JP2010254505A - Low temperature-fired, high-strength, low thermal expansion ceramic and method for producing the same - Google Patents
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本発明は、低温焼成高強度低熱膨張性磁器及びその製造方法に関する。さらに詳しく言えば、本発明は、多層基板用材料、構造材料として信頼性が高く、Ａｇ、Ａｕ、Ｃｕ等の低抵抗金属と同時焼成できる、低温焼成可能な高強度低熱膨張性磁器用組成物、その組成物から得られる磁器及びその製造方法に関するものである。 The present invention relates to a low-temperature fired high-strength low-thermal-expansion ceramic and a method for producing the same. More specifically, the present invention is highly reliable as a multilayer substrate material and structural material, and can be fired at the same time with a low resistance metal such as Ag, Au, Cu, etc., and can be fired at a low temperature. The present invention relates to a porcelain obtained from the composition and a method for producing the same.
近年、高度情報化時代を迎え、半導体素子には、高速化と共に、高集積化、及び実装の高密度化が求められている。高集積化や実装の高密度化のためには抵抗率の低い配線材料（Ａｇ、Ａｕ、Ｃｕ等）の使用が求められるが、これらの金属は融点が低いため、配線パターンの印刷後に基板を焼成する多層配線基板等では、低温焼成可能な基板材料を用いる必要がある。このため、電子機器用基板材料として従来広く用いられてきたアルミナ基板に代わる、低温焼成可能な材料が必要とされている。 In recent years, with the advent of advanced information technology, semiconductor devices are required to have higher integration, higher integration, and higher mounting density. The use of low-resistivity wiring materials (Ag, Au, Cu, etc.) is required for higher integration and higher packaging density. However, since these metals have a low melting point, the substrate is printed after the wiring pattern is printed. In a multilayer wiring board to be fired, it is necessary to use a substrate material that can be fired at a low temperature. Therefore, there is a need for a material that can be fired at a low temperature in place of an alumina substrate that has been widely used as a substrate material for electronic equipment.
最近では、ガラスと無機質フィラーとからなるガラスセラミックス材料が検討されている。例えば、特開２０００−１８８０１７号公報（特許文献１）には、ディオプサイド（ＣａＭｇＳｉ2Ｏ6）型結晶相を析出可能なガラス相と、フィラーとしてＭｇ及び／またはＺｎとＴｉとを含有する酸化物を含む１０００℃以下で焼成可能な磁器用組成物が開示されている。この種のガラスセラミックス材料は、８００〜１０００℃の温度で焼成することができるため、導体抵抗の低いＡｇ、Ａｕ、Ｃｕ等と同時焼成できるという特長がある。 Recently, glass ceramic materials composed of glass and inorganic fillers have been studied. For example, JP 2000-188017 A (Patent Document 1) contains a glass phase capable of precipitating a diopside (CaMgSi 2 O 6 ) type crystal phase and Mg and / or Zn and Ti as fillers. A porcelain composition containing an oxide that can be fired at 1000 ° C. or lower is disclosed. Since this type of glass ceramic material can be fired at a temperature of 800 to 1000 ° C., it has a feature that it can be fired simultaneously with Ag, Au, Cu or the like having a low conductor resistance.
高集積化に伴う半導体電子回路線幅の微細化が進み、シリコンウエハに電子回路を形成する露光装置用のＸ−Ｙステージには高精度で高い位置精度が要求され、露光装置用のＸ−Ｙステージ用のセラミックス材料や、シリコンウエハを載置する静電チャック用のセラミックス材料として、アルミナセラミックスや窒化珪素セラミックスが、従来、広く用いられてきた。前記静電チャック用のセラミックス材料としてコージェライトセラミックスが提案されている。 With the progress of miniaturization of semiconductor electronic circuit line width due to high integration, an XY stage for an exposure apparatus for forming an electronic circuit on a silicon wafer is required to have high precision and high positional accuracy. Conventionally, alumina ceramics and silicon nitride ceramics have been widely used as ceramic materials for Y stages and ceramic materials for electrostatic chucks on which silicon wafers are placed. Cordierite ceramics have been proposed as a ceramic material for the electrostatic chuck.
露光時の熱変形を軽減するためには、露光装置の使用温度での熱膨張性は低い方がよく、低熱膨張性のものが求められている。コージェライトセラミックスは、アルミナセラミックスや窒化珪素セラミックスと比較して、熱膨張性が低いが、剛性が小さいことが知られている。β−スポジュメンも剛性が小さい。 In order to reduce thermal deformation during exposure, it is better that the thermal expansion at the operating temperature of the exposure apparatus is low, and a low thermal expansion is required. Cordierite ceramics are known to be less rigid but less rigid than alumina ceramics or silicon nitride ceramics. β-spodumene is also less rigid.
雰囲気温度での熱膨張性が高いと、温度変化による変形により、シリコンウエハ回路形成時や検査時のウエハ支持体の位置決め精度に影響を与え、製品品質及び歩留りに問題が発生する。また、シリコンウエハ支持体に外部衝撃が加わると、支持体が振動し、振動した状態で回路形成や検査を行うと、精度が低下する。振動は、支持体の剛性が低いことに起因するので、支持体には高い強度が要求される。しかし、高強度化を進めると、逆に熱膨張性が大きくなる傾向があった。 If the thermal expansibility at the ambient temperature is high, the deformation due to the temperature change affects the positioning accuracy of the wafer support during the formation of the silicon wafer circuit or at the time of inspection, causing problems in product quality and yield. In addition, when an external impact is applied to the silicon wafer support, the support vibrates, and if circuit formation or inspection is performed in the vibrated state, the accuracy decreases. Since vibration is caused by the low rigidity of the support, the support is required to have high strength. However, when the strength is increased, the thermal expansibility tends to increase.
従来、コージェライトセラミックスやリチウムアルミノシリケートセラミックスは、低熱膨張性セラミックスとして知られている。しかし、コージェライトセラミックスは、原料粉末に焼結助剤を添加し、所定形状に成形後、１０００〜１４００℃の温度で焼成することによって製造する（特開平２−２２９７６０号公報：特許文献２）。また、リチウムアルミノシリケートセラミックスについては、β−スポジュメンは、原料を所定形状に成形後、１１００〜１４００℃の温度で焼成して製造する（特公昭５３−９６０５号公報：特許文献３）。 Conventionally, cordierite ceramics and lithium aluminosilicate ceramics are known as low thermal expansion ceramics. However, cordierite ceramics are manufactured by adding a sintering aid to a raw material powder, forming it into a predetermined shape, and firing it at a temperature of 1000 to 1400 ° C. (Japanese Patent Laid-Open No. Hei 2-229760: Patent Document 2). . As for lithium aluminosilicate ceramics, β-spodumene is produced by forming a raw material into a predetermined shape and firing it at a temperature of 1100 to 1400 ° C. (Japanese Patent Publication No. 53-9605: Patent Document 3).
このように、低温焼成可能で、使用温度での熱膨張性が低く、剛性が大きい低熱膨張性磁器が求められているが、熱膨張性が低いものは剛性が小さく、高強度化を進めると熱膨張性が大きくなる傾向があり、熱膨張性が低いものは焼成温度が高いといった問題があった。 Thus, there is a demand for low thermal expansion porcelain that can be fired at low temperature, has low thermal expansibility at the use temperature, and has high rigidity. There was a tendency that thermal expansibility tends to be large, and those having low thermal expansibility had a problem that the firing temperature was high.
従って、本発明の目的は、多層基板用材料、構造材料として信頼性の高い磁器であって、Ａｇ、Ａｕ、Ｃｕ等の低抵抗金属と同時焼成が可能であり、しかも高い機械的強度と低熱膨張性を実現する、低温焼成可能な高強度低熱膨張性磁器用組成物、その組成物から得られる磁器及びその製造方法の提供にある。 Accordingly, an object of the present invention is a highly reliable porcelain as a multilayer substrate material and a structural material, which can be co-fired with a low-resistance metal such as Ag, Au, Cu, and has high mechanical strength and low heat. An object of the present invention is to provide a low-strength, high-strength, low-temperature-expandable porcelain composition that realizes expansibility, a porcelain obtained from the composition, and a method for producing the same.
本発明者らは、上記課題を解決すべく鋭意検討した結果、ＬｉとＭｇとＡｌとＳｉとを特定の比率で含有する酸化物（焼成して前記酸化物を形成し得るＬｉ、Ｍｇ、Ａｌ、及びＳｉの化合物及び／または複合酸化物を含む。）を所定温度で仮焼し、粉砕した原料にＢi2Ｏ3を添加した組成物は、８５０〜９００℃程度の低温で焼成可能であり、かかる組成物を低温焼成して得られる磁器は、低熱膨張性と高強度を有することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that an oxide containing Li, Mg, Al, and Si in a specific ratio (Li, Mg, Al that can be fired to form the oxide). , And Si compounds and / or composite oxides) are calcined at a predetermined temperature, and a composition obtained by adding Bi 2 O 3 to the pulverized raw material can be fired at a low temperature of about 850 to 900 ° C. The porcelain obtained by firing such a composition at a low temperature has been found to have low thermal expansion and high strength, and the present invention has been completed.
すなわち、本発明は、下記の低温焼成可能な高強度低熱膨張性磁器用組成物、前記組成物を低温焼成した高強度低熱膨張性磁器及びその製造方法を提供する。
［１］（Ａ）Ｌｉ2Ｏまたは焼成したときにＬｉ2Ｏとなるリチウム化合物（ａ１）とＭｇＯまたは焼成したときにＭｇＯとなるマグネシウム化合物（ａ２）とＡｌ2Ｏ3（ａ３）とＳｉＯ2（ａ４）との混合物であって、ａ１とａ２とａ３とａ４の割合（質量％比）α：β：γ：δ＝７．６〜１３．２：４．０〜１０．３：１３．０〜３０．４：５３．７〜７２．８の範囲にある仮焼物７５〜９６質量％と
（Ｂ）Ｂｉ2Ｏ3４〜２５質量％を含有し、８５０〜９００℃の温度で焼成して式（１）
で示される高強度低熱膨張性磁器を生成する高強度低熱膨張性磁器用組成物。
［２］Ｌｉ2Ｏまたは焼成したときにＬｉ2Ｏとなるリチウム化合物（ａ１）とＭｇＯまたは焼成したときにＭｇＯとなるマグネシウム化合物（ａ２）とＡｌ2Ｏ3（ａ３）とＳｉＯ2（ａ４）との混合物を７５０〜１０００℃の温度で焼成した仮焼物を０．２〜５μｍに微粉砕して、これにＢｉ2Ｏ3を所定量混合して８５０〜９００℃で焼結させた前項１に記載の高強度低熱膨張性磁器用組成物。
［３］前記ａ１、ａ２、ａ３及びａ４の混合物の一部として、Ｌｉ2ＯとＡｌ2Ｏ3とＳｉＯ2との複合酸化物であるβ−スポジュメンを含む前項１または２に記載の高強度低熱膨張性磁器用組成物。
［４］式（１）
で示される組成を有する複合酸化物を含む高強度低熱膨張性磁器。
［５］前記複合酸化物が、β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、及びＭｇＯ・ＳｉＯ2系結晶相を含む前項４に記載の高強度低熱膨張性磁器。
［６］β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、及びＭｇＯ・ＳｉＯ2系結晶相を前記磁器の全体積の８０％以上含む前項５に記載の高強度低熱膨張性磁器。
［７］抗折強度が１５０ＭＰａ以上である前項４〜６のいずれか１項記載の高強度低熱膨張性磁器。
［８］２５〜４００℃における線熱膨張係数が０〜５×１０-6／℃である前項４〜７のいずれか１項記載の高強度低熱膨張性磁器。
［９］陽極接合時の伝導イオンをＬｉイオンとし、３００〜３５０℃の温度で陽極接合可能な、式（１）
で示される組成を有する複合酸化物を含む高強度低熱膨張性磁器。
［１０］
シリコン、ＧａＡｓ、コバール、Ａｌ、またはＴｉと陽極接合可能な前項９に記載の高強度低熱膨張性磁器。
［１１］（Ａ）Ｌｉ2Ｏまたは焼成したときにＬｉ2Ｏとなるリチウム化合物（ａ１）とＭｇＯまたは焼成したときにＭｇＯとなるマグネシウム化合物（ａ２）とＡｌ2Ｏ3（ａ３）とＳｉＯ2（ａ４）との混合物であって、ａ１とａ２とａ３とａ４の質量％比α：β：γ：δ＝７．６〜１３．２：４．０〜１０．３：１３．０〜３０．４：５３．７〜７２．８の範囲にある混合物を７５０〜１０００℃の温度で焼成粉砕した仮焼物７５〜９６質量％に
（Ｂ）Ｂｉ2Ｏ3４〜２５質量％を添加混合して、バインダーを含む成形助剤を加え所定形状に成形後、８５０〜９００℃で焼成して、式（１）
で示される組成を有する複合酸化物を形成することを特徴とする高強度低熱膨張性磁器の製造方法。
［１２］テープ成形法により成形した絶縁層形成用のグリーンシートを焼成する前項１１記載の高強度低熱膨張性磁器の製造方法。
That is, the present invention provides the following composition for high-strength low-thermal-expansion ceramics that can be fired at low temperature, high-strength low-thermal-expansion ceramics obtained by firing the composition at low temperatures, and a method for producing the same.
[1] (A) Li 2 O or lithium compound (a1) that becomes Li 2 O when fired, MgO or magnesium compound (a2) that becomes MgO when fired, Al 2 O 3 (a3), and SiO 2 (A4), a ratio of a1, a2, a3 and a4 (mass% ratio) α: β: γ: δ = 7.6 to 13.2: 4.0 to 10.3: 13. 0 to 30.4: 75 to 96% by mass of the calcined product in the range of 53.7 to 72.8 and 4 to 25% by mass of (B) Bi 2 O 3 and calcined at a temperature of 850 to 900 ° C. Formula (1)
A composition for high-strength low-thermal-expansion porcelain that produces a high-strength low-thermal-expansion porcelain represented by
[2] Li 2 O or lithium compound (a1) that becomes Li 2 O when fired, and MgO or magnesium compound (a2), Al 2 O 3 (a3), and SiO 2 (a4) that becomes MgO when fired The calcined product obtained by calcining the mixture with 750 to 1000 ° C. is finely pulverized to 0.2 to 5 μm, mixed with a predetermined amount of Bi 2 O 3 and sintered at 850 to 900 ° C. 2. A high-strength, low-thermal-expansion ceramic composition as described in 1.
[3] The high strength according to the above item 1 or 2, comprising β-spodumene which is a composite oxide of Li 2 O, Al 2 O 3 and SiO 2 as a part of the mixture of a1, a2, a3 and a4. A composition for low thermal expansion porcelain.
[4] Formula (1)
A high-strength, low-thermal-expansion porcelain containing a composite oxide having a composition represented by:
[5] The composite oxide is a β-spodumene crystal phase and / or a Li 2 O.Al 2 O 3 .SiO 2 crystal phase, a Li 2 O.SiO 2 crystal phase, and an MgO.SiO 2 crystal. 5. The high-strength low-thermal-expansion porcelain according to item 4 including a phase.
[6] The β-spodumene-based crystal phase and / or the Li 2 O.Al 2 O 3 .SiO 2 -based crystal phase, the Li 2 O.SiO 2 -based crystal phase, and the MgO.SiO 2 -based crystal phase are added to the entire porcelain. 6. The high-strength low-thermal-expansion porcelain according to 5 above, containing 80% or more of the product.
[7] The high-strength low-thermal-expansion ceramic according to any one of items 4 to 6, wherein the bending strength is 150 MPa or more.
[8] The high-strength low-thermal-expansion ceramic according to any one of items 4 to 7, wherein the linear thermal expansion coefficient at 25 to 400 ° C. is 0 to 5 × 10 −6 / ° C.
[9] Formula (1), in which conduction ions at the time of anodic bonding are Li ions, and anodic bonding is possible at a temperature of 300 to 350 ° C.
A high-strength, low-thermal-expansion porcelain containing a composite oxide having a composition represented by:
[10]
10. The high-strength, low-thermal-expansion ceramic according to item 9, which can be anodically bonded to silicon, GaAs, Kovar, Al, or Ti.
[11] (A) Li 2 O or lithium compound (a1) that becomes Li 2 O when fired, MgO or magnesium compound (a2) that becomes MgO when fired, Al 2 O 3 (a3), and SiO 2 A mixture of (a4) and the mass% ratio of a1, a2, a3 and a4 α: β: γ: δ = 7.6 to 13.2: 4.0 to 10.3: 13.0 to 30 .4: Add 75 to 96% by mass of (B) Bi 2 O 3 4 to 25% by mass to a calcined product obtained by calcining and pulverizing a mixture in the range of 53.7 to 72.8 at a temperature of 750 to 1000 ° C. Then, a molding aid containing a binder is added to form a predetermined shape, and then fired at 850 to 900 ° C. to obtain the formula (1)
A method for producing a high-strength, low-thermal-expansion ceramic, characterized in that a composite oxide having the composition shown in FIG.
[12] The method for producing a high-strength, low-thermal-expansion ceramic as described in 11 above, wherein a green sheet for forming an insulating layer formed by a tape forming method is fired.
本発明の低温焼成可能な高強度低熱膨張性磁器用組成物は、液相形成成分としてＢｉ2Ｏ3を用いることにより、β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、ＭｇＯ・ＳｉＯ2系結晶相を主相とする磁器において低温焼結性を実現した。従って、本発明の高強度低熱膨張性磁器用組成物は、８５０〜９００℃の低温で焼結でき、Ｃｕ、Ａｕ、Ａｇ等による配線を同時焼成により形成することができるため、低熱膨張性ＬＴＣＣ（Low Temperature Co-fired Ceramics ；低温同時焼成セラミック）基板として有用である。また、非常に高い機械的強度も有していることから、半導体製造工程等で使用される、露光装置用のＸ−Ｙステージ、静電チャック及びその構造部品、ミラー等の部材に適した高強度低熱膨張性セラミックスとしても有用である。さらに、３００〜３５０℃の温度でシリコン等に陽極接合が可能であるためＭＥＭＳ（Micro Electro Mechanical Systems）実装用基板としても有用である。 By using Bi 2 O 3 as a liquid phase-forming component, the high-strength and low-temperature-expandable porcelain composition according to the present invention is capable of forming a β-spodumene crystal phase and / or Li 2 O.Al 2 O 3. Low temperature sinterability was realized in a porcelain mainly composed of SiO 2 crystal phase, Li 2 O · SiO 2 crystal phase, and MgO · SiO 2 crystal phase. Therefore, the high strength and low thermal expansion ceramic composition of the present invention can be sintered at a low temperature of 850 to 900 ° C., and a wiring made of Cu, Au, Ag or the like can be formed by co-firing. It is useful as a substrate (Low Temperature Co-fired Ceramics). In addition, since it has very high mechanical strength, it is suitable for members such as XY stage for exposure equipment, electrostatic chuck and its structural parts, mirrors, etc. used in semiconductor manufacturing processes. It is also useful as a high strength low thermal expansion ceramic. Further, since anodic bonding to silicon or the like is possible at a temperature of 300 to 350 ° C., it is also useful as a substrate for mounting MEMS (Micro Electro Mechanical Systems).
［磁器用組成物及び磁器］
本発明の低温焼成可能な高強度低熱膨張性磁器用組成物は、
（Ａ）Ｌｉ2Ｏまたは焼成したときにＬｉ2Ｏとなるリチウム化合物（ａ１）とＭｇＯまたは焼成したときにＭｇＯとなるマグネシウム化合物（ａ２）とＡｌ2Ｏ3（ａ３）とＳｉＯ2（ａ４）との混合物であって、ａ１とａ２とａ３とａ４の割合（質量％比）α：β：γ：δ＝７．６〜１３．２：４．０〜１０．３：１３．０〜３０．４：５３．７〜７２．８の範囲にある仮焼物７５〜９６質量％と
（Ｂ）Ｂｉ2Ｏ3４〜２５質量％を含有し、８５０〜９００℃の温度で焼成して式（１）
The composition for high-strength low-thermal-expansion ceramics that can be fired at low temperature according to the present invention
(A) Li 2 O or lithium compound (a1) that becomes Li 2 O when fired, MgO or magnesium compound (a2), Al 2 O 3 (a3), and SiO 2 (a4) that becomes MgO when fired A ratio of a1, a2, a3 and a4 (mass% ratio) α: β: γ: δ = 7.6 to 13.2: 4.0 to 10.3: 13.0 to 30 .4: 75 to 96% by mass of the calcined product in the range of 53.7 to 72.8 and (B) Bi 2 O 3 4 to 25% by mass, and calcined at a temperature of 850 to 900 ° C. 1)
Ｌｉ、Ｍｇ、Ａｌ、及びＳｉを含有する混合物（ａ１とａ２とａ３とａ４との混合物）に対してＢｉ2Ｏ3を含有させることにより、８５０〜９００℃程度の低温で焼結（焼成緻密化）できる。 By containing Bi 2 O 3 in a mixture containing Li, Mg, Al, and Si (a mixture of a1, a2, a3, and a4), sintering (firing dense) is performed at a low temperature of about 850 to 900 ° C. ).
一般式（１）において、Ｂｉ2Ｏ3の割合ａ（質量比）は０．０４〜０．２５である。ｘが０．０４より不足すると焼結せず、０．２５より過剰だと強度が低下してしまう。 In the general formula (1), the ratio a (weight ratio) of Bi 2 O 3 is 0.04 to 0.25. If x is less than 0.04, sintering will not occur, and if it exceeds 0.25, the strength will decrease.
一般式（１）において、Ｌｉ2Ｏの割合α（質量％）は７．６〜１３．２であり、ＭｇＯの割合β（質量％）は４．０〜１０．３であり、Ａｌ2Ｏ3の割合γ（質量％）は１３．０〜３０．４であり、ＳｉＯ2の割合δ（質量％）は５３．７〜７２．８である。 In the general formula (1), the ratio α (mass%) of Li 2 O is 7.6 to 13.2, the ratio β (mass%) of MgO is 4.0 to 10.3, and Al 2 O ratio of 3 gamma (mass%) is from 13.0 to 30.4, the ratio of SiO 2 [delta] (mass%) is from 53.7 to 72.8.
αは７．６％より不足すると焼結せず、１３．２％より過剰だと熱膨張係数が大きくなってしまう。βは４．０％より不足だと焼結せず、１０．３％より過剰になると熱膨張が大きくなる。γは１３．０％より不足だと熱膨張が大きくなり、３０．４％より過剰だと焼結しない。δは５３．７〜７２．８％の範囲を外れると焼結しない。 If α is less than 7.6%, sintering does not occur, and if it exceeds 13.2%, the thermal expansion coefficient becomes large. If β is less than 4.0%, sintering does not occur, and if it exceeds 10.3%, thermal expansion increases. If γ is less than 13.0%, thermal expansion increases, and if it is more than 30.4%, sintering does not occur. If δ is out of the range of 53.7 to 72.8%, it does not sinter.
前記組成物からなる原料粉を仮焼して複合酸化物を形成し、これにＢｉ2Ｏ3を加え焼結させることにより、本発明の高強度低熱膨張性磁器を得ることができる。 The high-strength low-thermal-expansion ceramic of the present invention can be obtained by calcining the raw material powder made of the composition to form a composite oxide, and adding Bi 2 O 3 thereto and sintering it.
本発明の高強度低熱膨張性磁器は、式（１）
で示される組成を有する複合酸化物を含む。
The high-strength low-thermal-expansion porcelain of the present invention has the formula (1)
A composite oxide having a composition represented by:
本発明の高強度低熱膨張性磁器は、β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、及びＭｇＯ・ＳｉＯ2系結晶相を主体とし、さらにＢｉ2Ｏ3・ＳｉＯ2系結晶相乃至／及びガラス相から主として構成されるものである。 High-strength and low-thermal-expansion ceramic according to the present invention, beta-spodumene based crystal phase and / or Li 2 O · Al 2 O 3 · SiO 2 type crystal phase, Li 2 O · SiO 2 type crystal phase, and MgO · SiO 2 Mainly composed of a system crystal phase, and further mainly composed of a Bi 2 O 3 .SiO 2 system crystal phase or / and a glass phase.
ここで、「β−スポジュメン系結晶相」とは、β−スポジュメン結晶及びこれに類する組成及び結晶構造の結晶相、「Ｌｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相」とは、Ｌｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2結晶及びこれに類する組成及び結晶構造の結晶相、「Ｌｉ2Ｏ・ＳｉＯ2系結晶相」とは、Ｌｉ2Ｏ・ＳｉＯ2結晶及びこれに類する組成及び結晶構造の結晶相であり、その各々の結晶相には、前記各結晶を構成する主構成元素以外の他の元素を含む同型の結晶構造の結晶を含んでもよい。 Here, “β-spodumene-based crystal phase” means a β-spodumene crystal and a crystal phase having a composition and a crystal structure similar to this, and “Li 2 O.Al 2 O 3 .SiO 2 -based crystal phase” means Li 2 O.Al 2 O 3 .SiO 2 crystal and a crystal phase of a composition and crystal structure similar to this, “Li 2 O.SiO 2 crystal phase” means a Li 2 O.SiO 2 crystal and a similar composition and Each of the crystal phases may include a crystal having the same type of crystal structure including elements other than the main constituent elements constituting each of the crystals.
ＭｇＯ・ＳｉＯ2系結晶相、及びＢｉ2Ｏ3・ＳｉＯ2系結晶相についても同様であり、「ＭｇＯ・ＳｉＯ2系結晶相」とは、ＭｇＯ・ＳｉＯ2結晶及びこれに類する組成及び結晶構造の結晶相であり、「Ｂｉ2Ｏ3・ＳｉＯ2系結晶相」とは、Ｂｉ2Ｏ3・ＳｉＯ2結晶及び結晶構造の結晶相であり、その各々の結晶相には、前記各結晶を構成する主構成元素以外の他の元素を含む同型の結晶構造の結晶を含んでもよい。 The same applies to the MgO · SiO 2 crystal phase and the Bi 2 O 3 · SiO 2 crystal phase. The term “MgO · SiO 2 crystal phase” refers to an MgO · SiO 2 crystal and a similar composition and crystal structure. The “Bi 2 O 3 .SiO 2 -based crystal phase” is a crystal phase of Bi 2 O 3 .SiO 2 crystal and crystal structure, and each crystal phase includes the above crystals. A crystal having the same type of crystal structure including other elements than the main constituent element may be included.
各結晶相の具体的な含有比は、目標とする物性値を実現するものであれば特に限定されないが、通常は、β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、及びＭｇＯ・ＳｉＯ2系結晶相を磁器の全体積の９０％以上含み、好ましくは９５％以上含む。 The specific content ratio of each crystal phase is not particularly limited as long as it achieves a target physical property value. Usually, the β-spodumene crystal phase and / or Li 2 O.Al 2 O 3 .SiO 2 is used. 90% or more, preferably 95% or more of the total volume of the porcelain is contained in the two- based crystal phase, the Li 2 O · SiO 2 -based crystal phase, and the MgO · SiO 2 -based crystal phase.
本発明の高強度低熱膨張性磁器は、線熱膨張係数が０〜５×１０-6／℃、抗折強度が１５０ＭＰａ以上であり、８５０〜９００℃の温度範囲での低温焼成によって相対密度９５％以上まで緻密化されたものである。 The high-strength low thermal expansion ceramic of the present invention has a linear thermal expansion coefficient of 0 to 5 × 10 −6 / ° C., a bending strength of 150 MPa or more, and a relative density of 95 by low-temperature firing in a temperature range of 850 to 900 ° C. % Densified.
［磁器の製造方法］
本発明の高強度低熱膨張性磁器は、前記組成物からなる原料粉を７５０〜１０００℃で仮焼後粉砕して粉末とし、これにＢｉ2Ｏ3を加え、バインダーを含む成形助剤を加え所定形状に成形後、８５０〜９００℃の温度で焼成して複合酸化物を形成することにより製造できる。
[Manufacturing method of porcelain]
The high-strength, low-thermal-expansion ceramic of the present invention is prepared by calcining the raw material powder made of the above composition at 750 to 1000 ° C. and then pulverizing it, adding Bi 2 O 3 thereto, and adding a molding aid containing a binder. After forming into a predetermined shape, it can be manufactured by firing at a temperature of 850 to 900 ° C. to form a composite oxide.
主原料である、Ｌｉ2Ｏまたは焼成したときにＬｉ2Ｏとなるリチウム化合物と、ＭｇＯまたは焼成したときにＭｇＯとなるマグネシウム化合物と、Ａｌ2Ｏ3と、ＳｉＯ2とは、各金属酸化物の混合物でもよいが、β−スポジュメン等の複合酸化物にＭｇＯを必要量混合したものでもよい。出発原料として用い得る、Ｌｉ2Ｏまたは焼成したときにＬｉ2Ｏとなるリチウム化合物と、ＭｇＯまたは焼成したときにＭｇＯとなるマグネシウム化合物と、Ａｌ2Ｏ3と、ＳｉＯ2とは、前記各金属の酸化物粉末のほかに、焼結過程で酸化物を形成し得る塩、例えば炭酸塩、酢酸塩、硝酸塩や水酸化物等の形態、例えば炭酸リチウム（Ｌｉ2ＣＯ3）、炭酸マグネシウム（ＭｇＣＯ3）や水酸化マグネシウム（Ｍｇ（ＯＨ）2）等の形態で添加できる。 The main raw materials, Li 2 O or a lithium compound that becomes Li 2 O when fired, MgO or a magnesium compound that becomes MgO when fired, Al 2 O 3 , and SiO 2 are metal oxides. A mixture of MgO and a complex oxide such as β-spodumene may be used. Li 2 O that can be used as a starting material or a lithium compound that becomes Li 2 O when fired, MgO or a magnesium compound that becomes MgO when fired, Al 2 O 3 , and SiO 2 are each of the above metals In addition to the oxide powder, a salt capable of forming an oxide during the sintering process, such as carbonate, acetate, nitrate, hydroxide, etc., such as lithium carbonate (Li 2 CO 3 ), magnesium carbonate (MgCO 3) magnesium and hydroxide (Mg (OH) 2) can be added in the form of such.
前記主原料に対して、焼結助剤としてＢｉ2Ｏ3粉末を、好ましくは前記主原料が７５〜９６質量％、Ｂｉ2Ｏ3が４〜２５質量％の範囲となるように添加混合する。 Bi 2 O 3 powder as a sintering aid is added to and mixed with the main raw material, preferably so that the main raw material is in the range of 75 to 96% by mass and Bi 2 O 3 is in the range of 4 to 25% by mass. .
Ｌｉ2ＣＯ3、ＭｇＯ、Ａｌ2Ｏ3、ＳｉＯ2、Ｂｉ2Ｏ3等の原料粉末は、分散性を高め、望ましい強度や低熱膨張性を得るために、２．０μｍ以下、特に１．０μｍ以下の微粉末とすることが望ましい。 Raw material powders such as Li 2 CO 3 , MgO, Al 2 O 3 , SiO 2 , Bi 2 O 3 are 2.0 μm or less, particularly 1.0 μm, in order to increase dispersibility and obtain desirable strength and low thermal expansion. The following fine powder is desirable.
上記の割合で添加混合、７５０〜１０００℃で仮焼後粉砕した混合粉末にＢｉ2Ｏ3を加え、適宜バインダー、好ましくは有機バインダー、例えば、アクリル樹脂バインダー等や、可塑剤、例えば、ジブチルフタレート（ＤＢＰ）等のポリエステル樹脂など、必要に応じて、トルエン、メチルエチルケトン（ＭＥＫ）等の有機溶剤を添加した後、例えば、金型プレス、押し出し成形、ドクターブレード法、圧延法等により任意の形状に成形後、酸化雰囲気中、または窒素ガス、アルゴンガス等の非酸化性雰囲気中において、８５０〜９００℃の温度で、１〜３時間焼成することにより、相対密度９５％以上に緻密化することができる。 Bi 2 O 3 is added to the mixed powder added and mixed at the above ratio, calcined after calcination at 750 to 1000 ° C., and a binder, preferably an organic binder such as an acrylic resin binder, or a plasticizer such as dibutyl phthalate. After adding an organic solvent such as toluene and methyl ethyl ketone (MEK) as necessary, such as polyester resin such as (DBP), it can be formed into any shape by, for example, die pressing, extrusion molding, doctor blade method, rolling method, etc. After molding, in a non-oxidizing atmosphere such as nitrogen gas, argon gas or the like, it is densified to a relative density of 95% or more by firing at a temperature of 850 to 900 ° C. for 1 to 3 hours. it can.
この時の焼成温度が８５０℃より低いと、磁器が十分に緻密化せず、９００℃を越えると緻密化は可能であるが、Ａｇ、Ａｕ、Ｃｕ等の低融点導体を配線材料として用いることが難しくなる。 If the firing temperature at this time is lower than 850 ° C., the porcelain will not be sufficiently densified, and if it exceeds 900 ° C., densification is possible, but a low melting point conductor such as Ag, Au, Cu or the like should be used as the wiring material. Becomes difficult.
本発明によれば、Ｌｉ、Ｍｇ、Ａｌ、及びＳｉの複合酸化物である固相とＢｉ2Ｏ3・ＳｉＯ2系液相の活性な固液反応が生じる結果、少ない焼結助剤量で磁器を緻密化することができる。そのため非晶質相の量を最小限に抑えることができる。 According to the present invention, as a result of an active solid-liquid reaction between a solid phase that is a composite oxide of Li, Mg, Al, and Si and a Bi 2 O 3 · SiO 2 liquid phase, a small amount of sintering aid is required. Porcelain can be densified. Therefore, the amount of amorphous phase can be minimized.
このように本発明によれば、低温焼成した磁器中に、少なくともＬｉ、Ａｌ、及びＳｉを含むスポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、ＭｇＯ・ＳｉＯ2系結晶相、及びＢｉ2Ｏ3・ＳｉＯ2系結晶相を析出させることにより、強度が高い低熱膨張性磁器を得ることができる。 As described above, according to the present invention, a spodumene-based crystal phase containing at least Li, Al, and Si and / or a Li 2 O.Al 2 O 3 .SiO 2 -based crystal phase, Li 2 O -By precipitating the SiO 2 crystal phase, MgO · SiO 2 crystal phase, and Bi 2 O 3 · SiO 2 crystal phase, a low thermal expansion ceramic having high strength can be obtained.
［磁器用組成物及び磁器の用途］
本発明の磁器用組成物によれば８５０〜９００℃の低温焼成可能で、Ａｇ、Ａｕ、Ｃｕ等の低融点・低抵抗な導体との同時焼成が可能であり、本発明の磁器用組成物を焼結した磁器は、室温（ＲＴ＝２５℃）〜４００℃での線熱膨張係数が０〜５×１０-6／℃と小さく、かつ抗折強度が１５０ＭＰａ以上の高強度を有する。
[Use of porcelain composition and porcelain]
According to the porcelain composition of the present invention, it can be fired at a low temperature of 850 to 900 ° C., and can be simultaneously fired with a low melting point / low resistance conductor such as Ag, Au, Cu, etc. The porcelain composition of the present invention The sintered porcelain has a linear thermal expansion coefficient as small as 0 to 5 × 10 −6 / ° C. from room temperature (RT = 25 ° C.) to 400 ° C., and has a bending strength of 150 MPa or more.
すなわち、本発明磁器用組成物は、８５０〜９００℃で低温焼成可能であることから、特にＡｇ、Ａｕ、Ｃｕなどを配線する配線基板の絶縁基板として用いることができる。 That is, since the composition for porcelain of the present invention can be fired at a low temperature of 850 to 900 ° C., it can be used particularly as an insulating substrate for a wiring substrate for wiring Ag, Au, Cu and the like.
かかる本発明磁器用組成物を用いて配線基板を作製する場合には、例えば、前記のようにして調合した混合粉末とＢｉ2Ｏ3を公知のテープ成形法、例えばドクターブレード法、押し出し成形法等に従い、絶縁層形成用のグリーンシートを作製した後、そのシートの表面に配線回路層用として、Ａｇ、Ａｕ及びＣｕのうちの少なくとも１種の金属、特に、Ａｇ粉末を含む導体ペーストを用いて、グリーンシート表面にスクリーン印刷法等によって配線パターンを回路パターン状に印刷し、場合によってはシートにスルーホールやビアホール形成後、上記導体ペーストを充填する。その後、複数のグリーンシートを積層圧着した後、前記条件で焼成することにより、配線層と絶縁層とを同時に焼成することができる。 When producing a wiring board using such a composition for porcelain of the present invention, for example, the mixed powder and Bi 2 O 3 prepared as described above are formed by a known tape molding method such as a doctor blade method or an extrusion molding method. After producing a green sheet for forming an insulating layer according to the above, at least one metal of Ag, Au and Cu, particularly a conductor paste containing Ag powder is used for the wiring circuit layer on the surface of the sheet. Then, a wiring pattern is printed on the surface of the green sheet by a screen printing method or the like, and in some cases, the sheet is filled with the conductor paste after through holes and via holes are formed. Thereafter, the plurality of green sheets are laminated and pressure-bonded, and then fired under the above conditions, whereby the wiring layer and the insulating layer can be fired simultaneously.
さらに、本発明磁器によれば、雰囲気温度での熱膨張性が十分低いため、温度変化による変形が改善され、露光装置のＸ−Ｙステージやシリコンウエハ支持体の位置決め精度に付随する製品品質及び歩留りの問題も改善される。また、本発明磁器は剛性が高いので、これを適用することにより、外部衝撃が加わった場合の振動による精度低下の問題を改善することができる。 Furthermore, according to the porcelain of the present invention, since the thermal expansion at the ambient temperature is sufficiently low, deformation due to temperature change is improved, and the product quality associated with the positioning accuracy of the XY stage of the exposure apparatus and the silicon wafer support and Yield issues are also improved. In addition, since the porcelain of the present invention has high rigidity, by applying this, it is possible to improve the problem of accuracy reduction due to vibration when an external impact is applied.
このように、本発明磁器は、低温焼成が可能なばかりでなく、緻密で高強度を有し、かつ熱膨張性が低い。従って、本発明に係る磁器用組成物及び磁器は、半導体製造工程等で使用される、露光装置用のＸ−Ｙステージ、静電チャック及びその構造部品、ミラー等の部材に適した低熱膨張性セラミックスとしても最適である。 Thus, the porcelain of the present invention is not only capable of being fired at a low temperature, but also has a dense and high strength and low thermal expansion. Therefore, the composition for porcelain and the porcelain according to the present invention have low thermal expansion suitable for members such as an XY stage for an exposure apparatus, an electrostatic chuck and its structural parts, and a mirror used in a semiconductor manufacturing process and the like. It is also optimal as a ceramic.
［陽極接合］
本発明の高強度低熱膨張性磁器は、ＭＥＭＳ（Micro Electro Mechanical Systems）実装用基板の作成に必須な接合技術である陽極接合が可能である。
[Anodic bonding]
The high-strength, low-thermal-expansion porcelain of the present invention is capable of anodic bonding, which is a bonding technique essential for the production of MEMS (Micro Electro Mechanical Systems) mounting substrates.
陽極接合は、アルカリ金属を含むガラスとシリコンを接触させた状態で、ガラス中のナトリウムなどのアリカリ金属イオンが動き易い温度まで加熱し、シリコン側を正、ガラス側を負の電極に接続して数百〜千ボルト程度の直流電圧を印加することにより、ガラスとシリコンを接合する方法である。アルカリ金属イオンが負極側に移動した際に生じる非架橋酸素イオンとシリコンが静電的に引き合い、磁器−シリコン界面で化学結合を生じることにより、強固で信頼性の高い接合が得られる。 In anodic bonding, glass containing alkali metal is in contact with silicon, heated to a temperature at which ant potassium metal ions such as sodium in the glass move easily, and the silicon side is connected to the positive electrode and the glass side is connected to the negative electrode. This is a method of joining glass and silicon by applying a DC voltage of about several hundred to 1,000 volts. Non-bridging oxygen ions generated when alkali metal ions move to the negative electrode side and silicon are electrostatically attracted to form a chemical bond at the porcelain-silicon interface, whereby a strong and reliable bond can be obtained.
陽極接合する温度は、ＭＥＭＳに与える影響が少ないため３５０℃以下の低温が好適であり、例えば３００〜３３０℃またはそれ以下の低い接合温度が特に好適である。
本発明の高強度低熱膨張性磁器は、陽極接合時の伝導イオンを従来のＮａから、よりイオン半径の小さいＬｉに変えたことによって、ＭＥＭＳに与える影響の少ない好適な温度範囲（３００〜３５０℃）での陽極接合が可能である。
The temperature at which the anodic bonding is performed has a small influence on the MEMS, and therefore, a low temperature of 350 ° C. or lower is preferable, and a low bonding temperature of 300 to 330 ° C. or lower is particularly preferable.
The high-strength, low-thermal-expansion porcelain of the present invention has a suitable temperature range (300 to 350 ° C.) that has little influence on MEMS by changing the conductive ions at the time of anodic bonding from conventional Na to Li having a smaller ion radius. ) Anodic bonding is possible.
陽極接合はシリコンだけでなく、ＧａＡｓ、コバール、Ａｌ、Ｔｉなども接合可能であり、本発明の磁器においても特に制限されるものではない。 The anodic bonding can bond not only silicon but also GaAs, Kovar, Al, Ti and the like, and is not particularly limited in the porcelain of the present invention.
陽極接合においては、相手材との熱膨張による位置ずれ等が問題になることから、基板材料の線熱膨張係数は、相手材の線熱膨張係数と近似することが求められ、成形焼成後の材料の線熱膨張係数は相手材の線熱膨張係数の０．５％以内であることが好ましい。相手材がシリコンの場合には、本発明の磁器の線熱膨張係数は、０〜５．０×１０-6／℃、好ましくは３．０〜４．０×１０-6／℃、さらに好ましくは３．２〜３．８×１０-6／℃、特に好ましくは３．２〜３．５×１０-6／℃である。 In anodic bonding, misalignment due to thermal expansion with the counterpart material becomes a problem, so the linear thermal expansion coefficient of the substrate material is required to approximate the linear thermal expansion coefficient of the counterpart material. The linear thermal expansion coefficient of the material is preferably within 0.5% of the linear thermal expansion coefficient of the counterpart material. If the counterpart material is silicon, the linear thermal expansion coefficient of porcelain of the invention, 0 to 5.0 × 10 -6 / ° C., preferably 3.0~4.0 × 10 -6 / ℃, more preferably Is 3.2 to 3.8 × 10 −6 / ° C., particularly preferably 3.2 to 3.5 × 10 −6 / ° C.
以下に実施例及び比較例を挙げ、本発明を更に詳細に説明するが、これらは本発明を限定するものではない。 EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but these do not limit the present invention.
実施例１〜８及び比較例１〜９
平均粒径が１μｍ以下の、Ｌｉ2ＣＯ3、ＭｇＯ、Ａｌ2Ｏ3、ＳｉＯ2を酸化物換算の含有比が表１の割合となるようにボールミル中で混合し、７５０〜１０００℃で仮焼後、０．２〜５μｍまで微粉砕して粉末とした。これらの仮焼物に表１の割合でＢｉ2Ｏ3を添加し、有機バインダー（ポリビニルアルコール）、可塑剤（ジブチルフタレート）、トルエンを添加混合して、ドクターブレード法により厚さ１５０μｍのグリーンシートを作成した。このグリーンシートを５枚積層し、７０℃の温度で１５０ｋｇ／ｃｍ2の圧力を加えて熱圧着した。得られた積層体を大気中で、５００℃で脱バインダーした後、大気中で表１の温度条件下で焼成して多層基板用磁器を得た。
Examples 1-8 and Comparative Examples 1-9
Li 2 CO 3 , MgO, Al 2 O 3 , and SiO 2 having an average particle size of 1 μm or less were mixed in a ball mill so that the content ratio in terms of oxide would be the ratio shown in Table 1, and temporarily mixed at 750 to 1000 ° C. After firing, the powder was finely pulverized to 0.2 to 5 μm. Bi 2 O 3 is added to these calcined materials in the ratio shown in Table 1, an organic binder (polyvinyl alcohol), a plasticizer (dibutyl phthalate), and toluene are added and mixed, and a green sheet having a thickness of 150 μm is formed by a doctor blade method. Created. Five green sheets were laminated and thermocompression bonded by applying a pressure of 150 kg / cm 2 at a temperature of 70 ° C. The resulting laminate was debindered at 500 ° C. in the air, and then fired in the air under the temperature conditions shown in Table 1 to obtain a multilayer substrate porcelain.
得られた焼結体について嵩密度をアルキメデス法にて測定した。また、ＪＩＳＲ１６０１に基づき、磁器の３点曲げ強度（抗折強度）を測定した。ＴＭＡ（熱機械的分析）法にて室温（ＲＴ＝２５℃）から４００℃における線熱膨張係数を測定した。また、各試料についてＸ線回折測定を行い、標準試料のＸ線回折ピークとの比較によって磁器の構成相を同定した。これらの測定結果を表１に示す。 The bulk density of the obtained sintered body was measured by the Archimedes method. Moreover, based on JISR1601, the three-point bending strength (bending strength) of the porcelain was measured. The linear thermal expansion coefficient from room temperature (RT = 25 ° C.) to 400 ° C. was measured by the TMA (thermomechanical analysis) method. Further, X-ray diffraction measurement was performed for each sample, and the constituent phases of the porcelain were identified by comparison with the X-ray diffraction peak of the standard sample. These measurement results are shown in Table 1.
表１中、Lithium Silicate、Lithium Aluminum Silicate、Enstatite、Bismus Silicate、及びForsteriteは、各々下記結晶相を表す。
Lithium Silicate：Ｌｉ2ＳｉＯ3、Ｌｉ2Ｓｉ2Ｏ5など、
Lithium Aluminum Silicate ：スポジュメン（ＬｉＡｌＳｉ2Ｏ6）など、
Enstatite ：ＭｇＳｉＯ3、
Bismus Silicate：Eulytite、Ｂi2Ｏ2・ＳiＯ3など、
Forsterite：Ｍｇ2ＳｉＯ4。
In Table 1, Lithium Silicate, Lithium Aluminum Silicate, Enstatite, Bismus Silicate, and Forsterite each represent the following crystal phase.
Lithium Silicate: Li 2 SiO 3 , Li 2 Si 2 O 5 etc.
Lithium Aluminum Silicate: Spodumene (LiAlSi 2 O 6 ), etc.
Enstatite: MgSiO 3
Bismus Silicate: Eulytite, Bi 2 O 2 and SiO 3 etc.
Forsterite: Mg 2 SiO 4 .
表１の結晶相の欄に記載したように、実施例の磁器については、β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、ＭｇＯ・ＳｉＯ2系結晶相の各相の存在が確認された。 As described in the column of the crystal phase in Table 1, for the porcelain of the example, the β-spodumene crystal phase and / or the Li 2 O.Al 2 O 3 .SiO 2 crystal phase, Li 2 O.SiO 2 The existence of each phase of the system crystal phase and the MgO.SiO 2 system crystal phase was confirmed.
表１に示す結果から明らかなように、Ｌｉ2Ｏ、ＭｇＯ、Ａｌ2Ｏ3、ＳｉＯ2を本発明の組成範囲で含み、結晶相として、β−スポジュメン系結晶相及び／またはＬｉ2Ｏ・Ａｌ2Ｏ3・ＳｉＯ2系結晶相、Ｌｉ2Ｏ・ＳｉＯ2系結晶相、ＭｇＯ・ＳｉＯ2系結晶相が主として析出した本発明の低温焼成磁器は、いずれも線熱膨張係数が０〜５×１０-6／℃、抗折強度が１５０ＭＰａ以上の優れた値を示す高強度低熱膨張性磁器である。
これに対して、Ｌｉ2Ｏの含有量が過少の場合には焼結せず（比較例１）、過多の場合には線熱膨張係数が５×１０-6／℃を超え（比較例２）、ＭｇＯを含まない場合には焼結せず（比較例９）、ＭｇＯの含有量が過多の場合には線熱膨張係数が５×１０-6／℃を超え（比較例５〜６）、Ａｌ2Ｏ3の含有量が過多の場合には焼結しない（比較例７）。またＢｉ2Ｏ3の含有量が過少の場合には焼結せず（比較例３）、過多の場合には抗折強度が低くなる（比較例４）。
As is apparent from the results shown in Table 1, Li 2 O, MgO, Al 2 O 3 , SiO 2 are included in the composition range of the present invention, and the β-spodumene crystal phase and / or Li 2 O. The low-temperature fired ceramics of the present invention in which the Al 2 O 3 · SiO 2 crystal phase, Li 2 O · SiO 2 crystal phase, and MgO · SiO 2 crystal phase are mainly precipitated have a linear thermal expansion coefficient of 0 to 5 respectively. This is a high-strength, low-thermal-expansion ceramic exhibiting excellent values of × 10 −6 / ° C. and bending strength of 150 MPa or more.
On the other hand, when the content of Li 2 O is too small, it is not sintered (Comparative Example 1), and when it is excessive, the linear thermal expansion coefficient exceeds 5 × 10 −6 / ° C. (Comparative Example 2). ), When MgO is not contained, sintering is not performed (Comparative Example 9), and when the content of MgO is excessive, the linear thermal expansion coefficient exceeds 5 × 10 −6 / ° C. (Comparative Examples 5 to 6) When the content of Al 2 O 3 is excessive, it is not sintered (Comparative Example 7). Further, when the content of Bi 2 O 3 is too small, sintering is not performed (Comparative Example 3), and when it is excessive, the bending strength is low (Comparative Example 4).
［陽極接合の確認］
実施例で焼結した基板８水準を準備し、陽極接合性能を評価した。前記基板８水準、各１枚を２０ｍｍ□にダイシングし、板厚み０．３ｍｍに鏡面研磨した。この基板とシリコンとを加熱したホットプレート上でシリコンが正極、基板が負極になるように直流電圧（６００ＶＤＣ）を印加して陽極接合を行った。陽極接合回路上に電圧検出用の抵抗素子を挿入し、その抵抗素子にかかる電圧をモニタリングし、接合電流が接合時間とともにどのように変化するかをチェックした。
なお、焼き上がった状態の基板の表面粗さ（Ｒａ：中心線平均粗さ）は２００ｎｍ程度であったが、本発明では、鏡面研磨加工レベルを上げることにより、パイレックス（登録商標）ガラス（商品名；コーニング社製のホウケイ酸ガラス）と同等の表面粗さ（数ｎｍＲａ）にまで仕上げた。この鏡面研磨した基板を用いて、３００℃、３３０℃、及び３６０℃で陽極接合を行った。
得られた陽極接合体にガラス切りで傷をつけて手で分割し、破断面をＳＥＭで観察した。結果は表２に示す通り、全水準でシリコンと低温焼結基板が連続した破断面になっており、不連続点（デラミネーション）はなく、強固に接合できている（ＯＫ）ことが観察された。
[Confirmation of anodic bonding]
The substrate 8 level sintered in the examples was prepared, and the anodic bonding performance was evaluated. The substrate 8 level, each one was diced to 20 mm □, and mirror polished to a plate thickness of 0.3 mm. On this hot plate where the substrate and silicon were heated, anodic bonding was performed by applying a DC voltage (600 VDC) so that silicon was a positive electrode and the substrate was a negative electrode. A resistance element for voltage detection was inserted on the anode junction circuit, and the voltage applied to the resistance element was monitored to check how the junction current changed with the junction time.
Although the surface roughness (Ra: centerline average roughness) of the baked substrate was about 200 nm, in the present invention, by increasing the mirror polishing level, Pyrex (registered trademark) glass (product) Name: Finished to a surface roughness (several nmRa) equivalent to Corning Borosilicate Glass). Using this mirror-polished substrate, anodic bonding was performed at 300 ° C., 330 ° C., and 360 ° C.
The obtained anodic bonded body was scratched with glass and divided by hand, and the fractured surface was observed with SEM. As shown in Table 2, the results show that the silicon and the low-temperature sintered substrate have a continuous fracture surface at all levels, and there are no discontinuities (delaminations), and it is observed that they are firmly bonded (OK). It was.
比較のため、Ｎａを陽極接合時の伝導イオンとする低温焼成セラミックスとシリコンとを陽極接合した接合体についてデラミネーションの確認を行った。なお、比較のためのＬＴＣＣは次のようにして作製した。
すなわち、陽極接合できるガラスとして市販されているガラス粉末（ＳｉＯ2：８１．９〜８２．４質量％、Ａｌ2Ｏ3：２．９〜３．２質量％、Ｂ2Ｏ3：１０．５〜１１．０質量％、Ｎａ2Ｏ：３．９〜４．７質量％、Ｋ2Ｏ、Ｆｅ2Ｏ3、ＣａＯ、ＭｇＯはいずれも０．１％以下）５５〜６０質量％を平均粒径（Ｄ50）で０．６〜２．５μｍに粉砕し、平均粒径１〜３μｍのアルミナ粉末８〜２５質量％および平均粒径１〜３μｍのコージェライト粉末（ガラス再結晶タイプ）１８〜３４質量％と混合した。この混合物に溶剤としてトルエンを加えてボールミル中で分散したあと、バインダーとしてポリビニルアルコール、可塑剤としてジブチルフタレート（ＤＢＰ）を加えスラリーを作製した。得られたスラリーをドクターブレード法でシート状に成形し、乾燥し、厚み１２５μｍのグリーンシートを得た。これを所定の大きさに切断し、８層に積層後、大気中、８３５℃または８５０℃で１時間焼成を行い、Ｎａを陽極接合時の伝導イオンとするガラス・フィラー複合ＬＴＣＣ（ＢＳＷ）を作製した。この基板（ＢＳＷ）は、３３０℃で陽極接合できなかった（ＮＧ）。
For comparison, delamination was confirmed for a bonded body obtained by anodically bonding silicon with low-temperature fired ceramics using Na as a conductive ion during anodic bonding. The LTCC for comparison was produced as follows.
That is, the glass powder which is commercially available as a glass capable of anodic bonding (SiO 2: 81.9 to 82.4 wt%, Al 2 O 3: 2.9~3.2 wt%, B 2 O 3: 10.5 11.0 wt%, Na 2 O: 3.9~4.7 wt%, K 2 O, Fe 2 O 3, CaO, more than 0.1% any MgO is) an average particle of 55 to 60 wt% It is pulverized to 0.6 to 2.5 μm in diameter (D 50 ), 8 to 25 mass% of alumina powder having an average particle diameter of 1 to 3 μm, and cordierite powder (glass recrystallization type) having an average particle diameter of 1 to 3 μm 18 to Mixed with 34% by weight. Toluene was added to this mixture as a solvent and dispersed in a ball mill, and then polyvinyl alcohol as a binder and dibutyl phthalate (DBP) as a plasticizer were added to prepare a slurry. The obtained slurry was formed into a sheet by a doctor blade method and dried to obtain a green sheet having a thickness of 125 μm. This is cut into a predetermined size, laminated into 8 layers, fired at 835 ° C. or 850 ° C. for 1 hour in the air, and glass / filler composite LTCC (BSW) using Na as a conductive ion at the time of anodic bonding. Produced. This substrate (BSW) could not be anodically bonded at 330 ° C. (NG).
以上のように、従来のＮａイオンを陽極接合時の伝導イオンとする低温焼成セラミックス（ＬＴＣＣ）と比較して、陽極接合時の伝導イオンをＬｉイオンとした本発明の磁器によれば３５０℃以下の低温でも陽極接合できる。 As described above, according to the porcelain of the present invention in which the conductive ions at the time of anodic bonding are Li ions, compared to the conventional low-temperature fired ceramics (LTCC) using Na ions as the conductive ions at the time of anodic bonding, 350 ° C. or less. Anodic bonding is possible even at low temperatures.
本発明の磁器用組成物によれば、８５０〜９００℃の温度で焼結でき、Ａｇ、Ａｕ、Ｃｕ等の低融点・低抵抗な導体との同時焼成が可能であり、これを焼結することにより、室温（ＲＴ＝２５℃）〜４００℃での線熱膨張係数が０〜５×１０-6／℃と小さく、かつ抗折強度が１５０ＭＰａ以上と高い強度を有する本発明の高強度低熱膨張性磁器を提供できる。すなわち、本発明の磁器用組成物は、８５０〜９００℃の温度で焼結可能であることから、特にＡｇ、Ａｕ、Ｃｕなどを配線する配線基板の絶縁基板として用いることができるばかりでなく、焼結された高強度低熱膨張性磁器は、半導体製造工程等で使用される、露光装置用のＸ−Ｙステージ、静電チャック及びその構造部品、ミラー等の部材に適した高強度低熱膨張性セラミックスとして有用である。また３００〜３５０℃の温度で陽極接合が可能であり、ＭＥＭＳ実装用基板としても有用である。 According to the porcelain composition of the present invention, sintering can be performed at a temperature of 850 to 900 ° C., and simultaneous firing with a low melting point / low resistance conductor such as Ag, Au, or Cu is possible, and this is sintered. by room temperature (RT = 25 ℃) ~400 linear thermal expansion coefficient at ° C. is 0~5 × 10 -6 / ℃ and smaller, and high strength low thermal of the invention flexural strength having the above high strength 150MPa An expandable porcelain can be provided. That is, since the composition for porcelain of the present invention can be sintered at a temperature of 850 to 900 ° C., it can be used not only as an insulating substrate of a wiring substrate for wiring Ag, Au, Cu, etc. Sintered high-strength, low-thermal-expansion porcelain is a high-strength, low-thermal-expansion suitable for members such as XY stages for exposure equipment, electrostatic chucks and their structural parts, and mirrors used in semiconductor manufacturing processes. Useful as ceramics. Further, anodic bonding is possible at a temperature of 300 to 350 ° C., and it is also useful as a substrate for MEMS mounting.
Claims (12)
（Ｂ）Ｂｉ2Ｏ3４〜２５質量％を含有し、８５０〜９００℃の温度で焼成して式（１）
で示される高強度低熱膨張性磁器を生成する高強度低熱膨張性磁器用組成物。 (A) Li 2 O or lithium compound (a1) that becomes Li 2 O when fired, MgO or magnesium compound (a2), Al 2 O 3 (a3), and SiO 2 (a4) that becomes MgO when fired A ratio of a1, a2, a3 and a4 (mass% ratio) α: β: γ: δ = 7.6 to 13.2: 4.0 to 10.3: 13.0 to 30 .4: 75 to 96% by mass of the calcined product in the range of 53.7 to 72.8 and (B) Bi 2 O 3 4 to 25% by mass, and calcined at a temperature of 850 to 900 ° C. 1)
A composition for high-strength low-thermal-expansion porcelain that produces a high-strength low-thermal-expansion porcelain represented by
で示される組成を有する複合酸化物を含む高強度低熱膨張性磁器。 Formula (1)
A high-strength, low-thermal-expansion porcelain containing a composite oxide having a composition represented by:
で示される組成を有する複合酸化物を含む高強度低熱膨張性磁器。 Formula (1), in which the conduction ion at the time of anodic bonding is Li ion, and anodic bonding is possible at a temperature of 300 to 350 ° C.
A high-strength, low-thermal-expansion porcelain containing a composite oxide having a composition represented by:
（Ｂ）Ｂｉ2Ｏ3４〜２５質量％を添加混合して、バインダーを含む成形助剤を加え所定形状に成形後、８５０〜９００℃で焼成して、式（１）
で示される組成を有する複合酸化物を形成することを特徴とする高強度低熱膨張性磁器の製造方法。 (A) Li 2 O or lithium compound (a1) that becomes Li 2 O when fired, MgO or magnesium compound (a2), Al 2 O 3 (a3), and SiO 2 (a4) that becomes MgO when fired A mass ratio of a1, a2, a3 and a4 α: β: γ: δ = 7.6 to 13.2: 4.0 to 10.3: 13.0 to 30.4: the mixture in the range of 53.7 to 72.8 in the precalcination 75 to 96 wt% firing pulverized at a temperature of 750 to 1000 ° C. (B) was added and mixed Bi 2 O 3 4 to 25% by weight, a binder After forming into a predetermined shape by adding a molding auxiliary containing baked at 850 to 900 ° C., the formula (1)
A method for producing a high-strength, low-thermal-expansion ceramic, characterized in that a composite oxide having the composition shown in FIG.
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| JP2016172683A (en) * | 2015-03-12 | 2016-09-29 | 中国科学院上海硅酸塩研究所 | Low temperature simultaneous calcination ceramic material and manufacturing method therefor |
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