JP2000191369A - Components for semiconductor / liquid crystal manufacturing equipment - Google Patents
Components for semiconductor / liquid crystal manufacturing equipmentInfo
- Publication number
- JP2000191369A JP2000191369A JP37172698A JP37172698A JP2000191369A JP 2000191369 A JP2000191369 A JP 2000191369A JP 37172698 A JP37172698 A JP 37172698A JP 37172698 A JP37172698 A JP 37172698A JP 2000191369 A JP2000191369 A JP 2000191369A
- Authority
- JP
- Japan
- Prior art keywords
- yag
- zirconia
- alumina
- yttria
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title description 16
- 239000004065 semiconductor Substances 0.000 title description 16
- 239000004973 liquid crystal related substance Substances 0.000 title description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 90
- 230000007797 corrosion Effects 0.000 claims abstract description 73
- 238000005260 corrosion Methods 0.000 claims abstract description 73
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 230000035939 shock Effects 0.000 claims abstract description 27
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 claims 2
- 239000002223 garnet Substances 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 67
- 210000002381 plasma Anatomy 0.000 abstract description 37
- 229910052736 halogen Inorganic materials 0.000 abstract description 26
- 150000002367 halogens Chemical class 0.000 abstract description 26
- 239000000460 chlorine Substances 0.000 abstract description 15
- 238000005530 etching Methods 0.000 abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 8
- 239000011737 fluorine Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical group [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 37
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 37
- 230000008859 change Effects 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 10
- 150000004820 halides Chemical class 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910016569 AlF 3 Inorganic materials 0.000 description 3
- -1 Cl 4 Chemical compound 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体・液晶製造
装置において、内壁材（チャンバー）、マイクロ波導入
窓、シャワーヘッド、フォーカスリング、シールドリン
グ等をはじめとする半導体・液晶製造装置（エッチャー
やＣＶＤ等）の中でも特に腐食性ガス又はそのプラズマ
に対して高い耐食性を求められる部材に適用できるもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor / liquid crystal manufacturing apparatus including an inner wall material (chamber), a microwave introduction window, a shower head, a focus ring, a shield ring and the like. Among them, it can be applied to members requiring high corrosion resistance to corrosive gas or its plasma.
【０００２】[0002]
【従来の技術】半導体製造におけるドライエッチングプ
ロセスや成膜プロセスなどの各プロセスにおいて、プラ
ズマを利用した技術が盛んに使われている。半導体の製
造時におけるプラズマプロセスでは、特にエッチング、
クリーニング用として、反応性の高いフッ素系、塩素系
等のハロゲン系腐食性ガスが多用されている。これら腐
食性ガス及びプラズマに接触する部材には、高い耐食性
が要求される。従来より、被処理物以外でこれらの腐食
性ガス及びプラズマに接触する部材は、一般に石英ガラ
スやステンレス、アルミニウム等の耐食性金属が利用さ
れていた。さらには、アルミナ焼結体や窒化アルミニウ
ム焼結体、及びこれらセラミックス焼結体に炭化珪素等
のセラミック膜を被覆したものが耐食性が優れるとして
使用されていた（特公平５−５３８７２号、特開平３−
２１７０１６号、特開平８−９１９３２号参照）。2. Description of the Related Art In each process such as a dry etching process and a film forming process in semiconductor manufacturing, a technology utilizing plasma is actively used. In the plasma process during the manufacture of semiconductors, especially etching,
For cleaning, highly reactive fluorine-based, chlorine-based, and other halogen-based corrosive gases are frequently used. The members that come into contact with the corrosive gas and the plasma are required to have high corrosion resistance. Heretofore, members that come into contact with these corrosive gases and plasmas other than the object to be treated have generally been made of corrosion-resistant metals such as quartz glass, stainless steel, and aluminum. Further, alumina sintered bodies, aluminum nitride sintered bodies, and those obtained by coating these ceramics sintered bodies with a ceramic film such as silicon carbide have been used because of their excellent corrosion resistance (Japanese Patent Publication No. 5-53872, Japanese Unexamined Patent Publication No. 3-
21716, and JP-A-8-91932).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来か
ら用いられている石英ガラスやステンレスなどの金属を
使用した部材ではプラズマ中の耐食性が不充分で消耗が
激しく、特にフッ素系や塩素系プラズマに接すると接触
面がエッチングされ、表面性状が変化したり、光透過性
が必要とされる石英部材では、表面が次第に白く曇って
透光性が低下する等の問題を生じていた。However, members using metals such as quartz glass and stainless steel which have been used in the past have insufficient corrosion resistance in plasma and are intensely depleted. As a result, the contact surface is etched, the surface properties are changed, and in the case of a quartz member requiring light transmittance, the surface gradually becomes cloudy and the light transmittance decreases.
【０００４】上記問題を解決するために、アルミナ焼結
体や窒化アルミニウム焼結体、あるいは、カーボンや炭
化珪素焼結体表面に炭化珪素等のセラミック膜を被覆し
たものが考案されている。しかしながら、石英ガラスや
耐食性金属と比較するとハロゲン系腐食性ガスに対する
耐食性は優れるものの、やはりプラズマと接すると腐食
が徐々に進行して、セラミック焼結体の表面や結晶粒界
からハロゲン化物が蒸発し消耗していく。これはプラズ
マで生成されるアルミニウム成分あるいはシリコン成分
とハロゲン系ガスとのハロゲン化物の融点が低いためで
ある。この為、さらに耐食性の高い材料が望まれてい
た。[0004] In order to solve the above-mentioned problems, there have been proposed a sintered body of alumina, a sintered body of aluminum nitride, or a sintered body of carbon or silicon carbide coated with a ceramic film such as silicon carbide. However, although corrosion resistance to halogen-based corrosive gases is superior to quartz glass and corrosion-resistant metals, corrosion also gradually progresses in contact with plasma, and halide evaporates from the surface and crystal grain boundaries of the ceramic sintered body. Wears out. This is because the melting point of the halide of the aluminum component or silicon component and the halogen-based gas generated by the plasma is low. For this reason, materials with even higher corrosion resistance have been desired.
【０００５】また、ドライエッチングプロセスでは、前
述の耐食性だけでなくパーティクルの発生も問題となっ
ている。これは、発生したパーティクルがメタル配線の
断線や短絡等を発生させ、デバイス特性の劣化を引き起
こすためである。このパーティクルは、チャンバー内を
構成する内壁材やクランプリング等の部材がハロゲン系
腐食性ガスやプラズマにより腐食されることで発生す
る。即ち、腐食により蒸発したハロゲン化物が、チャン
バー内壁等に堆積を繰り返し、これが落下することでパ
ーティクルとなる。この為、この蒸発したハロゲン化物
がチャンバー内壁へ堆積するのを防ぐ目的で、ランプ等
を用いてチャンバー外壁を加熱し、ハロゲン化物を蒸発
・排気させることが行われている。この為、チャンバー
内に使用される部品は、耐食性だけでなく、耐熱衝撃性
も要求されるものがある。In the dry etching process, not only the above-mentioned corrosion resistance but also the generation of particles are problematic. This is because the generated particles cause disconnection or short circuit of the metal wiring and cause deterioration of device characteristics. These particles are generated when members such as an inner wall material and a clamp ring constituting the inside of the chamber are corroded by a halogen-based corrosive gas or plasma. That is, the halide evaporated by the corrosion repeatedly deposits on the inner wall of the chamber and the like, and drops to become particles. Therefore, in order to prevent the evaporated halide from depositing on the inner wall of the chamber, the outer wall of the chamber is heated by using a lamp or the like to evaporate and exhaust the halide. For this reason, some components used in the chamber require not only corrosion resistance but also thermal shock resistance.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、ハロゲン
系腐食性ガス及びそのプラズマに対する耐食性を具備
し、耐熱衝撃性も有するセラミック焼結体の具体的な構
成について検討を重ねた結果、イットリアとアルミナの
化合物を主結晶相とする焼結体が、ハロゲン系腐食性ガ
ス又はそのプラズマと反応してハロゲン化物を生成した
としても融点が高く安定であることから耐食性に優れる
ことを見出し、さらには、ジルコニア及びセリアを添加
することで耐食性を損なわずに耐熱衝撃性が向上するこ
とを見いだした。Means for Solving the Problems The present inventors have repeatedly studied the specific constitution of a ceramic sintered body having corrosion resistance to a halogen-based corrosive gas and its plasma and also having thermal shock resistance. A sintered body having a compound of yttria and alumina as a main crystal phase, having a high melting point and being stable even if it produces a halide by reacting with a halogen-based corrosive gas or its plasma, has been found to be excellent in corrosion resistance, Furthermore, it has been found that by adding zirconia and ceria, the thermal shock resistance is improved without impairing the corrosion resistance.
【０００７】また、セラミック焼結体に、多数の気孔が
あると腐食を受けやすく、耐食性が大きく低下すること
を見出した。[0007] It has also been found that if the ceramic sintered body has a large number of pores, it is susceptible to corrosion and the corrosion resistance is greatly reduced.
【０００８】即ち、本発明は、フッ素系や塩素系等のハ
ロゲン系腐食性ガス及びそのプラズマに曝される耐食性
部材を、イットリアとアルミナの化合物で形成し、その
主結晶相をＹＡＧ、あるいはＹＡＧとアルミナ、または
ＹＡＧとイットリアの混合相とし、ジルコニアを５００
〜５００００ｐｐｍ含むことを特徴とする。That is, according to the present invention, a corrosion-resistant member exposed to a halogen-based corrosive gas such as a fluorine-based or chlorine-based gas and its plasma is formed of a compound of yttria and alumina, and its main crystal phase is YAG or YAG. And alumina, or a mixed phase of YAG and yttria, and zirconia of 500
50,000 ppm.
【０００９】さらに、結晶粒径を１０μｍ以下に細かく
し、気孔率を０．２％以下としたことを特徴とする。Further, the present invention is characterized in that the crystal grain size is reduced to 10 μm or less, and the porosity is set to 0.2% or less.
【００１０】[0010]
【発明の実施の形態】本発明の耐食性セラミック部材
は、ハロゲン系腐食性ガスあるいはそのプラズマに曝さ
れる部材であり、ハロゲン系腐食性ガスとしては、ＳＦ
6 、ＣＦ4 、ＣＨＦ3 、ＣｌＦ3 、ＮＦ3 、Ｃ4 Ｆ8 、
ＨＦ等のフッ素系ガス、Ｃｌ2 、ＨＣｌ、ＢＣｌ3 、Ｃ
Ｃｌ4 等の塩素系ガス、あるいはＢｒ2 、ＨＢｒ、ＢＢ
ｒ3 等の臭素系ガスなどがある。そして、これらのハロ
ゲン系腐食性ガスが使用される雰囲気下でマイクロ波や
高周波が導入されるとこれらのガスがプラズマ化される
ことになる。BEST MODE FOR CARRYING OUT THE INVENTION The corrosion-resistant ceramic member of the present invention is a member exposed to a halogen-based corrosive gas or its plasma.
6 , CF 4 , CHF 3 , ClF 3 , NF 3 , C 4 F 8 ,
Fluorine gas such as HF, Cl 2 , HCl, BCl 3 , C
Chlorine gas such as Cl 4 , or Br 2 , HBr, BB
there is such as bromine-based gas of r 3 and the like. When microwaves or high frequencies are introduced in an atmosphere in which these halogen-based corrosive gases are used, these gases are turned into plasma.
【００１１】また、エッチング効果をより高めるため
に、ハロゲン系腐食性ガスとともに、Ａｒなどの不活性
ガスを導入してプラズマを発生させることもある。In order to further enhance the etching effect, plasma may be generated by introducing an inert gas such as Ar together with a halogen-based corrosive gas.
【００１２】本発明は、これらのハロゲン系腐食性ガス
又はそのプラズマに曝される部材をイットリアとアルミ
ナの化合物で形成したものであり、その主結晶相をＹＡ
Ｇ、あるいはＹＡＧとアルミナ、またはＹＡＧとイット
リアからなるセラミック焼結体としたものである。According to the present invention, the member exposed to the halogen-based corrosive gas or its plasma is formed of a compound of yttria and alumina, and its main crystal phase is YA.
G, or a ceramic sintered body made of YAG and alumina, or YAG and yttria.
【００１３】即ち、セラミック焼結体の結晶相を構成す
るイットリアとアルミナの化合物は、フッ素系ガスと反
応すると主にＹＦ3 、ＡｌＦ3 を生成し、また、塩素系
ガスと反応するとＹＣｌ3 、ＡｌＣｌ3 を生成するが、
イットリアのハロゲン化物の融点（ＹＦ3 ：１１５２
℃、ＹＣｌ3 ：６８０℃）は、従来の石英ガラスあるい
はアルミナ焼結体や窒化アルミニウム焼結体との反応に
より生成されるハロゲン化物の融点（ＳｉＦ4 ：−９０
℃、ＳｉＣｌ4 ：−７０℃、ＡｌＦ3 ：１０４０℃、Ａ
ｌＣｌ3 ：１７８℃）より高いために、ハロゲン系腐食
性ガスやプラズマに高温で曝されたとしても安定した耐
食性を具備する。That is, the compound of yttria and alumina constituting the crystal phase of the ceramic sintered body mainly produces YF 3 and AlF 3 when reacted with a fluorine-based gas, and YCl 3 and AlF 3 when reacted with a chlorine-based gas. Produces AlCl 3 ,
Melting point of yttria halide (YF 3 : 1152
° C, YCl 3 : 680 ° C) is the melting point (SiF 4 : -90) of the halide produced by the reaction with the conventional quartz glass or the sintered body of alumina or aluminum nitride.
℃, SiCl 4: -70 ℃, AlF 3: 1040 ℃, A
(1Cl 3 : 178 ° C.), so that it has stable corrosion resistance even when exposed to a halogen-based corrosive gas or plasma at a high temperature.
【００１４】しかしながら、イットリア単体では焼結性
が非常に低く、その気孔率は２％以上存在し、緻密体を
得ることはできない。このため、ハロゲン系腐食性ガス
やプラズマに対する耐食性も著しく低下する。また、ア
ルミナの成分についても、イットリアとの化合物とする
ことによりアルミナ成分のハロゲン化物生成が抑えられ
ることを見出した。そこで、本発明者らは、イットリア
とアルミナの化合物を主体とすることにより、ハロゲン
系腐食性ガスやプラズマとの反応により形成されるハロ
ゲン化物の融点を高くし、また結晶粒径を１０μｍ以下
とすることで、緻密化をはかり、気孔率も０．２％以下
にし耐食性を向上させた。ここで、イットリアとアルミ
ナの組成比率は下式に示す組成比においてＹＡＧが形成
される。そして、この比率を下式範囲以外に種々変化さ
せると、ＹＡＧとアルミナ、あるいはＹＡＧとイットリ
アの混合相が得られる。However, sinterability of yttria alone is very low, and its porosity is 2% or more, so that a dense body cannot be obtained. For this reason, the corrosion resistance to halogen-based corrosive gas and plasma is significantly reduced. It has also been found that the formation of a halide in the alumina component can be suppressed by using a compound with yttria for the alumina component. Thus, the present inventors have made the compound of yttria and alumina a main component to increase the melting point of the halide formed by the reaction with the halogen-based corrosive gas or plasma, and to reduce the crystal grain size to 10 μm or less. By doing so, densification was achieved, the porosity was reduced to 0.2% or less, and the corrosion resistance was improved. Here, YAG is formed at a composition ratio of yttria and alumina represented by the following formula. When this ratio is variously changed outside the range of the following formula, a mixed phase of YAG and alumina or YAG and yttria is obtained.
【００１５】 Ａ＋Ｂ＝１ 0.365 ≦Ａ≦0.385 0.615≦Ｂ≦0.635 ： 結晶相ＹＡＧ（モル量） ここで（Ａ）イットリア、（Ｂ）アルミナ さらに、本発明者は、イットリアとアルミナの化合物か
らなるセラミック焼結体の耐熱衝撃性を向上させるため
に、正方晶のジルコニアを５００〜５００００ｐｐｍ添
加することで、上記セラミックス焼結体の耐食性を損な
うことなく、耐熱衝撃性を高め、半導体・液晶製造装置
等に用いられる部材としての適用範囲をさらに広げたも
のである。A + B = 1 0.365 ≦ A ≦ 0.385 0.615 ≦ B ≦ 0.635: Crystalline phase YAG (molar amount) (A) Yttria, (B) Alumina Further, the present inventor further provided a ceramic comprising a compound of yttria and alumina. In order to improve the thermal shock resistance of the sintered body, by adding 500 to 50,000 ppm of tetragonal zirconia, the thermal shock resistance of the ceramic sintered body is increased without impairing the corrosion resistance of the ceramic sintered body. The range of application as a member used in the above is further expanded.
【００１６】即ち、ジルコニア成分を５００ｐｐｍ以上
含有させることにより、耐熱衝撃性が向上することを見
いだした。これは、イットリアとアルミナの化合物から
なる焼結体中にジルコニアを分散させることにより、熱
衝撃時に発生するクラックの進展をジルコニアが妨げる
ためである。That is, it has been found that the thermal shock resistance is improved by containing 500 ppm or more of the zirconia component. This is because, by dispersing zirconia in a sintered body made of a compound of yttria and alumina, zirconia hinders the progress of cracks generated at the time of thermal shock.
【００１７】詳細には、焼結体中のジルコニアを正方晶
の結晶形態で存在させ、熱衝撃により発生するクラック
の進展を正方晶のジルコニアが単斜晶へと相変態を起こ
すことでクラックの進展エネルギーを吸収させるのであ
る。上記ジルコニアを正方晶で安定化させるための安定
化剤としては、セリアを用いるのが良い。ジルコニアを
安定化させる助剤としてはイットリアやカルシア等もあ
るが、助剤としての効果を種々検討した結果、イットリ
アは本発明の焼結体においてはアルミナとの合成に使用
されるためジルコニアへの安定化効果がなく、カルシア
は耐食性の点で劣っており、セリアが最も効果的であっ
た。More specifically, zirconia in the sintered body is present in the form of a tetragonal crystal, and the propagation of cracks generated by thermal shock is reduced by the phase transformation of tetragonal zirconia to monoclinic. It absorbs the energy of progress. Ceria is preferably used as a stabilizer for stabilizing the zirconia with a tetragonal crystal. There are yttria and calcia as auxiliaries for stabilizing zirconia, but as a result of various studies on the effect as auxiliaries, yttria is used for synthesis with alumina in the sintered body of the present invention, so There was no stabilizing effect, calcia was inferior in corrosion resistance, and ceria was most effective.
【００１８】このジルコニアの添加量は、５００００ｐ
ｐｍ以下にする必要がある。これ以上となると、ジルコ
ニアの耐食性は劣ることからハロゲン系腐食性ガス又は
そのプラズマによる腐食を受けやすくなるからである。
ここで、セリアの添加量はジルコニア１００重量％に対
し、１重量％以上添加すれば、ジルコニア成分の安定化
がはかれる。また、セリアの効果としてはランプ加熱に
よりかかる１００〜２００℃の温度に対するジルコニア
の熱劣化を防ぐことにもつながる。イットリアとアルミ
ナの化合物としては、ＹＡＧ、あるいはＹＡＧとアルミ
ナ、またはＹＡＧとイットリアを主結晶としたセラミッ
ク焼結体がある。The amount of zirconia added is 50,000 p
pm or less. If it is more than this, the corrosion resistance of zirconia is inferior, so that it becomes susceptible to corrosion by halogen-based corrosive gas or its plasma.
Here, if the amount of ceria is 1% by weight or more based on 100% by weight of zirconia, the zirconia component can be stabilized. In addition, the effect of ceria also leads to preventing thermal deterioration of zirconia at a temperature of 100 to 200 ° C. caused by lamp heating. Examples of the compound of yttria and alumina include YAG, or a ceramic sintered body having YAG and yttria as main crystals.
【００１９】また、セラミック焼結体の気孔率を０．２
％以下とするのは気孔が存在すると、気孔のエッジが腐
食を受けやすく、気孔率が０．２％を越えると、腐食の
進行が加速されるためである。緻密化上げ、気孔率を
０．２％以下とするためには、一次原料を１〜２μｍ程
度にし焼結性を高める必要がある。これにより焼結体の
結晶粒径を１０μｍ以下とし、気孔率を０．２％以下と
することができる。The porosity of the ceramic sintered body is 0.2
The reason for the lower limit is that if the pores are present, the edges of the pores are susceptible to corrosion, and if the porosity exceeds 0.2%, the progress of corrosion is accelerated. In order to increase the density and reduce the porosity to 0.2% or less, it is necessary to increase the sinterability by using a primary material of about 1 to 2 μm. Thereby, the crystal grain size of the sintered body can be reduced to 10 μm or less, and the porosity can be reduced to 0.2% or less.
【００２０】なお、セラミック焼結体の結晶相について
はＸ線回折で、含有量についてはＩＣＰ発光分析又は蛍
光Ｘ線で、気孔率についてはアルキメデス法によりそれ
ぞれ求めることができる。The crystal phase of the ceramic sintered body can be determined by X-ray diffraction, the content can be determined by ICP emission analysis or fluorescent X-ray, and the porosity can be determined by Archimedes' method.
【００２１】本発明の耐食性セラミックス部材の応用例
として、図１にエッチング装置内部の略図を示す。部品
番号１はチャンバーを、２はクランプリングを、３は下
部電極を、４はウェハーを、５は高周波コイルを示す。
この中で、部品番号１や２に示すような、ハロゲン系腐
食性ガスやそのプラズマに曝される部分に、本発明の耐
食性セラミックス部材を適用すれば、優れた耐食性を示
し、また熱衝撃による割れ等も発生しなかった。FIG. 1 shows a schematic view of the interior of an etching apparatus as an application example of the corrosion-resistant ceramic member of the present invention. Part number 1 indicates a chamber, 2 indicates a clamp ring, 3 indicates a lower electrode, 4 indicates a wafer, and 5 indicates a high-frequency coil.
Among them, when the corrosion-resistant ceramic member of the present invention is applied to a part exposed to a halogen-based corrosive gas or its plasma as shown in part numbers 1 and 2, excellent corrosion resistance is exhibited, No cracks or the like occurred.
【００２２】[0022]
【実施例】実施例１ 本発明の耐食性部材として、ジルコニア５０００ｐｐ
ｍ、セリア５０ｐｐｍを含んだＹＡＧ、ＹＡＧとイット
リアの混合相、ＹＡＧとアルミナの混合相からなるセラ
ミック焼結体と、ＹＡＧを主結晶相としてジルコニア、
セリアの添加量を変化させたセラミック焼結体と、従来
の耐食性部材として、石英ガラス、純度９９．５ｗｔ％
のアルミナ焼結体、及び純度９９．９ｗｔ％のアルミナ
焼結体、ジルコニア、セリアを含まないＹＡＧをそれぞ
れ用意し、フッ素系及び塩素系腐食性ガス下でプラズマ
に曝した時の耐食性について実験を行った。EXAMPLE 1 5000 pp of zirconia was used as a corrosion-resistant member of the present invention.
m, YAG containing 50 ppm ceria, a ceramic sintered body composed of a mixed phase of YAG and yttria, a mixed phase of YAG and alumina, zirconia with YAG as a main crystal phase,
A ceramic sintered body in which the added amount of ceria is changed, and quartz glass as a conventional corrosion-resistant member, a purity of 99.5 wt%
An alumina sintered body of 99.9% by weight and a sintered body of 99.9% by weight, YAG containing no zirconia and ceria were prepared, respectively, and the corrosion resistance when exposed to plasma under a fluorine-based or chlorine-based corrosive gas was examined. went.
【００２３】本実験では、本発明及び従来の耐食性部材
を直径３０ｍｍ×厚み３ｍｍに製作した後、表面にラッ
プ加工を施して鏡面にしたものを試料とし、この試料を
ＲＩＥ（Ｒｅａｃｔｉｖｅ Ｉｏｎ Ｅｔｃｈｉｎｇ）
装置にセットしてＳＦ6 ガス雰囲気下及びＣｌ2 ガス雰
囲気下でプラズマ中に３時間曝した後、処理前後の重量
の減少量から１分間当たりのエッチングレートを算出し
た。エッチングレートの数値は、９９．９ｗｔ％のアル
ミナ焼結体のエッチングレートを１としたときの相対比
較で示す。In this experiment, the present invention and the conventional corrosion-resistant member were manufactured to have a diameter of 30 mm × thickness of 3 mm, and then lapping the surface to make a mirror surface, which was used as a sample. The sample was subjected to RIE (Reactive Ion Etching).
After being set in an apparatus and exposed to plasma in an SF 6 gas atmosphere and a Cl 2 gas atmosphere for 3 hours, the etching rate per minute was calculated from the weight loss before and after the treatment. The numerical value of the etching rate is shown as a relative comparison when the etching rate of the 99.9 wt% alumina sintered body is set to 1.
【００２４】各試料の特性及びそれぞれの結果は表１に
示すとおりである。The properties of each sample and the results are as shown in Table 1.
【００２５】この結果、本発明の耐食性部材Ｎｏ２〜８
は、Ｃｌ2 ガス、ＳＦ6 ガス、いずれの腐食性ガスに対
しても、従来の耐食性部材と比較して優れた耐食性を有
していた。傾向としては、イットリアの含有量が増えて
いくほど優れた耐食性を示すことがわかる。しかし、イ
ットリアのみのＮｏ１は緻密体が得られず、気孔率も５
％と大きい為、耐食性が劣化している。また、Ｎｏ９〜
１２も、Ｃｌ2 ガス、ＳＦ6 ガス、いずれの腐食性ガス
に対しても、従来の耐食性部材と比較して優れた耐食性
を有していた。ジルコニアの添加量としては５００００
ｐｐｍを越えるとＮｏ１３にみられるように、ＳＦ6 ガ
スに対する耐食性が本発明範囲外のＮｏ１５：アルミナ
と同程度までに劣化してしまう。As a result, the corrosion-resistant members No. 2 to 8 of the present invention
Had excellent corrosion resistance to Cl 2 gas and SF 6 gas, both corrosive gases, as compared with conventional corrosion-resistant members. As a tendency, it can be seen that the higher the yttria content, the more excellent the corrosion resistance. However, in the case of No. 1 containing only yttria, a dense body was not obtained, and the porosity was 5%.
%, The corrosion resistance is degraded. Also, No9 ~
Sample No. 12 also had superior corrosion resistance to Cl 2 gas and SF 6 gas, both corrosive gases, as compared to conventional corrosion resistant members. The addition amount of zirconia is 50,000
If it exceeds ppm, as shown in No. 13, the corrosion resistance to SF 6 gas is deteriorated to the same extent as that of No. 15: alumina outside the range of the present invention.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例２ 次に、本発明の耐食性部材の耐熱衝撃性について実験を
行った。本実験では、表１に記載のＮｏ９〜１４の焼結
体を用いて、３×４×４０の抗折試験片を作製し、所定
の温度に加熱した後、水中投下し、焼結体表面に発生す
るクラックの有無で耐熱衝撃性を評価した。なお、クラ
ックの有無については、探傷液により判断し、クラック
の入らない最高温度差を耐熱衝撃温度△Ｔとした。Example 2 Next, an experiment was conducted on the thermal shock resistance of the corrosion-resistant member of the present invention. In this experiment, 3 × 4 × 40 bending test pieces were prepared using the sintered bodies Nos. 9 to 14 shown in Table 1, heated to a predetermined temperature, dropped in water, and subjected to surface treatment. The thermal shock resistance was evaluated based on the presence or absence of cracks occurring in the test pieces. The presence or absence of cracks was judged by the flaw detection liquid, and the maximum temperature difference at which cracks did not occur was defined as the thermal shock temperature ΔT.
【００２８】各試料の実験結果は表２に示すとおりであ
る。The experimental results of each sample are as shown in Table 2.
【００２９】この結果、ジルコニア及びセリアを添加し
ないＮｏ１４との比較において、本発明のＮｏ１０〜Ｎ
ｏ１２は、耐熱衝撃性の向上がみられた。その効果はＮ
ｏ９、Ｎｏ１０にみられるように、ジルコニア５００ｐ
ｐｍ以上、セリア５ｐｐｍ以上の添加が必要である。そ
の傾向としては、添加量が増えるほど耐熱衝撃性は向上
していく。しかしながら、Ｎｏ１３においては、添加量
増量に伴うマイクロクラック増加により耐熱衝撃性は向
上するものの、表１にみられるように耐食性は逆に著し
く劣化するため、添加量はジルコニア５００００ｐｐｍ
以下、セリア５００ｐｐｍ以下とすることが好ましい。As a result, in comparison with No. 14 in which zirconia and ceria were not added, No. 10 to No.
For o12, improvement in thermal shock resistance was observed. The effect is N
o9, No10, zirconia 500p
pm or more and ceria of 5 ppm or more are required. The tendency is that the thermal shock resistance improves as the amount of addition increases. However, in No. 13, although the thermal shock resistance is improved due to the increase in the microcrack accompanying the increase in the amount of addition, the corrosion resistance is significantly deteriorated as shown in Table 1, so the amount of addition of zirconia is 50,000 ppm.
Hereinafter, it is preferable that ceria be 500 ppm or less.
【００３０】今回、主結晶相にＹＡＧを用いて実験を行
ったが、その他のＹＡＧとイットリア、またはアルミナ
の何れかの混合相により構成されるセラミック焼結体に
ついてもメカニズム的に同様の結果となることは言うま
でもない。In this experiment, YAG was used as the main crystal phase, but other ceramic sintered bodies composed of a mixed phase of YAG and yttria or alumina showed similar mechanical results. Needless to say.
【００３１】[0031]
【表２】 [Table 2]
【００３２】実施例３ さらに、表１に記載の試料Ｎｏ．７におけるセラミック
焼結体を用い、焼成温度を制御して気孔率を異ならせた
時の耐食性について実施例１と同様の条件にて実験を行
った。エッチングレートの数値は、９９．９ｗｔ％のア
ルミナ焼結体のエッチングレートを１としたときの相対
比較で示す。Example 3 Further, the sample Nos. An experiment was conducted on the corrosion resistance when the porosity was varied by controlling the firing temperature using the ceramic sintered body of Example 7 under the same conditions as in Example 1. The numerical value of the etching rate is shown as a relative comparison when the etching rate of the 99.9 wt% alumina sintered body is set to 1.
【００３３】各試料の特性及びそれぞれの結果は表３に
示すとおりである。The characteristics of each sample and the results are as shown in Table 3.
【００３４】この結果、本発明の焼結体は、結晶粒径が
１０μｍ以下、気孔率０．２％以下の耐食性部材は、Ｃ
ｌ2 ガス、ＳＦ6 ガス、いずれの腐食性ガスに対して
も、従来の耐食性部材と比較して優れた耐食性を有して
いた。As a result, in the sintered body of the present invention, the corrosion-resistant member having a crystal grain size of 10 μm or less and a porosity of 0.2% or less
It had excellent corrosion resistance to l 2 gas and SF 6 gas, both corrosive gases, as compared with conventional corrosion resistant members.
【００３５】今回、主結晶相にＹＡＧを用いて実験を行
ったが、その他のＹＡＧとイットリア、またはアルミナ
の何れかの混合相により構成されるセラミック焼結体に
ついてもメカニズム的に同様の結果（ボイドのエッジか
ら腐食が進行していく）となることは言うまでもない。In the present experiment, YAG was used as the main crystal phase. Other ceramic sintered bodies composed of a mixed phase of YAG, yttria, or alumina have similar mechanical results ( It goes without saying that corrosion progresses from the edge of the void).
【００３６】[0036]
【表３】 [Table 3]
【００３７】[0037]
【発明の効果】以上詳述したとおり、本発明の耐食性セ
ラミック部材は、ハロゲン系腐食性ガス又はそのプラズ
マに曝される耐食性部材を、イットリアとアルミナの化
合物より形成し、その主結晶相をＹＡＧ（イットリウム
・アルミニウム・ガーネット）、あるいはＹＡＧとアル
ミナ、またはＹＡＧとイットリアとする焼結体で形成す
ることで耐食性を向上させ、副成分としてジルコニアを
５００〜５００００ｐｐｍ含ませることで、耐熱衝撃性
も向上させ、さらには、結晶粒径を１０μｍ以下とし、
気孔率を０．２％以下とすることで、プラズマに対する
耐食性を向上させることができる。As described in detail above, the corrosion-resistant ceramic member of the present invention is formed by forming a corrosion-resistant member exposed to a halogen-based corrosive gas or its plasma from a compound of yttria and alumina, and its main crystal phase is YAG. (Yttrium aluminum garnet) or a sintered body of YAG and alumina or YAG and yttria to improve corrosion resistance, and by including 500 to 50,000 ppm of zirconia as an accessory component, to improve thermal shock resistance And further, the crystal grain size is 10 μm or less,
By setting the porosity to 0.2% or less, corrosion resistance to plasma can be improved.
【図１】本発明の耐食性セラミック部材の応用例である
エッチング装置内部の概略図である。FIG. 1 is a schematic view of the inside of an etching apparatus which is an application example of the corrosion-resistant ceramic member of the present invention.
１．チャンバー ２．クランプリング ３．下部電極 ４．ウェハー ５．高周波コイル 1. Chamber 2. Clamp ring 3. Lower electrode 4. Wafer 5. High frequency coil
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年１２月２８日（１９９９．１２．
２８）[Submission date] December 28, 1999 (1999.12.
28)
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Correction target item name] Name of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【発明の名称】半導体・液晶製造装置用部材[Title of the Invention] Member for semiconductor / liquid crystal manufacturing equipment
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００８】即ち、本発明は、フッ素系や塩素系等のハ
ロゲン系腐食性ガスおよびそのプラズマに曝される半導
体・液晶製造装置用部材を、イットリアとアルミナの化
合物で形成し、その主結晶相をＹＡＧ、あるいはＹＡＧ
とアルミナ、またはＹＡＧとイットリアの混合相とし、
安定化剤としてセリアを含むジルコニアを５００〜５０
０００重量ｐｐｍ含むことを特徴とする。That is, according to the present invention, a member for a semiconductor / liquid crystal manufacturing apparatus exposed to a halogen-based corrosive gas such as a fluorine-based or chlorine-based gas and its plasma is formed of a compound of yttria and alumina, and a main crystal phase thereof is formed. To YAG or YAG
And alumina, or a mixed phase of YAG and yttria,
500-50 zirconia containing ceria as a stabilizer
000 ppm by weight.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１０】本発明の半導体・液晶製造装置用部材は、
ハロゲン系腐食性ガスあるいはそのプラズマに曝される
部材であり、ハロゲン系腐食性ガスとしては、ＳＦ6 、
ＣＦ4 、ＣＨＦ3 、ＣｌＦ3 、ＮＦ3 、Ｃ4 Ｆ8 、ＨＦ
等のフッ素系ガス、Ｃｌ2 、ＨＣｌ、ＢＣｌ3 、ＣＣｌ
4 等の塩素系ガス、あるいはＢｒ2 、ＨＢｒ、ＢＢｒ3
等の臭素系ガスなどがある。そして、これらのハロゲン
系腐食性ガスが使用される雰囲気下でマイクロ波や高周
波が導入されるとこれらのガスがプラズマ化されること
になる。[0010] The member for a semiconductor / liquid crystal manufacturing apparatus of the present invention comprises:
The member is exposed to a halogen-based corrosive gas or its plasma. Examples of the halogen-based corrosive gas include SF 6 ,
CF 4 , CHF 3 , ClF 3 , NF 3 , C 4 F 8 , HF
Fluorine gas such as Cl 2 , HCl, BCl 3 , CCl
Chlorine gas such as 4 or Br 2 , HBr, BBr 3
And the like. When microwaves or high frequencies are introduced in an atmosphere in which these halogen-based corrosive gases are used, these gases are turned into plasma.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１６】即ち、ジルコニア成分を５００重量ｐｐｍ
以上含有させることにより、耐熱衝撃性が向上すること
を見出した。これは、イットリアとアルミナの化合物か
らなる焼結体中にジルコニアを分散させることにより、
熱衝撃時に発生するクラックの進展をジルコニアが妨げ
るためである。That is, the zirconia component is added in an amount of 500 ppm by weight.
It has been found that the thermal shock resistance is improved by the above-mentioned content. This is by dispersing zirconia in a sintered body consisting of a compound of yttria and alumina,
This is because zirconia hinders the progress of cracks generated during thermal shock.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】このジルコニアの添加量は、５００００重
量ｐｐｍ以下にする必要がある。これ以上となると、ジ
ルコニアの耐食性は劣ることからハロゲン系腐食性ガス
又はそのプラズマによる腐食を受けやすくなるからであ
る。ここで、セリアの添加量はジルコニア１００重量％
に対し、１重量％以上添加すれば、ジルコニア成分の安
定化がはかれる。また、セリアの効果としてはランプ加
熱によりかかる１００〜２００℃の温度に対するジルコ
ニアの熱劣化を防ぐことにもつながる。イットリアとア
ルミナの化合物としては、ＹＡＧ、あるいはＹＡＧとア
ルミナ、またはＹＡＧとイットリアを主結晶としたセラ
ミック焼結体がある。The amount of zirconia added must be 50,000 ppm by weight or less. If it is more than this, the corrosion resistance of zirconia is inferior, so that it becomes susceptible to corrosion by halogen-based corrosive gas or its plasma. Here, the amount of ceria added is 100% by weight of zirconia.
On the other hand, if more than 1% by weight is added, the zirconia component is stabilized. In addition, the effect of ceria also leads to preventing thermal deterioration of zirconia at a temperature of 100 to 200 ° C. caused by lamp heating. Examples of the compound of yttria and alumina include YAG, or a ceramic sintered body having YAG and yttria as main crystals.
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２１[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２１】本発明の半導体・液晶製造装置用部材の例
として、図１にエッチング装置内部の略図を示す。部品
番号１はチャンバーを、２はクランプリングを、３は下
部電極を、４はウェハーを、５は高周波コイルを示す。
この中で、部品番号１や２に示すような、ハロゲン系腐
食性ガスやプラズマに曝される部分に、本発明の半導体
・液晶製造装置用部材を適用すれば、優れた耐食性を示
し、また熱衝撃による割れ等も発生しなかった。FIG. 1 shows a schematic view of the inside of an etching apparatus as an example of a member for a semiconductor / liquid crystal manufacturing apparatus according to the present invention. Part number 1 indicates a chamber, 2 indicates a clamp ring, 3 indicates a lower electrode, 4 indicates a wafer, and 5 indicates a high-frequency coil.
Among them, when the member for semiconductor / liquid crystal manufacturing equipment of the present invention is applied to a portion exposed to a halogen-based corrosive gas or plasma as shown in part numbers 1 and 2, excellent corrosion resistance is exhibited, and No cracks or the like due to thermal shock occurred.
【手続補正９】[Procedure amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２２[Correction target item name] 0022
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２２】[0022]
【実施例】実施例１ 本発明の半導体・液晶製造装置用部材として、ジルコニ
ア５０００重量ｐｐｍ、セリア５０ｐｐｍを含んだＹＡ
Ｇ、ＹＡＧとイットリアの混合相、ＹＡＧとアルミナの
混合相からなるセラミック焼結体と、ＹＡＧを主結晶相
としてジルコニア、セリアの添加量を変化させたセラミ
ック焼結体と、従来の半導体・液晶製造装置用部材とし
て、石英ガラス、純度９９．５ｗｔ％のアルミナ焼結
体、及び純度９９．９ｗｔ％のアルミナ焼結体、ジルコ
ニア、セリアを含まないＹＡＧをそれぞれ用意し、フッ
素系及び塩素系の腐食性ガス下でプラズマに曝した時の
耐食性について実験を行った。EXAMPLE 1 A YA containing 5000 ppm by weight of zirconia and 50 ppm of ceria was used as a member for a semiconductor / liquid crystal manufacturing apparatus of the present invention.
G, a ceramic sintered body composed of a mixed phase of YAG and yttria, a mixed phase of YAG and alumina, a ceramic sintered body in which YAG is used as a main crystal phase and the added amount of zirconia and ceria is changed, and a conventional semiconductor / liquid crystal Quartz glass, 99.5 wt% pure alumina sintered body, 99.9 wt% pure alumina sintered body, zirconia and ceria-free YAG were prepared as members for the manufacturing apparatus. An experiment was conducted on the corrosion resistance when exposed to plasma under a corrosive gas.
【手続補正１０】[Procedure amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Correction target item name] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２３】本実験では、本発明及び従来の半導体製造
装置用部材を、直径３０ｍｍ×厚み３ｍｍに製作した
後、表面にラップ加工を施して鏡面にしたものを試料と
し、この試料をＲＩＥ（Ｒｅａｃｔｉｖｅ Ｉｏｎ Ｅ
ｔｃｈｉｎｇ）装置にセットしてＳＦ6 ガス雰囲気下及
びＣｌ2 ガス雰囲気下でプラズマ中に３時間曝した後、
処理前後の重量の減少値から１分間当たりのエッチング
レートを算出した。エッチングレートの数値は、９９．
９ｗｔ％のアルミナ焼結体のエッチングレートを１とし
たときの相対比較で示す。In this experiment, the members of the present invention and the conventional semiconductor manufacturing apparatus were manufactured to have a diameter of 30 mm × thickness of 3 mm, and then lapping was performed on the surface to make a mirror surface, and this sample was subjected to RIE (Reactive). Ion E
After setting in a device and exposing it to plasma under SF 6 gas atmosphere and Cl 2 gas atmosphere for 3 hours,
The etching rate per minute was calculated from the weight reduction value before and after the treatment. The numerical value of the etching rate is 99.
This is shown as a relative comparison when the etching rate of an alumina sintered body of 9 wt% is set to 1.
【手続補正１１】[Procedure amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２５[Correction target item name] 0025
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２５】この結果、本発明の半導体・液晶製造装置
用部材Ｎｏ．２〜８は、ＳＦ6 ガス、Ｃｌ2 ガス、いず
れの腐食性ガスに対しても、従来の半導体・液晶製造装
置用部材と比較して優れた耐食性を有していた。傾向と
しては、イットリアの含有量が増えていくほど優れた耐
食性を示すことがわかる。しかし、イットリアのみのＮ
ｏ．１は緻密体が得られず、気孔率も５％と大きいた
め、耐食性が劣化している。また、Ｎｏ．９〜１２も、
ＳＦ6 ガス、Ｃｌ2 ガス、いずれの腐食性ガスに対して
も、従来の半導体・液晶製造装置用部材と比較して優れ
た耐食性を有していた。ジルコニアの添加量としては５
００００重量ｐｐｍを超えると、Ｎｏ．１３に見られる
ように、ＳＦ6 ガスに対する耐食性が本発明範囲外のＮ
ｏ．１５のアルミナ焼結体と同程度まで劣化してしま
う。As a result, the member no. Nos. 2 to 8 had excellent corrosion resistance to SF 6 gas, Cl 2 gas, and any corrosive gas as compared with conventional members for semiconductor / liquid crystal manufacturing apparatuses. As a tendency, it can be seen that the higher the yttria content, the more excellent the corrosion resistance. However, N of Yttria only
o. In No. 1, since a dense body was not obtained and the porosity was as large as 5%, the corrosion resistance was deteriorated. In addition, No. 9 to 12
It had excellent corrosion resistance to SF 6 gas, Cl 2 gas, and any corrosive gas as compared with conventional members for semiconductor / liquid crystal manufacturing equipment. The addition amount of zirconia is 5
If the amount exceeds 0000 ppm by weight, no. As can be seen from FIG. 13, the corrosion resistance to SF 6 gas is out of the range of the present invention.
o. It deteriorates to the same degree as the alumina sintered body of No. 15.
【手続補正１２】[Procedure amendment 12]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２７[Correction target item name] 0027
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２７】実施例２ 次に、本発明の半導体・液晶製造装置用部材の耐熱衝撃
性について実験を行った。本実験では、表１に記載のＮ
ｏ．９〜１４の焼結体を用いて、３×４×４０の抗折試
験片を作製し、所定の温度に加熱した後、水中投下し、
焼結体表面に発生するクラックの有無で耐熱衝撃性を評
価した。なお、クラックの有無については、探傷液によ
り判断し、クラックの入らない最高温度差を耐熱衝撃温
度ΔＴとした。Example 2 Next, an experiment was conducted on the thermal shock resistance of the member for a semiconductor / liquid crystal manufacturing apparatus of the present invention. In this experiment, N
o. Using a sintered body of 9 to 14, a 3 × 4 × 40 bending test piece was prepared, heated to a predetermined temperature, and then dropped in water.
The thermal shock resistance was evaluated based on the presence or absence of cracks generated on the surface of the sintered body. The presence or absence of cracks was judged by the flaw detection liquid, and the maximum temperature difference at which cracks did not occur was defined as the thermal shock temperature ΔT.
【手続補正１３】[Procedure amendment 13]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３０[Correction target item name] 0030
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３０】この結果、ジルコニア及びセリアを添加し
ないＮｏ．１４との比較において、本発明のＮｏ．１０
〜１２は、耐熱衝撃性の向上が見られた。その効果はＮ
ｏ．９、Ｎｏ．１０に見られるように、ジルコニア５０
０重量ｐｐｍ以上、セリア５ｐｐｍ以上の添加が必要で
ある。その傾向としては、添加量が増えるほど耐熱衝撃
性は向上していく。しかしながら、Ｎｏ．１３において
は、添加量増量に伴うマイクロクラックの増加により耐
熱衝撃性は向上するものの、表１に見られるように耐食
性は逆に著しく劣化するため、添加量はジルコニア５０
０００重量ｐｐｍ以下、セリア５００ｐｐｍ以下とする
ことが好ましい。[0030] As a result, No. 3 containing no zirconia and ceria was added. 14 in comparison with No. 14 of the present invention. 10
In Nos. To 12, improvement in thermal shock resistance was observed. The effect is N
o. 9, No. As seen in Figure 10, zirconia 50
It is necessary to add 0 ppm by weight or more and 5 ppm or more of ceria. The tendency is that the thermal shock resistance improves as the amount of addition increases. However, no. In No. 13, although the thermal shock resistance was improved due to the increase in the microcrack accompanying the increase in the amount of addition, the corrosion resistance was significantly deteriorated as shown in Table 1, so the amount of addition was zirconia 50.
It is preferable that the content be 000 ppm by weight or less and ceria 500 ppm or less.
【手続補正１４】[Procedure amendment 14]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３７[Correction target item name] 0037
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３７】以上詳述したとおり、本発明によれば、ハ
ロゲン系腐食性ガス又はそのプラズマに曝される半導体
・液晶製造装置用部材を、イットリアとアルミナの化合
物より形成し、その主結晶相をＹＡＧ（イットリウム・
アルミニウム・ガーネット）、あるいはＹＡＧとアルミ
ナ、またはＹＡＧとイットリアとする焼結体で形成する
ことで耐食性を向上させ、副成分としてセリアを安定化
剤に含むジルコニアを５００〜５００００重量ｐｐｍ含
有させることで、耐熱衝撃性も向上させ、さらには、結
晶粒径を１０μｍ以下とし、気孔率を０．２％以下とす
ることで、プラズマに対する耐食性を向上させることが
できる。As described above in detail, according to the present invention, a member for a semiconductor / liquid crystal manufacturing apparatus exposed to a halogen-based corrosive gas or its plasma is formed from a compound of yttria and alumina, and its main crystal phase is changed. YAG (Yttrium
Aluminum garnet), or a sintered body of YAG and alumina, or YAG and yttria to improve corrosion resistance and to contain zirconia containing ceria as a stabilizer as a secondary component in an amount of 500 to 50,000 ppm by weight. By improving the thermal shock resistance, and further by setting the crystal grain size to 10 μm or less and the porosity to 0.2% or less, corrosion resistance to plasma can be improved.
Claims (5)
とし、副成分としてジルコニアを５００〜５００００ｐ
ｐｍ含むことを特徴とする耐食性セラミック部材。1. A compound comprising yttria and alumina as a main crystal phase, and zirconia as an auxiliary component in an amount of 500 to 50,000 p.
A corrosion-resistant ceramic member containing pm.
含むことを特徴とする請求項１記載の耐食性セラミック
部材。2. The corrosion-resistant ceramic member according to claim 1, wherein said zirconia contains ceria as a stabilizer.
アルミニウム・ガーネット）、ＹＡＧとアルミナ、また
はＹＡＧとイットリアからなることを特徴とする請求項
１記載の耐食性セラミック部材。3. The method according to claim 2, wherein the main crystal phase is YAG (yttrium
2. The corrosion-resistant ceramic member according to claim 1, comprising aluminum garnet, YAG and alumina, or YAG and yttria.
を特徴とする請求項１乃至３記載の耐食性セラミック部
材4. The corrosion-resistant ceramic member according to claim 1, wherein the thermal shock resistance ΔT is 100 ° C. or higher.
０．２％以下であることを特徴とする請求項１乃至３記
載の耐食性セラミック部材。5. The corrosion-resistant ceramic member according to claim 1, wherein the average crystal grain size is 10 μm or less and the porosity is 0.2% or less.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10371726A JP3046288B1 (en) | 1998-12-28 | 1998-12-28 | Components for semiconductor / liquid crystal manufacturing equipment |
| US09/450,162 US6383964B1 (en) | 1998-11-27 | 1999-11-29 | Ceramic member resistant to halogen-plasma corrosion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10371726A JP3046288B1 (en) | 1998-12-28 | 1998-12-28 | Components for semiconductor / liquid crystal manufacturing equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3046288B1 JP3046288B1 (en) | 2000-05-29 |
| JP2000191369A true JP2000191369A (en) | 2000-07-11 |
Family
ID=18499199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10371726A Expired - Fee Related JP3046288B1 (en) | 1998-11-27 | 1998-12-28 | Components for semiconductor / liquid crystal manufacturing equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3046288B1 (en) |
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