JP2000281454A - Ceramic with low thermal expansion and high rigidity - Google Patents
Ceramic with low thermal expansion and high rigidityInfo
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- JP2000281454A JP2000281454A JP11090758A JP9075899A JP2000281454A JP 2000281454 A JP2000281454 A JP 2000281454A JP 11090758 A JP11090758 A JP 11090758A JP 9075899 A JP9075899 A JP 9075899A JP 2000281454 A JP2000281454 A JP 2000281454A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体製造プロセ
スにおける露光装置のステージ部品、チャック、構造部
品、ミラー等の部材や天体望遠鏡等の光学部品や精密測
定機用治工具等に適した低熱膨張高剛性セラミックスに
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low thermal expansion suitable for a stage component, a chuck, a structural component, a member such as a mirror, an optical component such as an astronomical telescope, a jig tool for a precision measuring machine, etc. Related to high rigidity ceramics.
【０００２】[0002]
【従来の技術】ＬＳＩなどの製造工程において、シリコ
ンウェハに配線を形成する工程において、ウェハを支持
または保持するためのサセプタ、真空チャックや絶縁リ
ングとしてあるいはその他の治具等として、これまでア
ルミナや窒化珪素や炭化珪素が比較的安価で、化学的に
も安定であるため広く用いられている。また、露光装置
のＸ−Ｙテーブル等としても従来よりアルミナや窒化珪
素などのセラミックスが同様に用いられている。2. Description of the Related Art In the process of forming wiring on a silicon wafer in the manufacturing process of LSIs and the like, a susceptor for supporting or holding the wafer, a vacuum chuck, an insulating ring, or other jigs, etc. Silicon nitride and silicon carbide are widely used because they are relatively inexpensive and chemically stable. Further, ceramics such as alumina and silicon nitride have conventionally been used similarly as an XY table of an exposure apparatus.
【０００３】また、最近では、コージェライトの低熱膨
張性を利用し、半導体製造用部品として応用すること
が、特開平１−１９１４２２号や特公平６−９７６７５
号で提案されている。特開平１−１９１４２２号によれ
ば、Ｘ線マスクにおけるマスク基板に接着する補強リン
グとして、ＳｉＯ2 、インバーなどに加え、コージェラ
イトによって形成しメンブレンの応力を制御することが
提案されている。また、特公平６−９７６７５号では、
ウェハを載置する静電チャック用基板としてアルミナや
コージェライト系焼結体を使用することが提案されてい
る。Recently, it has been proposed to use cordierite as a semiconductor manufacturing component by utilizing its low thermal expansion property, as disclosed in JP-A-1-191422 and JP-B-6-97675.
No. has been proposed. According to Japanese Patent Application Laid-Open No. 1-1191422, it is proposed that a reinforcing ring to be bonded to a mask substrate in an X-ray mask is formed of cordierite in addition to SiO 2 , invar and the like to control the stress of the membrane. In Japanese Patent Publication No. 6-97675,
It has been proposed to use an alumina or cordierite-based sintered body as a substrate for an electrostatic chuck on which a wafer is mounted.
【０００４】従来、低熱膨張材料として、コージェライ
トやリチウムアルミノシリケート（以降、ＬＡＳと表
記）、リン酸ジルコニウム系材料のリン酸ジルコニルや
リン酸ジルコニウムカリウム（以降、ＫＺＰと表記）が
よく知られている。Conventionally, cordierite and lithium aluminosilicate (hereinafter referred to as LAS), zirconyl phosphate-based materials zirconyl phosphate and potassium zirconium phosphate (hereinafter referred to as KZP) are well known as low thermal expansion materials. I have.
【０００５】コージェライト系焼結体は特公昭５７−３
６２９号、特開平２−２２９７６０号等で報告されてお
り、コージェライト粉末あるいはコージェライトを形成
するＭｇＯ、Ａｌ2 Ｏ3 、ＳｉＯ2 粉末を配合・合成し
て、これに焼結助剤として希土類酸化物やＳｉＯ2 、Ｍ
ｇＯなどを添加し、所定形状に成形後、１０００〜１４
００℃の温度で焼成することによって得られることが知
られている。ＬＡＳ系焼結体で特にβ−スポジュメンに
ついては、特公昭５３−９６０５、特公昭５６−１６４
０７０等で報告されており、天然原料を使用して、所定
形状に成形後、１１００〜１４００℃で焼成することに
よって得られることが知られている。A cordierite-based sintered body is disclosed in Japanese Patent Publication No. Sho 57-3
No. 629, JP-A-2-229760, etc., in which cordierite powder or MgO, Al 2 O 3 , SiO 2 powder which forms cordierite is blended and synthesized, and rare earth is used as a sintering aid. Oxide, SiO 2 , M
After adding gO or the like and molding into a predetermined shape, 1000 to 14
It is known that it can be obtained by firing at a temperature of 00 ° C. In particular, β-spodumene in a LAS-based sintered body is disclosed in JP-B-53-9605 and JP-B-56-164.
070 and the like, and it is known that it can be obtained by forming a predetermined shape using a natural raw material and then firing at 1100 to 1400 ° C.
【０００６】リン酸ジルコニル及び、リン酸ジルコニル
−ジルコン化合物については、特公平４−１１５０２、
特公平４−９４３、特公平６−４５１１等で報告されて
おり、リン酸ジルコニルには焼結助剤としてＺｎＯ、Ｍ
ｇＯ、Ｂｉ2 Ｏ3 等を添加し、また、リン酸ジルコニル
−ジルコン化合物にも焼結助剤としてＺｎＯ、ＭｇＯ、
Ｂｉ2 Ｏ3 等を添加、所定形状に成形後、１２００〜１
７００℃で焼成することによって得られることが知られ
ている。ＫＺＰは、特公平４−６９１０２で報告されて
おり、負の熱膨張特性を有する材料である。リン酸ジル
コニルと炭酸カリウムの合成によって得られるＫＺＰ原
料は、焼結助剤にＭｇＯ等を使用して、１１００〜１３
００℃での焼成によって得られることが知られている。As for zirconyl phosphate and zirconyl phosphate-zircon compound, Japanese Patent Publication No. 4-1502,
JP-B 4-943, JP-B 6-4511, and the like. Zirconyl phosphate has ZnO, M as a sintering aid.
gO, Bi 2 O 3, etc. are added, and ZnO, MgO,
After adding Bi 2 O 3 etc. and molding into a predetermined shape,
It is known that it can be obtained by firing at 700 ° C. KZP is reported in Japanese Patent Publication No. 4-69102 and is a material having negative thermal expansion characteristics. The KZP raw material obtained by synthesizing zirconyl phosphate and potassium carbonate is made from 1100 to 13 using MgO or the like as a sintering aid.
It is known that it can be obtained by firing at 00 ° C.
【０００７】[0007]
【発明が解決しようとする課題】近年、ＬＳＩにおける
高集積化に伴い、線幅・デザインルールの微細化が急速
に進められ、その線幅は０．３５μｍから０．１０μｍ
まで微細化しつつある。そして、Ｓｉウェハに微細な線
幅を形成するための露光装置に対して、高い精度が要求
されるようになり、たとえば露光装置のステージ用部材
においては１０ｎｍ未満の位置決め精度が要求され、露
光の位置合わせ誤差の低減が製品の品質向上や歩留まり
向上、高スループットの実現の大きな要素技術として捉
えられている。In recent years, along with the high integration of LSIs, the line width and the design rule have been rapidly miniaturized, and the line width has been reduced from 0.35 μm to 0.10 μm.
It is getting finer. High precision is required for an exposure apparatus for forming a fine line width on a Si wafer. For example, positioning accuracy of less than 10 nm is required for a stage member of the exposure apparatus, Reduction of alignment errors is regarded as a major elemental technology for improving product quality, improving yield, and achieving high throughput.
【０００８】半導体製造装置用部材として、一般に用い
られてきたアルミナ、窒化珪素などのセラミックスは、
金属に較べて軽量で熱膨張が小さく、剛性も大きい。そ
れぞれの比重はアルミナが３．８、窒化珪素が３．２と
軽量である。しかしながら、露光装置の軽量化、また、
ステージ等の駆動系部材の軽量化によるモーター負荷低
減、振動抑制のためにより軽量材が必要とされてきてい
る。Ceramics such as alumina and silicon nitride which have been generally used as members for semiconductor manufacturing equipment are:
Lighter weight, lower thermal expansion and higher rigidity than metal. The specific gravities are 3.8 for alumina and 3.2 for silicon nitride, which are lightweight. However, the lightening of the exposure apparatus,
Lighter materials are required to reduce motor load by reducing the weight of drive system members such as stages and to suppress vibration.
【０００９】一方、露光装置の使用温度近傍の１０〜４
０℃の熱膨張率はアルミナが約５．０×１０-6／℃、窒
化珪素が約１．５×１０-6／℃であり、デザインルール
の微細化とともに露光時の熱変形を軽減するために、よ
り低熱膨張材が必要とされてきている。[0009] On the other hand, 10 to 4 near the operating temperature of the exposure apparatus.
The coefficient of thermal expansion at 0 ° C. is about 5.0 × 10 −6 / ° C. for alumina and about 1.5 × 10 −6 / ° C. for silicon nitride. Therefore, a lower thermal expansion material has been required.
【００１０】これに対して、コージェライト系焼結体は
熱膨張率が０〜０．２×１０-6／℃であり、また、結晶
化ガラスは熱膨張率が０．０×１０-6／℃であり、アル
ミナや窒化珪素に比較して熱膨張率が低い。しかしなが
ら、剛性の点では、アルミナが約３５０ＧＰａ、窒化珪
素が約３００ＧＰａであるのに対し、多孔質コージェラ
イトが７０〜９０ＧＰａ、また、結晶化ガラスは９０〜
９５ＧＰａと低いため、製造装置として用いる場合、変
形や固有振動数低下に伴う共振発生による位置決め時間
増加が懸念される。On the other hand, the cordierite-based sintered body has a coefficient of thermal expansion of 0 to 0.2 × 10 −6 / ° C., and the crystallized glass has a coefficient of thermal expansion of 0.0 × 10 −6. / ° C, and has a lower coefficient of thermal expansion than alumina or silicon nitride. However, in terms of rigidity, alumina is about 350 GPa and silicon nitride is about 300 GPa, whereas porous cordierite is 70 to 90 GPa, and crystallized glass is 90 to 90 GPa.
Since it is as low as 95 GPa, when it is used as a manufacturing apparatus, there is a concern that the positioning time will increase due to the occurrence of resonance due to deformation and a decrease in natural frequency.
【００１１】また、ＬＡＳ系焼結体のβ−スポジュメン
は、比重２．０〜２．４、熱膨張率は０．３〜２．７×
１０-6／℃、磁器が気孔を有するもので−０．３〜−
１．０×１０-6／℃と低い値を示すが、ヤング率は６０
〜８０ＧＰａと低いものである。リン酸ジルコニルやリ
ン酸ジルコニル−ジルコン化合物は、比重３．５〜３．
６、熱膨張率０．０〜２．０×１０-6／℃、ヤング率１
５０〜１８０ＧＰａを示す。比重が大きい割にヤング率
はアルミナの半分程度であり、固有振動数の低下が懸念
される。The β-spodumene of the LAS sintered body has a specific gravity of 2.0 to 2.4 and a coefficient of thermal expansion of 0.3 to 2.7 ×
10 -6 / ° C, porcelain with pores -0.3 to-
It shows a low value of 1.0 × 10 −6 / ° C., but has a Young's modulus of 60
It is as low as ~ 80 GPa. Zirconyl phosphate or zirconyl phosphate-zircon compound has a specific gravity of 3.5 to 3.0.
6. Thermal expansion coefficient 0.0 to 2.0 × 10 -6 / ° C, Young's modulus 1
Indicates 50 to 180 GPa. Although the specific gravity is large, the Young's modulus is about half that of alumina, and there is a concern that the natural frequency may decrease.
【００１２】ＫＺＰもまた、結晶軸方向の熱膨張の異方
性による低熱膨張特性を顕す材料である。ＫＺＰは比重
３．１〜３．２、熱膨張率−２．５〜−２．８×１０-6
／℃、ヤング率１１０〜１３０ＧＰａを示す。ＫＺＰの
熱膨張特性は、負の熱膨張特性を示しているが、その絶
対値は窒化珪素の熱膨張率１．５×１０-6／℃と比較し
て大きく、温度変化に対する寸法変化は大きい材料と言
える。KZP is also a material exhibiting low thermal expansion characteristics due to anisotropy of thermal expansion in the crystal axis direction. KZP has a specific gravity of 3.1 to 3.2 and a coefficient of thermal expansion of −2.5 to −2.8 × 10 −6.
/ ° C and a Young's modulus of 110 to 130 GPa. Although the thermal expansion characteristic of KZP shows a negative thermal expansion characteristic, its absolute value is larger than the thermal expansion coefficient of silicon nitride of 1.5 × 10 −6 / ° C., and the dimensional change with temperature change is large. It is a material.
【００１３】以上のように、露光装置用部材として軽量
・低熱膨張・高剛性特性が要求されてきており、部材特
性は比重３．２以下、熱膨張係数が０ｐｐｍに限りなく
近く、剛性は鋳物の１３０ＧＰａ以上が求められている
が、これらを満足する材料は見当たらなかった。As described above, light-weight, low thermal expansion, and high rigidity characteristics have been demanded as members for an exposure apparatus. The member characteristics have a specific gravity of 3.2 or less, a coefficient of thermal expansion of almost 0 ppm, and a rigidity of a cast material. Of 130 GPa or more was found, but no material satisfying these was found.
【００１４】従って、本発明は低熱膨張を有するととも
に剛性の高いセラミックスとその製造方法を提供するこ
とを目的とするものである。Accordingly, an object of the present invention is to provide a ceramic having low thermal expansion and high rigidity, and a method for producing the same.
【００１５】[0015]
【課題を解決するための手段】本発明は、正の熱膨張特
性を有しかつ高剛性特性を有する材料と負の熱膨張特性
を有する材料とを複合化することにより、低熱膨張特性
と高剛性特性を有する材料を得るようにした。SUMMARY OF THE INVENTION The present invention combines a material having a positive thermal expansion characteristic and a material having a high stiffness characteristic with a material having a negative thermal expansion characteristic to thereby obtain a low thermal expansion characteristic and a high thermal expansion characteristic. A material having rigid properties was obtained.
【００１６】即ち、本発明の低熱膨張高剛性セラミック
スは、負の熱膨張特性を有するＬｉＡｌＳｉＯ4 と、正
の熱膨張特性を有しかつ高剛性特性を有するＳｉ3 Ｎ4
又はＳｉＣと、ＭｇＯの３成分から成ることを特徴とす
る。That is, the low thermal expansion and high rigidity ceramics of the present invention are composed of LiAlSiO 4 having negative thermal expansion characteristics and Si 3 N 4 having positive thermal expansion characteristics and high rigidity characteristics.
Alternatively, it is characterized by comprising three components of SiC and MgO.
【００１７】また、本発明の低熱膨張高剛性セラミック
スは、ＬｉＡｌＳｉＯ4 ６０〜９０体積％、窒化珪素１
０〜４０体積％、ＭｇＯ１〜３体積％の組成からなり、
比重２．４〜２．７、熱膨張係数が−０．１〜０．９×
１０-6／℃、ヤング率１３０〜１７５ＧＰａとなること
を特徴とする。The low-thermal-expansion high-rigidity ceramic according to the present invention comprises 60 to 90% by volume of LiAlSiO 4 ,
0-40% by volume, composed of MgO1-3% by volume,
Specific gravity 2.4-2.7, coefficient of thermal expansion -0.1-0.9x
10 -6 / ° C and a Young's modulus of 130 to 175 GPa.
【００１８】また本発明の低熱膨張高剛性セラミックス
は、ＬｉＡｌＳｉＯ4 ７０〜９０体積％、炭化珪素１０
〜３０体積％、ＭｇＯ１〜３体積％の組成からなり、比
重２．４〜２．５、熱膨張係数が−０．１〜１．３×１
０-6／℃、ヤング率１３０〜１４５ＧＰａとなることを
特徴とする。The low-thermal-expansion high-rigidity ceramic according to the present invention comprises 70 to 90% by volume of LiAlSiO 4 ,
-30% by volume, MgO1-3% by volume, specific gravity 2.4-2.5, coefficient of thermal expansion -0.1-1.3 × 1
0 -6 / ° C and a Young's modulus of 130 to 145 GPa.
【００１９】[0019]
【発明の実施の形態】本発明の低熱膨張高剛性セラミッ
クスは、軽量高剛性特性を有する窒化珪素もしくは炭化
珪素と、ＬＡＳとして知られる一般式ＬｉＡｌＳｉＯ4
で表される複合酸化物とを主成分とし、焼結助剤成分と
してＭｇＯを１〜３体積％含むものである。BEST MODE FOR CARRYING OUT THE INVENTION The low thermal expansion and high rigidity ceramics of the present invention are composed of silicon nitride or silicon carbide having light weight and high rigidity characteristics and a general formula LiAlSiO 4 known as LAS.
And MgO as a sintering aid component in an amount of 1 to 3% by volume.
【００２０】焼結助剤をＭｇＯとするＬｉＡｌＳｉＯ4
は、０〜２０℃で熱膨張率−０．８〜−０．２×１０-6
／℃、ヤング率１００〜１２０ＧＰａという特性を有す
る。これを熱膨張率１．５×１０-6／℃、ヤング率３０
０ＧＰａの窒化珪素と配合することにより、または熱膨
張率２．５×１０-6／℃、ヤング率４００ＧＰａの炭化
珪素と配合することにより、全体特性は、体積比率から
の積算値となる。LiAlSiO 4 using MgO as a sintering aid
Has a coefficient of thermal expansion of -0.8 to -0.2 × 10 -6 at 0 to 20 ° C.
/ ° C and a Young's modulus of 100 to 120 GPa. The thermal expansion coefficient is 1.5 × 10 −6 / ° C., Young's modulus is 30.
By compounding with 0 GPa of silicon nitride or with silicon carbide having a coefficient of thermal expansion of 2.5 × 10 −6 / ° C. and a Young's modulus of 400 GPa, the overall characteristics are integrated values from the volume ratio.
【００２１】従って、例えば熱膨張率０．０×１０-6／
℃とするためには、ＬｉＡｌＳｉＯ 4 ４４体積％と窒化
珪素５６体積％となる組成で得られ、この組成でのヤン
グ率２１６ＧＰａとなる。また、同様にＬｉＡｌＳｉＯ
4 ８６体積％と炭化珪素１４体積％で熱膨張率０．０×
１０-6／℃、ヤング率１５０ＧＰａとなる。Therefore, for example, a coefficient of thermal expansion of 0.0 × 10-6/
° C, LiAlSiO Four44% by volume and nitriding
It is obtained with a composition of 56% by volume of silicon.
216 GPa. Similarly, LiAlSiO
Four86 × by volume and 14% by volume of silicon carbide have a coefficient of thermal expansion of 0.0 ×
10-6/ ° C and a Young's modulus of 150 GPa.
【００２２】実際には、焼結助剤のＭｇＯが添加される
ため、全体特性は３成分での積算値となる。ＭｇＯ磁器
特性は、比重３．４〜３．５、熱膨張率は２０〜１００
０℃の測定範囲で１３〜１４×１０-6／℃、ヤング率２
７０〜２８０ＧＰａであり、熱膨張率の測定温度領域の
差はあるものの窒化珪素、炭化珪素、ＬＡＳと比較する
と熱膨張率ははるかに大きいといえる。従って、磁器特
性の熱膨張率０．０×１０-6／℃を満たすためにＭｇＯ
添加量は限定される。Actually, since the sintering aid MgO is added, the overall characteristics are integrated values of three components. MgO porcelain has a specific gravity of 3.4 to 3.5 and a coefficient of thermal expansion of 20 to 100.
13-14 × 10 -6 / ° C in the measurement range of 0 ° C, Young's modulus 2
70 to 280 GPa, and it can be said that the coefficient of thermal expansion is much larger than that of silicon nitride, silicon carbide, and LAS, although there is a difference in the measurement temperature range of the coefficient of thermal expansion. Therefore, in order to satisfy the thermal expansion coefficient of 0.0 × 10 −6 / ° C. of the porcelain characteristics, MgO
The amount added is limited.
【００２３】なお、上記のように最終焼結体の特性は各
成分の体積比率で決まることから、本発明では各成分の
好ましい組成比を体積％で限定してある。これに対し、
製造時の調合比率や、最終焼結体を分析した時の組成比
は重量％で示されるため、各成分の比重を用いて体積％
に換算すれば良い。Since the characteristics of the final sintered body are determined by the volume ratio of each component as described above, the preferred composition ratio of each component is limited to volume% in the present invention. In contrast,
Since the mixing ratio at the time of manufacture and the composition ratio when the final sintered body is analyzed are indicated by weight%, the volume% is calculated using the specific gravity of each component.
What should be converted to
【００２４】また、本発明の低熱膨張高剛性セラミック
スは、上記各成分以外に、原料中や製造工程で混入する
不可避不純物を含んでいても良い。Further, the low thermal expansion and high rigidity ceramics of the present invention may contain unavoidable impurities which are mixed in the raw material or in the production process, in addition to the above components.
【００２５】本発明の低熱膨張高剛性セラミックスの製
造方法は、平均粒径が１μｍ未満の窒化珪素粉末と平均
粒径５〜７μｍのＬｉＡｌＳｉＯ4 と平均粒径１μｍ未
満のＭｇＯを所定の比率で添加調合する。各成分を配合
した後、ボールミルなどにより平均粒径２μｍ未満とな
るように混合・粉砕し、所定形状に成形後、窒素雰囲気
下で１１００〜１２００℃で熱処理行うことによって、
比重２．４〜２．７、熱膨張率−０．１〜０．９×１０
-6／℃、ヤング率１３０〜１７５ＧＰａのセラミックス
が得られる。The method for producing a low-thermal-expansion high-rigidity ceramic according to the present invention is characterized in that a silicon nitride powder having an average particle size of less than 1 μm, LiAlSiO 4 having an average particle size of 5 to 7 μm, and MgO having an average particle size of less than 1 μm are added at a predetermined ratio. Mix. After blending each component, it is mixed and pulverized by a ball mill or the like so as to have an average particle size of less than 2 μm, formed into a predetermined shape, and then heat-treated at 1100 to 1200 ° C. under a nitrogen atmosphere.
Specific gravity 2.4 to 2.7, coefficient of thermal expansion -0.1 to 0.9 × 10
-6 / ° C., ceramics Young's modulus 130~175GPa is obtained.
【００２６】もしくは、平均粒径が１μｍ未満の炭化珪
素と平均粒径５〜７μｍのＬｉＡｌＳｉＯ4 と平均粒径
１μｍ未満のＭｇＯを所定の比率で添加調合する。各成
分を配合した後、ボールミルなどにより平均粒径２μｍ
未満となるように混合・粉砕し、所定形状に成形後、窒
素雰囲気下で１１００〜１２００℃で熱処理行うことに
よって、比重２．４〜２．５、熱膨張率−０．１〜１．
０×１０-6／℃、ヤング率１３０〜１４５ＧＰａのセラ
ミックスが得られる。Alternatively, silicon carbide having an average particle size of less than 1 μm, LiAlSiO 4 having an average particle size of 5 to 7 μm, and MgO having an average particle size of less than 1 μm are added and mixed at a predetermined ratio. After blending each component, average particle size 2μm by ball mill
And then heat-treated in a nitrogen atmosphere at 1100 to 1200 ° C. to obtain a specific gravity of 2.4 to 2.5 and a coefficient of thermal expansion of −0.1 to 1.
Ceramics having 0 × 10 −6 / ° C. and a Young's modulus of 130 to 145 GPa are obtained.
【００２７】[0027]
【実施例】実施例１ 窒化珪素とＬｉＡｌＳｉＯ4 の複合化に先立ち、ＭｇＯ
からなる焼結助剤の最適化について確認を行った。EXAMPLE 1 Prior to the compounding of silicon nitride and LiAlSiO 4 , MgO
The optimization of the sintering aid consisting of was confirmed.
【００２８】平均粒径０．９μｍで純度９９．９％以上
の窒化珪素粉末と平均粒径６．４μｍのＬｉＡｌＳｉＯ
4 粉末を体積比率で７５：２５に処方し、ＭｇＯを表１
の仕様にて配合し、ボールミルにより２４時間混合・粉
砕した後、造粒・乾燥行った。その原料粉末を所定の形
状に成形した後、窒素雰囲気下で焼成し、複合磁器の外
観及び比重、熱膨張率、ヤング率の磁器特性について評
価を行った。Silicon nitride powder having an average particle size of 0.9 μm and a purity of 99.9% or more, and LiAlSiO having an average particle size of 6.4 μm
4 Powder was formulated in a volume ratio of 75:25, and MgO was added in Table 1.
After being mixed and pulverized by a ball mill for 24 hours, granulation and drying were performed. After the raw material powder was formed into a predetermined shape, it was fired in a nitrogen atmosphere, and the appearance, specific gravity, coefficient of thermal expansion, and Young's modulus of the composite porcelain were evaluated.
【００２９】評価の結果、ＭｇＯ添加量０体積％または
５体積％では、無欠陥または緻密な磁器を得ることはで
きず、１〜３体積％で緻密な磁器を得ることが出来た。
また、磁器特性における比重が高く、熱膨張率が０に近
く、ヤング率が高いという理由によりＭｇＯの添加量は
２体積％が最適値に近いと判断した。As a result of the evaluation, no defect-free or dense porcelain could be obtained when the amount of MgO added was 0% by volume or 5% by volume, but a dense porcelain could be obtained at 1-3% by volume.
Further, it was determined that the addition amount of MgO was close to the optimum value of 2% by volume because the specific gravity in the porcelain characteristics was high, the coefficient of thermal expansion was close to 0, and the Young's modulus was high.
【００３０】以上のＭｇＯ添加量のテストに基づき、以
後の複合化テストのＭｇＯ添加量は２体積％とした。Based on the above MgO addition amount test, the MgO addition amount in the subsequent composite test was set to 2% by volume.
【００３１】[0031]
【表１】 [Table 1]
【００３２】次に複合化仕様評価を行った。平均粒径
０．９μｍで純度９９．９％以上の窒化珪素粉末、６．
４μｍのＬｉＡｌＳｉＯ4 粉末、平均粒径０．７μｍの
ＭｇＯを窒化珪素粉末とＬｉＡｌＳｉＯ4 粉末の総量に
対し２体積％とし、表２の仕様で配合し、ボールミルに
より２４時間混合・粉砕した後、造粒・乾燥行った。そ
の原料粉末を所定の形状に成形した後、窒素雰囲気下に
て焼成し、複合磁器の外観及び比重・熱膨張率・ヤング
率の磁器特性について評価を行った。Next, the composite specification was evaluated. 5. silicon nitride powder having an average particle size of 0.9 μm and a purity of 99.9% or more;
After mixing 4 μm of LiAlSiO 4 powder and MgO having an average particle diameter of 0.7 μm with respect to the total amount of the silicon nitride powder and the LiAlSiO 4 powder, 2 vol% was blended according to the specifications in Table 2, and mixed and pulverized for 24 hours by a ball mill. Granulated and dried. After the raw material powder was formed into a predetermined shape, it was fired in a nitrogen atmosphere, and the appearance of the composite porcelain and the porcelain characteristics such as specific gravity, thermal expansion coefficient and Young's modulus were evaluated.
【００３３】評価の結果を表２に示す。ＬｉＡｌＳｉＯ
4 ：窒化珪素＝６０：４０〜９０：１０で熱膨張率−
０．１〜０．９×１０-6／℃、ヤング率１３０〜１７５
ＧＰａとなる欠陥のない磁器が得られた。Table 2 shows the results of the evaluation. LiAlSiO
4 : Coefficient of thermal expansion when silicon nitride = 60:40 to 90:10
0.1-0.9 × 10 -6 / ° C, Young's modulus 130-175
A porcelain free of GPa was obtained.
【００３４】[0034]
【表２】 [Table 2]
【００３５】実施例２ 次に炭化珪素とＬｉＡｌＳｉＯ4 の複合化における焼結
助剤の最適化を行った。Example 2 Next, the sintering aid in the compounding of silicon carbide and LiAlSiO 4 was optimized.
【００３６】平均粒径０．７μｍで純度９９．９％以上
の炭化珪素粉末と平均粒径６．４μｍのＬｉＡｌＳｉＯ
4 粉末を体積比率で８０：２０に処方し、ＭｇＯを表３
の仕様にて配合し、ボールミルにより２４時間混合・粉
砕した後、造粒・乾燥行った。その原料粉末を所定の形
状に成形した後、窒素雰囲気下で焼成し、複合磁器の外
観及び比重・熱膨張率・ヤング率の磁器特性について評
価行った。Silicon carbide powder having an average particle size of 0.7 μm and a purity of 99.9% or more, and LiAlSiO having an average particle size of 6.4 μm
4 Powder was formulated in a volume ratio of 80:20, and MgO
After being mixed and pulverized by a ball mill for 24 hours, granulation and drying were performed. After the raw material powder was formed into a predetermined shape, it was fired in a nitrogen atmosphere, and the appearance of the composite porcelain and the porcelain characteristics such as specific gravity, coefficient of thermal expansion and Young's modulus were evaluated.
【００３７】評価の結果、０体積％または５体積％で
は、無欠陥または緻密な磁器を得ることはできず、Ｍｇ
Ｏ添加量１〜３体積％で緻密な磁器を得ることが出来
た。また、磁器特性における比重が高く、熱膨張率が０
に近く、ヤング率が高いという理由によりＭｇＯの添加
量は２体積％が最適値に近いと判断した。以上のＭｇＯ
添加量のテストに基づき、以後の複合化テストのＭｇＯ
添加量は２体積％とした。As a result of the evaluation, if it is 0% by volume or 5% by volume, no defect-free or dense porcelain cannot be obtained.
A dense porcelain could be obtained with an O content of 1 to 3% by volume. Further, the specific gravity in the porcelain characteristics is high and the coefficient of thermal expansion is 0
It was determined that the addition amount of MgO was close to the optimum value of 2% by volume because of the high Young's modulus. The above MgO
Based on the test of the amount of addition,
The addition amount was 2% by volume.
【００３８】[0038]
【表３】 [Table 3]
【００３９】平均粒径０．７μｍで純度９９．９％以上
の炭化珪素粉末、６．４μｍのＬｉＡｌＳｉＯ4 粉末、
平均粒径０．７μｍのＭｇＯを窒化珪素粉末とＬｉＡｌ
ＳｉＯ4 粉末の総量に対し２体積％とし、表４の仕様で
配合し、ボールミルにより２４時間混合・粉砕した後、
造粒・乾燥を行った。その原料粉末を所定の形状に成形
した後、窒素雰囲気下にて焼成し、複合磁器の外観及び
比重・熱膨張率・ヤング率の磁器特性について評価行っ
た。Silicon carbide powder having an average particle diameter of 0.7 μm and a purity of 99.9% or more, LiAlSiO 4 powder of 6.4 μm,
MgO having an average particle size of 0.7 μm is mixed with silicon nitride powder and LiAl
2 vol% with respect to the total amount of the SiO 4 powder, blended according to the specifications in Table 4, mixed and pulverized by a ball mill for 24 hours,
Granulation and drying were performed. After the raw material powder was formed into a predetermined shape, it was fired in a nitrogen atmosphere, and the appearance of the composite porcelain and the porcelain characteristics such as specific gravity, coefficient of thermal expansion and Young's modulus were evaluated.
【００４０】評価の結果を表４に示す。ＬｉＡｌＳｉＯ
4 ：炭化珪素＝７０：３０〜９０：１０で熱膨張率−
０．１〜０．９×１０-6／℃、ヤング率１３０〜１４５
ＧＰａとなる欠陥のない磁器が得られた。Table 4 shows the results of the evaluation. LiAlSiO
4 : Thermal expansion coefficient at silicon carbide = 70:30 to 90:10-
0.1-0.9 × 10 -6 / ° C, Young's modulus 130-145
A porcelain free of GPa was obtained.
【００４１】[0041]
【表４】 [Table 4]
【００４２】[0042]
【発明の効果】以上、詳述したとおり、本発明によれ
ば、窒化珪素とＬｉＡｌＳｉＯ4 の複合化により、熱膨
張率−０．１〜０．９×１０-6／℃、ヤング率１３０〜
１７５ＧＰａ、比重２．４〜２．７となる低熱膨張高剛
性セラミックスを得ることができる。また、炭化珪素と
ＬｉＡｌＳｉＯ4 の複合化により、熱膨張率−０．１〜
０．９×１０-6／℃、ヤング率１３０〜１４５ＧＰａ、
比重２．４〜２．５となる低熱膨張高剛性セラミックス
を得ることができる。Effect of the Invention] above, as detailed, according to the present invention, the composite of silicon nitride and LiAlSiO 4, the coefficient of thermal expansion -0.1~0.9 × 10 -6 / ℃, Young's modulus 130 to
A low-thermal-expansion high-rigidity ceramic having 175 GPa and a specific gravity of 2.4 to 2.7 can be obtained. In addition, the composite of silicon carbide and LiAlSiO 4 provides a thermal expansion coefficient of −0.1 to
0.9 × 10 −6 / ° C., Young's modulus 130 to 145 GPa,
A low thermal expansion and high rigidity ceramic having a specific gravity of 2.4 to 2.5 can be obtained.
【００４３】この低熱膨張高剛性セラミックスを高微細
な回路を形成するためのウェハの支持または支持台を構
成する露光装置用部品、例えば、ステージ部品、真空チ
ャック、ミラーとして用いることにより温度変化に対し
て寸法安定性に優れ、変形・振動の影響が極めて少な
く、半導体素子製造の品質と量産性を高めることができ
る。The low thermal expansion and high rigidity ceramic is used as a part for an exposure apparatus, for example, a stage part, a vacuum chuck, and a mirror, which constitutes a support or a support for a wafer for forming a fine circuit, so that it can withstand temperature changes. As a result, the dimensional stability is excellent, the influence of deformation and vibration is extremely small, and the quality and mass productivity of semiconductor device manufacturing can be improved.
Claims (5)
Ｃと、ＭｇＯの３成分から成ることを特徴とする低熱膨
張高剛性セラミックス。1. A method according to claim 1, wherein the first and second layers are LiAlSiO 4 and Si 3 N 4 or Si 3
A low-thermal-expansion high-rigidity ceramic comprising C and three components of MgO.
3 Ｎ4 １０〜４０体積％を主成分とし、これらに対しＭ
ｇＯ１〜３体積％を含むことを特徴とする請求項１記載
の低熱膨張高剛性セラミックス。2. 60% to 90% by volume of LiAlSiO 4 , Si
3 N 4 10 to 40 vol% of the main component, M for these
The low-thermal-expansion high-rigidity ceramic according to claim 1, comprising 1 to 3% by volume of gO1.
ヤング率１３０〜１７５ＧＰａ、比重２．４〜２．７で
あることを特徴とする請求項２記載の低熱膨張高剛性セ
ラミックス3. coefficient of thermal expansion-0.1 to 0.9 × 10 −6 / ° C.
The low thermal expansion and high rigidity ceramic according to claim 2, wherein the ceramic has a Young's modulus of 130 to 175 GPa and a specific gravity of 2.4 to 2.7.
Ｃ１０〜３０体積％を主成分とし、これらに対しＭｇＯ
１〜３体積％を含むことを特徴とする請求項１記載の低
熱膨張高剛性セラミックス。 4. 70% to 90% by volume of LiAlSiO 4 , Si
C10 to 30% by volume as a main component, and MgO
The low-thermal-expansion high-rigidity ceramic according to claim 1, comprising 1 to 3% by volume.
ヤング率１３０〜１４５ＧＰａ、比重２．４〜２．５で
あることを特徴とする請求項４記載の低熱膨張高剛性セ
ラミックス。5. Coefficient of thermal expansion-0.1 to 1.0 × 10 −6 / ° C.
The low thermal expansion and high rigidity ceramic according to claim 4, wherein the ceramic has a Young's modulus of 130 to 145 GPa and a specific gravity of 2.4 to 2.5.
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| JP4540239B2 (en) * | 2001-01-31 | 2010-09-08 | 京セラ株式会社 | Aluminosilicate sintered body and stress relieving member using the same |
| WO2004074939A1 (en) * | 2003-02-21 | 2004-09-02 | Nihon Ceratec Co., Ltd. | Exposure apparatus for liquid crystal panel and exposure apparatus |
| WO2020013266A1 (en) * | 2018-07-12 | 2020-01-16 | 京セラ株式会社 | Complex |
| KR20210016040A (en) * | 2018-07-12 | 2021-02-10 | 교세라 가부시키가이샤 | Complex |
| CN112368431A (en) * | 2018-07-12 | 2021-02-12 | 京瓷株式会社 | Composite body |
| JP6999813B2 (en) | 2018-07-12 | 2022-01-19 | 京セラ株式会社 | Complex |
| CN112368431B (en) * | 2018-07-12 | 2022-09-16 | 京瓷株式会社 | Composite body |
| KR102545364B1 (en) | 2018-07-12 | 2023-06-20 | 교세라 가부시키가이샤 | complex |
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| JP4025455B2 (en) | 2007-12-19 |
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