比較した。これらのガラス組成物を熔融し、厚さ１ｍｍ×２５ｍｍ角の板状に加工し、その両面を光学研磨した。その試料における泡の個数をカウントし、その結果を表３に示す。 The glasses of Comparative Example 4 (C4) and Comparative Example 5 (C5) are both compositions containing 60% SiO 2 . The bubble quality was compared between the glass composition of these comparative examples having a high SiO 2 content and the glass composition of the present invention (Example 17). These glass compositions were melted and processed into a 1 mm × 25 mm square plate shape, and both surfaces thereof were optically polished. The number of bubbles in the sample was counted, and the results are shown in Table 3.
（表３）
―――――――――――――――――
泡個数 泡品質
―――――――――――――――――
実施例17 ０ ○
比較例４ ＞100 ×
比較例５ ＞100 ×
―――――――――――――――――
(Table 3)
―――――――――――――――――
Foam count Foam quality ―――――――――――――――――
Example 17 0 ○
Comparative Example 4> 100 ×
Comparative Example 5> 100 ×
―――――――――――――――――
実施例１６（Ｅ１６）におけるＳｉＯ2含有率は５５％であり、比較例２と比較例３との含有率と比較して、５％少ないに過ぎない。しかし、その清澄性の差は大きい。すなわち、比較例２と比較例３のガラス組成物には、熔融時に脱泡し切れずに残った多数の泡が観察された。これに対して、同条件で熔融した実施例１６のガラス組成物中に残留する泡は観察されなかった。 The SiO 2 content in Example 16 (E16) is 55%, which is only 5% less than the content in Comparative Example 2 and Comparative Example 3. However, the difference in clarity is large. That is, in the glass compositions of Comparative Example 2 and Comparative Example 3, a large number of bubbles remaining without being completely degassed during melting were observed. On the other hand, bubbles remaining in the glass composition of Example 16 melted under the same conditions were not observed.
（陽極接合）
シリコンとガラスとの陽極接合は、次のように実施した。
上述したようにして作製した本発明の実施例１９のガラス組成物を、２０ｍｍ×２０ｍｍ×厚さ１ｍｍのガラス基板に加工し、その両面を鏡面研磨した。これをシリコンウェハ上に載せ、４００℃程度に加熱しつつ、シリコン側を陽極、ガラス側を陰極として１ｋＶ程度の直流電圧を数十分印加した。電圧印加終了後、徐々に温度を室温まで下げた。ガラスとシリコンウェハとの接合状態を確認した。
(Anodic bonding)
Anodic bonding of silicon and glass was performed as follows.
The glass composition of Example 19 of the present invention produced as described above was processed into a glass substrate of 20 mm × 20 mm × thickness 1 mm, and both surfaces thereof were mirror-polished. While this was placed on a silicon wafer and heated to about 400 ° C., several tens of volts of DC voltage was applied with the silicon side as the anode and the glass side as the cathode. After the voltage application was completed, the temperature was gradually lowered to room temperature. The bonding state between the glass and the silicon wafer was confirmed.
その結果、実施例１９のガラスでは、陽極接合に必要な量のアルカリ金属イオンを含んでおり、パイレックス（登録商標）と同様に陽極接合することができた。
しかも、実施例１９では、シリコンとの熱膨張率差が、図1に示すように、５００℃で（−０．３２×１０-4）と、この温度域まで非常に小さいことが分かる。パイレックス（登録商標）では、（−１．９０×１０-4）である。したがって、シリコンとの接合面に発生する残留応力も、パイレックス（登録商標）のそれと比較して、小さくすることができる。
As a result, the glass of Example 19 contained an amount of alkali metal ions necessary for anodic bonding and could be anodic bonded in the same manner as Pyrex (registered trademark) .
Moreover, in Example 19, the thermal expansion coefficient difference with silicon is very small up to this temperature range at 500 ° C. (−0.32 × 10 −4 ) as shown in FIG. In Pyrex (registered trademark) , it is (−1.90 × 10 −4 ). Therefore, the residual stress generated on the bonding surface with silicon can be reduced as compared with that of Pyrex (registered trademark) .
図１に、実施例１９のガラス（○：実線）、パイレックス（登録商標）（●：破線）、シリコン（×：実線）における、単位長さ当りの伸び率の温度依存性のグラフを示す。 FIG. 1 shows a graph of the temperature dependence of the elongation per unit length in the glass of Example 19 (◯: solid line), Pyrex (registered trademark) (●: broken line), and silicon (×: solid line).
図２に、実施例１９のガラス（○：実線）、パイレックス（登録商標）（●：破線）、シリコン（×：実線）における、熱膨張係数の温度依存性のグラフを示す。 In FIG. 2, the graph of the temperature dependence of the thermal expansion coefficient in the glass of Example 19 ((circle): solid line), Pyrex (trademark) (-: broken line), and silicon (x: solid line) is shown.
図３に、実施例１９のガラス（○：実線）とパイレックス（登録商標）（●：破線）における、シリコンとの単位長さ当りの伸び率の差に関する、温度依存性のグラフを示す。これは、シリコンとの熱膨張特性の差を明確に示すためのグラフである。 FIG. 3 shows a graph of temperature dependence regarding the difference in elongation rate per unit length between silicon (Example: solid line) of Example 19 and Pyrex (registered trademark) (●: broken line). This is a graph for clearly showing the difference in thermal expansion characteristics from silicon.
まず、パイレックス（登録商標）では、３００℃程度まではシリコンよりも膨張しやすく、一方３００℃を超えると、シリコンよりも膨張しにくいという特性を持っていることが分かる。シリコンとパイレックス（登録商標）との陽極接合は、通常４００℃程度以上で行われる。４００℃以上の温度域から室温まで冷却すると、初めはシリコンの方がより縮み、３００℃程度以下になると逆にパイレックス（登録商標）の方が大きく縮む。結果として、接合された試料の界面には応力が残留し、これを用いたＭＥＭＳデバイスの温度特性の悪化や、デバイスそのものの歪を引き起こす可能性がある。 First, it can be seen that Pyrex (registered trademark) has a characteristic that it expands more easily than silicon up to about 300 ° C., and has a characteristic that it does not easily expand more than silicon when it exceeds 300 ° C. Anodic bonding of silicon and Pyrex (registered trademark) is usually performed at about 400 ° C. or higher. When cooling from a temperature range of 400 ° C. or more to room temperature, silicon shrinks more at first, and when it becomes about 300 ° C. or less, Pyrex (registered trademark) shrinks more greatly. As a result, stress remains at the interface of the bonded sample, which may cause deterioration of the temperature characteristics of the MEMS device using the sample and distortion of the device itself.
Claims (4)
ＳｉＯ2：２５〜５５％、
Ｂ2Ｏ3：２０〜４５％、
Ａｌ2Ｏ3：１５〜２５％、
ＣａＯ＋ＭｇＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ：３〜１８％、
Ｌｉ2Ｏ＋Ｎａ2Ｏ：１〜３％、
を含んでなり、かつ５０℃〜３５０℃における熱膨張係数が５０×１０-7Ｋ-1以下であるガラス組成物。 Displayed in mol%,
SiO 2 : 25 to 55%,
B 2 O 3 : 20 to 45%,
Al 2 O 3: 15~25%,
CaO + MgO + SrO + BaO + ZnO: 3 to 18%,
Li 2 O + Na 2 O: 1-3%
And a thermal expansion coefficient at 50 ° C. to 350 ° C. of 50 × 10 −7 K −1 or less.
前記ＳｉＯ2が４５〜５５％、
前記Ｂ2Ｏ3が２０〜３０％、
前記（ＣａＯ＋ＭｇＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ）が３〜１３％、
であり、かつ前記熱膨張係数が４０×１０-7Ｋ-1以下である請求項１に記載のガラス組成物。 Displayed in mol%,
The SiO 2 is 45 to 55%,
20-30% of the B 2 O 3
(CaO + MgO + SrO + BaO + ZnO) is 3 to 13%,
The glass composition according to claim 1, wherein the thermal expansion coefficient is 40 × 10 −7 K −1 or less.
前記ＳｉＯ2が５０〜５５％、
前記Ａｌ2Ｏ3が１５〜２０％、
前記（ＣａＯ＋ＭｇＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ）が３〜５％、
前記（Ｌｉ2Ｏ＋Ｎａ2Ｏ）が２〜３％、
である請求項２に記載のガラス組成物。 Displayed in mol%,
The SiO 2 is 50 to 55%,
15-20% of the Al 2 O 3 ,
(CaO + MgO + SrO + BaO + ZnO) is 3 to 5%,
(Li 2 O + Na 2 O) is 2 to 3%,
The glass composition according to claim 2.
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