JP3550306B2

JP3550306B2 - Plasma resistant member and method of manufacturing the same

Info

Publication number: JP3550306B2
Application number: JP33722598A
Authority: JP
Inventors: 一憲竹之内
Original assignee: Kyocera Corp
Current assignee: Kyocera Corp
Priority date: 1998-11-27
Filing date: 1998-11-27
Publication date: 2004-08-04
Anticipated expiration: 2018-11-27
Also published as: JP2000164572A

Description

【０００１】
【発明の属する技術分野】
本発明は、フッ素系や塩素系や臭素系や酸素系や水素系ガスを用いたドライエッチング装置及び磁界や高周波誘導により高密度プラズマを用いたドライエッチング装置の内壁部材であるドームやチャンバーやリング、またＥＣＲ（ＥｌｅｃｔｒｏｎＣｙｃｌｏｔｒｏｎＲｅｓｏｎａｎｃｅ）−ＣＶＤ装置の反応容器であるチャンバー、さらにＡｒＦやＫｒＦエキシマレーザーの発光管の内壁部材、被処理物を支持する支持体などの治具として使用される半導体製造装置や液晶製造装置の耐プラズマ性や半導電性が必要とされる部材に関するものである。
【０００２】
【従来の技術】
半導体メモリーＤＲＡＭの高集積化技術は３年を１世代として、デザインルールを各世代ごとに０．６〜０．７倍に微細化し、ウェハー面積を各世代毎に１．３倍拡大することにより、量産性を向上させてきている。
【０００３】
半導体のメモリー線幅の微細化のために、露光装置で使用する波長を短くすることが必要となると共に、アスペクト比の高いエッチングが必要となる。この高いアスペクト比のエッチングを行うために、高密度プラズマが使用されつつある。高密度プラズマにおける物理的かつ化学的なエッチングによるパーティクルや不純物の発生を防止するために、プラズマに暴露される部材に対し耐プラズマ性や高純度化が要求されている。
【０００４】
従来は半導体製造装置のドライエッチング装置やＥＣＲプラズマＣＶＤ装置のプラズマ照射部となるチャンバーやドームの内壁部材には高純度のＳｉＯ_２石英ガラス材やポリシリコン、またエキシマレーザー発光管のプラズマ照射部となる内壁部材には高純度ＳｉＯ_２石英ガラス材が採用されていた。
【０００５】
また、半導体製造装置内でウェハーを支持固定するハンドリング治具やサセプターやヒーター用の材料としてはアルミナ焼結体、アルミナと炭化チタン複合セラミックスやサファイヤ、窒化アルミニウム焼結体、またはＣＶＤ等の方法によりこれらの表面被膜を形成したもの、具体的には炭化珪素焼結体にＣＶＤ法で炭化珪素膜を被膜したものや安価なセラミックス焼結体にＤＬＣ（ＤｉａｍｏｎｄＬｉｋｅＣａｒｂｏｎ）を被膜したものが使用されている。
【０００６】
半導体メモリー製造におけるプラズマプロセスでは、フッ素系や塩素系や臭素系や酸素系や水素系ガスが使用される。これらのガスは単体あるいは混合して使用され、半導体素子のエッチングや装置のクリーニングに利用されている。
【０００７】
これらの腐食性ガスに接触する部材は、高い耐プラズマ性、低パーティクル、高純度化が必要とされている。また高周波誘導を用いた高密度ドライエッチング装置では内壁材に高周波の透過や吸収をコントロールするために内壁材と外壁材との間に導電性の変化を持たせる等の方法が提案されており、これらを兼ね備えた各種材料が検討されている。
【０００８】
具体的にはＳｉ酸化膜のエッチングでは材料の高純度化と耐プラズマ性向上を目的として、原材料を高純度化し、低ＯＨ基化を行った純度９９．９９％を用いたＳｉＯ_２石英ガラスや結晶質の石英が採用されてきている。
【０００９】
しかし、従来から使用されてきたガラスや高純度ＳｉＯ_２石英ガラス材ではプラズマ中での耐プラズマ性が不十分で消耗が激しく、特にフッ素あるいは塩素プラズマに接するとその接触面がエッチングされ、表面性状の変化や酸素の解離により、エッチング条件が変化する等の問題が生じていた。
【００１０】
そこで、アルミナや窒化アルミや炭化珪素や窒化珪素やＭｇＡｌ_２Ｏ_４やＹＡＧ等のセラミックス材料は従来の石英ガラスと比較して耐プラズマ性に優れていることから、半導体製造装置の各種プロセスで使用されてきている。これらのセラミックス材料の特徴を生かし、より優れた耐プラズマ性や高純度化を実現するための方法が検討されている。その方法の一つとして特開平１−２５２５８０では炭化珪素を緻密なカーボン容器中で焼成する方法が紹介されている。また、より高いレベルの高純度化を行うために、同材質や比較的熱膨張の近い材料の基体表面にＣＶＤやＰＶＤ等の方法により高純度化膜を成膜する方法が提案されている。中でも高純度化を狙って、高純度炭化珪素に炭化珪素ＣＶＤを施すという内容が特公平７−８８２６５に開示されている。
【００１１】
また、フッ素や塩素系プラズマに対して耐プラズマ性に優れる周期律表第３ａ族元素を主成分とするセラミックス材料とすることが特開平９−２９５８６３号に提案され、周期律表第３ａ族元素とＡｌやＳｉの複合酸化物を主成分とするセラミックス材料を使用することが特開平１０−４５４６７号に提案され、その材料の不純物を０．１重量％以下とする高純度化が特願平９−３２８４４９で提案されている。また、周期律表第２ａ，３ａ族の複合酸化物を使用することが特開平１０−４５４６１で提案されている。更に、第２ａ，３ａ，３ｂ族の複合酸化物を使用した例が特開平１０−６７５５４で提案されている。より具体的には、耐プラズマ性に優れるＹＡＧを使用した部材が特願平９−４２６０４で提案されている。現在、さらに化学的に安定である共有結合性の高い窒化珪素や炭化珪素、炭化硼素の適用が進められている。
【００１２】
ところで、アルミナやＭｇＡｌ_２Ｏ_４やＹＡＧの酸化物セラミックス、炭化珪素や炭化硼素の炭化物セラミックス、窒化珪素や窒化アルミの窒化物セラミックスなどの各材料は従来の石英ガラスと比較して耐プラズマ性に優れるものの、純度面では高純度石英ガラスに劣り、高温でプラズマと接すると腐食が徐々に進行して、焼結体の表面で起こる選択的なエッチングで取り残された粒界や結晶粒子の脱落が起こり、パーティクル発生の一因となる問題が懸念されている。
【００１３】
パーティクルはイオン衝撃などの物理的な作用により発生したり、あるいは化学的な気相反応で生成した反応生成物が解離や再解離を繰り返すことにより発生し、メタル配線の断線や短絡、パターン欠陥を発生させ、半導体素子の劣化や歩留まりの低下を引き起こすばかりか、半導体メモリーの高集積化の大きな障害となっている。特に、ドライエッチングプロセスではパーティクル発生が最大のトラブル原因となっており、パーティクルが一度発生すると、真空を開放してドームやチャンバーの中を拭き取り洗浄する作業が必要となり、多大な工数的なロスが発生していた。
【００１４】
従って、前述のようなセラミックス耐プラズマ材においても、メモリー線幅０．２５μｍ以下の高集積化には不十分となってきており、満足しうる耐プラズマ性が達成されず、パーティクル等の問題が残っている。この問題解決には腐食性ガスのプラズマが作用する表面を耐プラズマ性に優れる低欠陥で高純度の均一な被膜で形成する方法が有効であり、高純度炭化珪素の上に炭化珪素ＣＶＤ膜を形成する方法が提案されている。
【００１５】
一方、高周波誘導型の高密度プラズマにおいては異なる周波数の高周波を導入し、片方の高周波は透過し、もう一つの高周波は遮断するためにドームやチャンバーやリングの内壁部材に導電性の変化を付与するような複層構造のドームやチャンバー、リングが要求されている。
【００１６】
【発明が解決しようとする課題】
これらの部材としては、筒状体の内周面と端面に耐プラズマ性の被膜を形成したものが求められている。
【００１７】
ところが、これらの部材の内周面と端面に耐プラズマ性被膜を形成することは、被膜が均一に形成出来ない、内周面と端面の境界から被膜の剥離が生ずるなどの不都合があり、また効率良く被膜を形成することが困難であった。
【００１８】
本発明者は上記事情に鑑み、耐プラズマ性や抵抗値異なる導電材の複層化が必要とされる片封止円筒ドーム形状や両端開放円管リング形状をした基体のプラズマ中に暴露される主たる表面及びプラズマシール面が前記特性に優れた被膜で形成された複層構造の耐プラズマ性部材を製作するに当たり、製品のプラズマ中に暴露される部分及びプラズマシール面部分の被膜が均一に形成でき、かつ製品の周縁部での剥離が起こりにくい安定した特性を示す製品形状と複数個の製品に安定して被膜を形成できる製造方法を見いだした。
【００１９】
さらにプラズマ雰囲気への不純物混入を防止し、高清浄状態に保持するにはプラズマ暴露面に加えてプラズマシール面を高純度化しておく必要がある。プラズマシール面に高純度で耐プラズマ性に優れた被膜を形成した状態で、かつシールのための加圧力点との位置関係を適正に設定することにより、プラズマ雰囲気の高清浄化が達成され、不純物の混入を防止することができる。
【００２０】
本発明は、上記知見に基づいて完成されたものであり、その目的はプラズマに暴露される面やプラズマシール面からのパーティクルが発生せず、高純度で優れた耐プラズマ性を達成する被膜を形成した長期信頼性の複層構造の耐プラズマ性部材や、部分的に抵抗値の異なる導電材の複層構造を持つ耐プラズマ性部材を提供することにある。
【００２１】
【課題を解決するための手段】
本発明の複層構造の耐プラズマ性部材は、片封止あるいは両端開放の筒状体からなり、該筒状体の内周面と端面のシール面に耐プラズマ性の被膜を備えるとともに、外周面に上記筒状体のシール面とは異なる高さの突起部が形成されていることを特徴とする。
また、上記突起部はシール面の外周側から連続的に傾斜する面を有し、この突起部にも耐プラズマ性被膜を備えたことを特徴とする。
さらに、上記耐プラズマ性被膜が、炭化珪素、炭化硼素、窒化珪素、窒化アルミ、ＹＡＧ、ＭｇＡｌ _２Ｏ _４等の一種以上で構成されたことを特徴とする。
一方、本発明の耐プラズマ性部材の製造方法は、片封止あるいは両端開放の筒状体の外周面に突起部を形成し、この突起部を筒状の支持部材の上面に載置した状態で、上記筒状体の内周面および端面のシール面に耐プラズマ性被膜を形成することを特徴とするものである。
上記突起部上に更に支持部材と他の筒状体を積層し、複数の筒状体に同時に耐プラズマ性被膜を形成することを特徴とするものである。
【００２２】
【発明の実施の形態】
以下、本発明の実施形態を図によって説明する。
【００２３】
図１（Ａ），（Ｂ）は片封止円筒ドーム形状の平面図と断面図、図１（Ｃ），（Ｄ）は両端開放円管リング形状の平面図と断面図を示しており、筒状体１（図１（Ｂ）では片側封止部１ａと一体）は、内周面２、外周面３、突起部４、端面（シール面）１０を有し、内周面２とシール面１０に耐プラズマ性の被膜９を備えている。両者とも内周面２がプラズマに暴露される領域であり、プラズマ雰囲気のシール面１０より外周側で、かつプラズマシール面と異なる高さを持つプラズマに暴露されない外周面３に突起部４を有している。この突起部４は、詳細を後述するように成膜時の支持に使用され、かつ装置に取付ける時にはシール用の弾性部材が挿入可能である。
【００２４】
この筒状体１は、炭化珪素、炭化硼素、窒化珪素、窒化アルミ、ＹＡＧ、ＭｇＡｌ_２Ｏ_４等を焼成させて作製し、ＣＶＤによって、炭化珪素、炭化硼素、窒化珪素、窒化アルミ、ＹＡＧ、ＭｇＡｌ_２Ｏ_４等の体プラズマ性被膜９を基体表面に形成する。
【００２５】
基体のＣＶＤ装置への設置方法を図２（Ａ）および（Ｂ）に示す。ＣＶＤ装置の製品支持台７上に円筒状の支持部材５を設置し、筒状体１の突起部４を支持部材５に当接させて支持し、さらに筒状体１の突起部４上に２個目の支持部材５、さらにその上に２個目の筒状体１を置き、その筒状体１の突起部４を支持部材５で支持することを繰り返し、複数の基体を段積みして、ＣＶＤ装置反応容器の中に配置する。
【００２６】
前記のように筒状体１に突起部４を設けて支持部材５で支持することにより複数の筒状体１を上下方向に段積みして効率良く成膜することが可能となり、内周面２とシール面１０の両方に均一に成膜することができる。また支持部材５の実支持部６は突起部４と全面接触するよりも、不連続先接触又は不連続点接触としておくことが好ましい。
【００２７】
図１、図２の突起部４はシール面１０の外周側に段差を形成した形で構成されている。段差の形成理由はシール面１０を高純度のＣＶＤ膜で形成するためである。図１、図２ではシール面１０と突起部４に段差を形成しているが、図３に示すようにシール面１０にシールのための平面部を残し、連続的に傾斜する形状でも、目的を達成できる。
【００２８】
図１と同様に図３（Ａ），（Ｂ）は片封止円筒ドーム形状の平面図と断面図、図３（Ｃ），（Ｄ）は両端開放円管リング形状の平面図と断面図を示しており、筒状体１（図３（Ｂ）では片側封止部１ａと一体）は、内周面２、外周面３、突起部４、端面（シール面）１０を有し、内周面２とシール面１０に耐プラズマ性の被膜９を備えている。つまりプラズマ雰囲気シール面１０の平面部でシールし、その平面部より外周側で、かつ平面部と異なる高さの位置を持つ突起部４であることが重要な条件である。
【００２９】
図４（Ａ），（Ｂ）は上記筒状体１を装置に取り付けた様子を示している。そして図４（Ａ），（Ｂ）に示すように装置取付時にはシール面１０上に位置し、支持部材５の当接位置よりも内周側に位置する加圧力点１１より加圧するように設定し、さらに突起部４の位置する箇所に弾性部材１４を挿入することにより高い気密性を確保すると共に、被膜９が形成された内周側プラズマシール面側から強固に固定することができる。従って、プラズマに曝される雰囲気を清浄に保つことができる。
【００３０】
成膜用突起部４に当接する支持部材５の当接位置より内周側の領域はプラズマ発生雰囲気のシール面として利用可能である。成膜用突起部４と支持部材５の当接位置をシール面１０を固定する加圧力点１１よりも外周側へ位置させることにより、全面に被膜が形成されたシール面１０となり、そして少なくとも支持部材５当接面の位置より外周側にシール用の弾性部材１４を配置後、シール面１０を固定することにより、被膜が形成された内周側プラズマシール面側から強固に固定することができる。従ってプラズマに曝される雰囲気を清浄に保つことができる。
【００３１】
さらに、被膜９が形成される内周面２とシール面１０が交わる周縁部１３に２０μｍ以上のＣ面あるいはＲ面を形成したことにより、周縁部１３で発生しやすい被膜剥離を防止することができる。
【００３２】
続いて、本発明の製法を詳細に説明する。
【００３３】
本発明の耐プラズマ性部材は、炭化珪素焼結体及び炭化硼素焼結体の筒状体１の表面に炭化珪素、炭化硼素の被膜を形成したものであって、これにより減圧下でフッ素系又は塩素系、臭素系、酸素系、水素系の単体あるいは混合ガスにマイクロ波や高周波電圧を印可することでプラズマ化された状態であっても優れた耐プラズマ性が達成される。フッ素系ガスにはＳＦ_６、ＣＦ_４、ＣｌＦ_３、ＨＦ、ＮＦ_３等があり、塩素系ガスにはＣｌ_２、ＢＣｌ_３、ＨＣｌ等があり、上記ガスに酸素や水素及びその化合物が混合されたものである。
【００３４】
被膜を形成する手段は、公知の成膜技術、たとえばＣＶＤ法を用いれば良く、炭化珪素の場合にはＣＨ_３ＳｉＣｌ_３原料ガス、炭化硼素の場合にはＢＣｌ_３とＣ_６Ｈ_６混合原料ガスを基体を配置した反応容器内に導入し、エネルギー源として熱を加えて化学反応を起こさせて、それぞれの膜を基体表面に形成する。この時に加える熱は化学反応を引き起こし、膜質、結晶方位を制御するために、その温度は１０００度を超え、１５００度に至る場合もある。このような高温条件下で被膜形成が行われるために、筒状体体１と被膜９は同一材質で構成することが好ましく、異材質を用いる場合には両者の熱膨張係数が近い値を持ち、さらにはその間に中間層を設けて、被膜の残留応力を小さくし、さらに被膜に圧縮の残留応力が残る組合せが好ましい。
【００３５】
上述のＣＶＤ法を用いて、片封止円筒ドーム形状や両端開放円管リング形状の筒状体１のプラズマ中に暴露される主たる表面及びプラズマ発生雰囲気のシール面１０に前記特性に優れた被膜９を形成する際に、筒状体１のシール面１０より外周側で、かつ異なる高さを持つプラズマ中に暴露されない面に成膜用の突起部４を形成し、筒状体１の突起部４に当接する支持部材５が不連続線接触、不連続点接触となるように設置し、支持部材５の曲げ強度を２０ＭＰａ以上のカーボン材とすることにより、解体性に優れた段積み可能な製造方法を実現できる。
【００３６】
以上述べた形態および製法により、腐食ガスのプラズマに対して優れた耐プラズマ性、低パーティクル性を可能とし、長時間の寿命が実現可能な耐プラズマ性部材を提供することができる。
【００３７】
本発明の耐プラズマ性部材を応用したエッチング装置を図５に示す。チャンバー２１内で、下部電極２３上にウェハー２４を載置してクランプリング２２で押さえ、外部に高周波コイル２５を備えた構造となっている。このうち、チャンバー２１に上述した本発明の耐プラズマ性部材を使用することができる。
【００３８】
【実施例】
実施例１
本発明実施例として図１に示すものを作製した。筒状体１の概略寸法は図１（Ａ），（Ｂ）の片封止円筒ドームの突起部４を含む最大外径が３８０ｍｍ、突起部４を除いた外周面３の外径が３５０ｍｍ、内周面２の内径が３２０ｍｍ、全高６５ｍｍ、内径側の深さ５０ｍｍ、図１（Ｃ），（Ｄ）の両端開放円管リングの突起部４を含む最大外径が３８０ｍｍ、突起部４を除いた外周面３の外径が３５０ｍｍ、内周面２の内径が３２０ｍｍ、全高が５０ｍｍである。
【００３９】
筒状体１は炭化珪素、炭化硼素で作製した。炭化珪素焼結体は純度９９．５％のα型炭化珪素粉末に炭化硼素を０．６重量％、炭素源２重量％添加して、ＣＩＰ成形を行い、非酸化雰囲気中２０６０℃で焼成した。一方、炭化硼素焼結体の基体はホットプレスを用いて焼成した。具体的には純度９９．９％炭化硼素粉末に少量の硼素を添加した原料をカーボン型に入れて、焼成温度２２００℃、成形圧力２００Ｋｇ／ｃｍ^２の条件で焼成を行った。
【００４０】
支持部材５の材料に、曲げ強度が５０ＭＰａ、４０ＭＰａ、３０ＭＰａ、２０ＭＰａ、１０ＭＰａの高純度カーボンを使用した。一方、支持部材５の実支持部６と突起部４の接触状態が全周面接触、不連続面接触、不連続線接触、不連続点接触となるものを用意した。
【００４１】
全周面接触の支持部材５は外径３８０ｍｍ、内径３６０ｍｍ、実支持部６の幅は１０ｍｍ、高さは片封止円筒ドーム形状用に１２５ｍｍと両端開放円管リング形状用に１００ｍｍである。支持部材５の高さ方向にはガスの流れをスムーズにするための開口部８が形成されている。不連続面接触の支持部材５は全周面接触とほぼ形状は同じであるが、実支持部６の幅は１０ｍｍのままで、円周方向に１６分割した円弧の長さの実支持部６を円周方向に均等に４箇所配置し、実支持部６以外の部分には高さ方向に５ｍｍの切り込みを入れたものである。不連続線接触の支持部材５の実支持部６の円周方向の配置は不連続面接触に同じで、実支持部６の幅方向に半径Ｒ５加工を施したものである。不連続点接触の支持部材５は円周方向に均等に４分割する位置に半径Ｒ５の半球形状の突起を配置したものである。
【００４２】
以上の支持部材５の曲げ強度と接触状態の組合せでＣＶＤ装置の反応容器内に４段の段積みをし、１２００℃の温度条件下で減圧状態にし、炭化珪素の場合にはＣＨ_３ＳｉＣｌ_３原料ガス、炭化硼素の場合にはＢＣｌ_３とＣ_６Ｈ_６混合原料ガスを反応容器内に導入し、エネルギー源として前記の熱を加えて化学反応をさせることにより、それぞれの膜を筒状体表面に被膜厚み４００μｍとなるように形成した。
【００４３】
所定の成膜終了後、反応容器を開放して段積みした筒状体１と支持部材５の解体を行った結果、炭化珪素焼結体基体上に炭化珪素の被膜、炭化硼素焼結体基体上に炭化硼素の被膜をした場合も材質によらず、実支持部６の接触状態と支持部材５の材質強度で解体性及び実支持部６の変形、支持部材５の破損が決定される結果を示した。その実支持部６の接触状態と支持部材５の強度でまとめた結果を表１に示す。
【００４４】
全周面接触した支持部材５を用いた場合、突起部４と支持部材５を容易に解体することができず、支持部材５の突起部４側を切断して解体するという大掛かりな作業を必要とした。不連続面接触の場合は全周面接触と比べて、切断作業はし易くなったものの、大掛かりな切断作業を無くすには至らなかった。これに対し不連続線接触、及び不連続点接触構造を持った支持部材５の場合、軽い衝撃を与える事で支持部材５と突起部４を分離する事ができ、解体作業を容易にすることができた。しかしながら不連続線接触、不連続点接触の場合、支持部材５の強度が１０ＭＰａと低い場合は、高温での実支持部６の変形が発生し、解体性の劣化、及び解体時に与える衝撃で支持部材５の破損が発生し、支持部材５の繰り返し使用に対しても追加工することが必要となった。
【００４５】
したがって、支持部材５の突起部４側の実支持部６を不連続線接触、不連続点接触とすることで、ＣＶＤ成膜後の突起部４と支持部材５の解体性が大幅に改善でき、支持部材５の曲げ強度を２０ＭＰａ以上とすることで、筒状体１の段積み成膜時の高温クリープによる変形を防止することができ、良好な解体性と支持部材５の繰り返し利用性を可能とすることができる。
【００４６】
【表１】

【００４７】
実施例２
実施例１で示した片封止円筒ドーム形状の炭化珪素焼結体からなる筒状体のプラズマ雰囲気シール面の周縁部１３のＣ面及びＲ面を１０μｍ、２０μｍ、４０μｍ、６０μｍ、８０μｍ、１００μｍとして、突起部４を不連続点接触の曲げ強度５０ＭＰａのカーボン支持部材５を用いて、４００μｍ厚みの炭化珪素被膜をＣＶＤ法で形成した製品を各５個製作した。成膜後解体及びシール面の研磨加工後の周縁部１３の被膜剥離を確認した。表２にその結果を示す。周縁部１３のＣ面及びＲ面を１０μｍとした時の製品に被膜の剥離が見られる。炭化珪素焼結体の周縁部１３は被膜形成時に厚く成膜されることから、成膜時の膜応力の影響による剥離、成膜後の解体時の衝突による剥離、また研磨加工時に研削砥石と被膜９面である被加工面が離れるときに発生する加工欠陥によるものが見られた。
【００４８】
このように、周縁部１３に２０μｍ以上のＣ面もしくはＲ面を形成した場合、膜応力や衝突や加工時の衝撃による被膜剥離を防止することができた。
【００４９】
【表２】

【００５０】
実施例３
実施例１及び２と同時に作成した４００μｍの被膜を形成した３０ｍｍ角で３ｍｍ厚みの試験片を準備して耐プラズマ性の評価を行った。ＲＩＥ装置の試料台を冷却することにより、試験片の冷却を行いながら、Ｃｌ_２ガスプラズマによる腐食試験を実施した。比較として従来から使用されているアルミナセラミックスも同時に評価を行った。表３にアルミナセラミックスの腐食率を基準として、炭化珪素試験片に炭化珪素ＣＶＤ膜、炭化硼素試験片に炭化硼素ＣＶＤ膜の腐食率の比率を示す。前記ＣＶＤ被膜を形成した製品は従来のアルミナセラミックスと比較して１／４０〜１／５０の低い腐食率を実現できている。
【００５１】
【表３】

【００５２】
以上、本実施例では炭化珪素焼結体、炭化硼素焼結体の基体上にＣＶＤ法により炭化珪素、炭化硼素の被膜を形成した例について述べてきたが、本発明の突起部４を設けた基体形状や支持部材形状は窒化珪素、窒化アルミやＹＡＧ及びＭｇＡｌ_２Ｏ_４等の耐プラズマ性に優れた絶縁材料で構成された基体にその被膜を形成した部材にも適用することが可能なものである。炭化珪素や炭化硼素の場合には基体に高純度カーボンを用いることも可能であるが、この場合には基体側カーボンが支持部材側カーボンより高強度な材料組合せとする必要がある。基本的には同一材料の基体と被膜で構成するべきであるが、異材料を組み合わせる場合には、基体と被膜の間にその中間の熱膨張係数を持つ中間層を形成して、基体と被膜の密着力を向上させる方法を採用することも可能である。
【００５３】
また、本発明の支持部材では一体型の形状を示したが、重要な点は基体突起部に損傷を与えること無く、基体との解体性を向上させることであり、支持部材と基体突起部の接触面が不連続線接触、不連続点接触で構成されたものであり、一体型に捕らわれるものでは無い。
【００５４】
【発明の効果】以上詳述した通り、本発明によれば、成膜作業での多数個取りを可能として、被膜剥離の少ない製品を、安定して提供できる。
【図面の簡単な説明】
【図１】本発明の耐プラズマ性部材を示しており、（Ａ），（Ｃ）は平面図、（Ｂ），（Ｄ）は断面図である。
【図２】（Ａ）（Ｂ）は本発明の耐プラズマ性部材に被膜を形成するために、ＣＶＤ装置へ設置する際の各部材の配置図である。
【図３】本発明の他の実施形態を示しており、（Ａ），（Ｃ）は平面図、（Ｂ），（Ｄ）は断面図である。
【図４】（Ａ），（Ｂ）は本発明の耐プラズマ性部材を半導体製造装置へ設置した際の概略図である。
【図５】本発明の耐プラズマ性部材を用いる半導体製造装置の概略図である。
【符号の説明】
１：筒状体
１ａ：片側封止部
２：内周面
３：外周面
４：突起部
５：支持部材
６：実支持部
７：支持台
８：開口部
９：被膜
１０：端面（シール面）
１１：加圧力点
１３：周縁部[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a dome, chamber, or ring as an inner wall member of a dry etching apparatus using a fluorine-based, chlorine-based, bromine-based, oxygen-based, or hydrogen-based gas and a dry etching apparatus using a high-density plasma by a magnetic field or high-frequency induction. In addition, a semiconductor manufacturing apparatus used as a jig such as a chamber that is a reaction vessel of an ECR (Electron Cyclotron Resonance) -CVD apparatus, an inner wall member of an arc tube of an ArF or KrF excimer laser, and a support for supporting an object to be processed. And members that require plasma resistance and semi-conductivity of a liquid crystal manufacturing apparatus.
[0002]
[Prior art]
The high integration technology of semiconductor memory DRAM is to reduce the design rule by 0.6 to 0.7 times for each generation and expand the wafer area by 1.3 times for each generation, with three years as one generation. , And mass productivity has been improved.
[0003]
In order to miniaturize the memory line width of a semiconductor, it is necessary to shorten the wavelength used in the exposure apparatus and to perform etching with a high aspect ratio. High density plasma is being used to perform this high aspect ratio etching. In order to prevent the generation of particles and impurities due to physical and chemical etching in high-density plasma, members exposed to plasma are required to have plasma resistance and high purity.
[0004]
Conventionally, high-purity SiO ₂ quartz glass and polysilicon, and plasma irradiation parts of excimer laser arc tubes are used for the inner wall members of chambers and domes that become the plasma irradiation parts of semiconductor manufacturing equipment dry etching equipment and ECR plasma CVD equipment. A high-purity SiO ₂ quartz glass material was used for the inner wall member.
[0005]
In addition, as a material for a handling jig, a susceptor, and a heater for supporting and fixing a wafer in a semiconductor manufacturing apparatus, an alumina sintered body, alumina and titanium carbide composite ceramics, sapphire, aluminum nitride sintered body, or a method such as CVD is used. Those having a surface coating formed thereon, specifically, a silicon carbide sintered body coated with a silicon carbide film by a CVD method, or an inexpensive ceramic sintered body coated with DLC (Diamond Like Carbon) are used. I have.
[0006]
In a plasma process in semiconductor memory production, a fluorine-based, chlorine-based, bromine-based, oxygen-based, or hydrogen-based gas is used. These gases are used alone or as a mixture, and are used for etching of semiconductor elements and cleaning of equipment.
[0007]
Members that come into contact with these corrosive gases are required to have high plasma resistance, low particles, and high purity. Also, in a high-density dry etching apparatus using high-frequency induction, a method has been proposed in which the inner wall material has a change in conductivity between the inner wall material and the outer wall material in order to control the transmission and absorption of high frequency to the inner wall material. Various materials having these properties have been studied.
[0008]
Specifically, in the etching of the Si oxide film, for the purpose of increasing the purity of the material and improving the plasma resistance, SiO ₂ quartz glass using a purity of 99.99% with a high purity of the raw material and a low OH group is used. Crystalline quartz has been employed.
[0009]
However, conventionally used glass or high-purity SiO ₂ quartz glass material has insufficient plasma resistance in plasma and is extremely consumed. In particular, when it comes into contact with fluorine or chlorine plasma, the contact surface is etched, and the surface properties are deteriorated. Changes and oxygen dissociation have caused problems such as changes in etching conditions.
[0010]
Therefore, ceramic materials such as alumina, aluminum nitride, silicon carbide, silicon nitride, MgAl ₂ O _4, and YAG are more excellent in plasma resistance than conventional quartz glass, and are used in various processes of semiconductor manufacturing equipment. Have been. Methods for realizing better plasma resistance and higher purity by utilizing the characteristics of these ceramic materials are being studied. As one of the methods, Japanese Patent Application Laid-Open No. 1-252580 discloses a method of firing silicon carbide in a dense carbon container. Further, in order to achieve a higher level of purification, a method of forming a highly purified film on a substrate surface of the same material or a material having relatively close thermal expansion by a method such as CVD or PVD has been proposed. Above all, Japanese Patent Publication No. 7-88265 discloses that silicon carbide CVD is performed on high-purity silicon carbide with the aim of achieving high purity.
[0011]
Japanese Patent Application Laid-Open No. 9-295863 proposes a ceramic material containing a Group 3a element of the Periodic Table having excellent plasma resistance to fluorine or chlorine-based plasma as a main component. Japanese Patent Application Laid-Open No. 10-45467 proposes the use of a ceramic material containing a composite oxide of Al and Si as a main component. 9-328449. Japanese Patent Application Laid-Open No. 10-45461 proposes to use a complex oxide of Groups 2a and 3a of the periodic table. Japanese Patent Application Laid-Open No. H10-67554 proposes an example using a complex oxide of Groups 2a, 3a and 3b. More specifically, a member using YAG having excellent plasma resistance has been proposed in Japanese Patent Application No. 9-42604. At present, application of silicon nitride, silicon carbide, and boron carbide, which are chemically stable and have high covalent bonding properties, is being promoted.
[0012]
By the way, materials such as oxide ceramics of alumina, MgAl ₂ O _4, and YAG, carbide ceramics of silicon carbide and boron carbide, and nitride ceramics of silicon nitride and aluminum nitride are more plasma-resistant than conventional quartz glass. Although it is excellent, it is inferior to high-purity quartz glass in terms of purity, and when exposed to plasma at high temperature, corrosion gradually progresses, and grain boundaries and crystal particles left behind by selective etching that occurs on the surface of the sintered body are dropped. There is a concern about problems that may occur and contribute to the generation of particles.
[0013]
Particles are generated by physical action such as ion bombardment, or by the repeated dissociation and re-dissociation of reaction products generated by a chemical vapor phase reaction. This causes not only deterioration of the semiconductor element and reduction of the yield, but also a major obstacle to the high integration of the semiconductor memory. In particular, particle generation is the biggest cause of trouble in the dry etching process, and once particles are generated, it is necessary to open the vacuum and wipe the inside of the dome and chamber and clean it, resulting in enormous man-hour loss. Had occurred.
[0014]
Therefore, even with the above-mentioned ceramic anti-plasma material, it has become insufficient for high integration with a memory line width of 0.25 μm or less, satisfactory plasma resistance is not achieved, and problems such as particles and the like occur. Remaining. To solve this problem, it is effective to form a surface on which the plasma of corrosive gas acts with a low-defect, high-purity uniform film having excellent plasma resistance. A silicon carbide CVD film is formed on high-purity silicon carbide. Methods of forming have been proposed.
[0015]
On the other hand, in high-frequency induction-type high-density plasma, different frequencies are introduced, one of which is transmitted, and the other is cut off. Domes, chambers and rings with a multilayer structure are required.
[0016]
[Problems to be solved by the invention]
As these members, those having a plasma-resistant coating formed on the inner peripheral surface and the end surface of the cylindrical body are required.
[0017]
However, forming a plasma-resistant coating on the inner peripheral surface and the end surface of these members has disadvantages such as the inability to form a uniform coating and peeling of the coating from the boundary between the inner peripheral surface and the end surface. It was difficult to efficiently form a coating.
[0018]
In view of the above circumstances, the present inventor is exposed to the plasma of a substrate having a single-sealed cylindrical dome shape or a circular ring shape with open ends, which requires a multilayer of conductive materials having different plasma resistances and resistance values. When manufacturing a plasma-resistant member with a multilayer structure in which the main surface and the plasma sealing surface are formed of a film having the above-mentioned characteristics, the film exposed to the plasma and the film of the plasma sealing surface are uniformly formed. We have found a product shape that can be formed and exhibit stable characteristics in which peeling does not easily occur at the peripheral portion of the product, and a manufacturing method that can form a coating film on a plurality of products stably.
[0019]
Further, in order to prevent impurities from being mixed into the plasma atmosphere and maintain a high clean state, it is necessary to purify the plasma sealing surface in addition to the plasma exposed surface. High purity of the plasma atmosphere is achieved by setting the plasma seal surface with a high-purity coating with excellent plasma resistance and by properly setting the positional relationship with the pressure point for sealing. Contamination can be prevented.
[0020]
The present invention has been completed on the basis of the above findings, and its purpose is to provide a coating that does not generate particles from a surface exposed to plasma or a plasma sealing surface and that achieves high purity and excellent plasma resistance. It is an object of the present invention to provide a plasma resistant member having a multilayer structure having a long-term reliability and a multilayer structure of conductive materials having partially different resistance values.
[0021]
[Means for Solving the Problems]
The plasma-resistant member having a multilayer structure according to the present invention is formed of a single-sided or open-ended cylindrical body, and has a plasma-resistant coating on an inner peripheral surface and an end surface sealing surface of the cylindrical body. The surface is formed with a projection having a height different from the sealing surface of the cylindrical body.
Further, the projection has a surface that is continuously inclined from the outer peripheral side of the sealing surface, and the projection is also provided with a plasma-resistant coating.
Further, the plasma-resistant coating is characterized by comprising at least one of silicon carbide, boron carbide, silicon nitride, aluminum nitride, YAG, MgAl ₂ O _{4 and the} like.
On the other hand, in the method for producing a plasma-resistant member of the present invention, a projection is formed on the outer peripheral surface of a single-sided or open-ended cylindrical body, and the projection is mounted on the upper surface of a cylindrical support member. A plasma-resistant coating is formed on the inner peripheral surface and the end surface of the cylindrical body.
The present invention is characterized in that a support member and another cylindrical body are further laminated on the protrusion, and a plasma-resistant coating is simultaneously formed on a plurality of cylindrical bodies.
[0022]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0023]
1 (A) and 1 (B) are a plan view and a cross-sectional view of a single-sealed cylindrical dome shape, and FIGS. 1 (C) and 1 (D) are a plan view and a cross-sectional view of a circular tube ring shape with both ends open. The tubular body 1 (integrated with the one-side sealing portion 1a in FIG. 1B) has an inner peripheral surface 2, an outer peripheral surface 3, a projection 4, and an end surface (seal surface) 10, and is sealed with the inner peripheral surface 2 The surface 10 is provided with a plasma-resistant coating 9. In both cases, the inner peripheral surface 2 is a region to be exposed to plasma, and has a projection 4 on the outer peripheral surface 3 which is on the outer peripheral side from the sealing surface 10 in the plasma atmosphere and which is not exposed to plasma having a height different from the plasma sealing surface. are doing. As will be described in detail later, the projection 4 is used to support the film formation, and an elastic member for sealing can be inserted when the projection 4 is attached to the apparatus.
[0024]
This cylindrical body 1 is manufactured by firing silicon carbide, boron carbide, silicon nitride, aluminum nitride, YAG, MgAl ₂ O _{4, and the} like, and is made of silicon carbide, boron carbide, silicon nitride, aluminum nitride, YAG, A body plasma coating 9 such as MgAl ₂ O ₄ is formed on the substrate surface.
[0025]
FIGS. 2A and 2B show a method of installing the substrate in the CVD apparatus. A cylindrical support member 5 is installed on a product support table 7 of the CVD apparatus, and the projection 4 of the tubular body 1 is supported by contacting the support member 5. The second support member 5 and the second cylindrical body 1 are further placed thereon, and the protrusions 4 of the cylindrical body 1 are repeatedly supported by the support member 5 to repeatedly stack a plurality of substrates. Then, it is placed in a CVD apparatus reaction vessel.
[0026]
As described above, the projections 4 are provided on the cylindrical body 1 and supported by the support member 5, so that the plurality of cylindrical bodies 1 can be stacked vertically and efficiently formed into a film, and the inner peripheral surface can be efficiently formed. 2 and the sealing surface 10 can be uniformly formed. Further, it is preferable that the actual support portion 6 of the support member 5 be in discontinuous first contact or discontinuous point contact, rather than in full contact with the protrusion 4.
[0027]
The projection 4 in FIGS. 1 and 2 is formed in a form in which a step is formed on the outer peripheral side of the sealing surface 10. The reason for forming the step is to form the sealing surface 10 with a high-purity CVD film. In FIGS. 1 and 2, a step is formed between the sealing surface 10 and the projecting portion 4. However, as shown in FIG. Can be achieved.
[0028]
As in FIG. 1, FIGS. 3A and 3B are a plan view and a cross-sectional view of a one-sided cylindrical dome shape, and FIGS. 3C and 3D are a plan view and a cross-sectional view of a circular pipe ring shape with both ends open. The cylindrical body 1 (integrated with the one-side sealing portion 1a in FIG. 3B) has an inner peripheral surface 2, an outer peripheral surface 3, a projection 4, and an end surface (seal surface) 10, A plasma-resistant coating 9 is provided on the peripheral surface 2 and the sealing surface 10. In other words, it is an important condition that the projections 4 are sealed at the flat surface of the plasma atmosphere sealing surface 10 and are located on the outer peripheral side of the flat surface and have a height different from that of the flat surface.
[0029]
FIGS. 4A and 4B show a state in which the tubular body 1 is attached to an apparatus. Then, as shown in FIGS. 4A and 4B, when the apparatus is mounted, the pressure is set to be higher than the pressure point 11 which is located on the seal surface 10 and is located on the inner peripheral side of the contact position of the support member 5. In addition, by inserting the elastic member 14 at a position where the protrusion 4 is located, high airtightness can be ensured, and the film 9 can be firmly fixed from the inner peripheral side plasma sealing surface side. Therefore, the atmosphere exposed to the plasma can be kept clean.
[0030]
A region on the inner peripheral side of the contact position of the support member 5 contacting the film-forming projection 4 can be used as a sealing surface for a plasma generation atmosphere. By positioning the contact position between the film-forming projection 4 and the support member 5 on the outer peripheral side from the pressing point 11 for fixing the sealing surface 10, the sealing surface 10 having a coating formed on the entire surface is formed, and at least the support surface is formed. After the elastic member 14 for sealing is arranged on the outer peripheral side from the position of the contact surface of the member 5, the sealing surface 10 is fixed, so that the inner peripheral plasma sealing surface on which the coating is formed can be firmly fixed. . Therefore, the atmosphere exposed to the plasma can be kept clean.
[0031]
Further, by forming a C-plane or an R-plane of 20 μm or more on the peripheral portion 13 where the inner peripheral surface 2 on which the coating 9 is formed and the sealing surface 10 intersect, it is possible to prevent the peeling of the coating which easily occurs on the peripheral portion 13. it can.
[0032]
Subsequently, the production method of the present invention will be described in detail.
[0033]
The plasma-resistant member of the present invention is obtained by forming a coating of silicon carbide and boron carbide on the surface of a cylindrical body 1 of a silicon carbide sintered body and a boron carbide sintered body. Alternatively, by applying a microwave or a high-frequency voltage to a chlorine-based, bromine-based, oxygen-based, or hydrogen-based simple substance or a mixed gas, excellent plasma resistance can be achieved even in a plasma state. Fluorine-based gas includes SF ₆ , CF ₄ , ClF ₃ , HF, NF _3, etc. Chlorine-based gas includes Cl ₂ , BCl ₃ , HCl, and the like, and oxygen, hydrogen and a compound thereof are mixed with the above gas. It is a thing.
[0034]
As a means for forming the film, a known film forming technique, for example, a CVD method may be used. In the case of silicon carbide, a source gas of CH ₃ SiCl ₃ is used, and in the case of boron carbide, a source gas of BCl ₃ and C ₆ H _{6 is used.} Is introduced into a reaction vessel in which a substrate is arranged, and heat is applied as an energy source to cause a chemical reaction to form respective films on the surface of the substrate. The heat applied at this time causes a chemical reaction, and the temperature may exceed 1,000 degrees and reach 1500 degrees in order to control the film quality and crystal orientation. In order to form a film under such a high temperature condition, it is preferable that the tubular body 1 and the film 9 are made of the same material. Further, a combination in which an intermediate layer is provided therebetween to reduce the residual stress of the coating film and further the residual stress of compression remains in the coating film is preferable.
[0035]
By using the above-mentioned CVD method, a film excellent in the above-mentioned properties is applied to a main surface exposed to plasma and a sealing surface 10 in a plasma generating atmosphere of a cylindrical body 1 having a single-sealed cylindrical dome shape or a tubular ring shape having both ends open. When forming the projections 9, the projections 4 for film formation are formed on the outer peripheral side of the sealing surface 10 of the cylindrical body 1 and on the surface that is not exposed to plasma having different heights. The support member 5 in contact with the portion 4 is installed so as to have discontinuous line contact and discontinuous point contact, and the bending strength of the support member 5 is made of carbon material of 20 MPa or more, so that stacking with excellent dismantling capability is possible. A simple manufacturing method can be realized.
[0036]
According to the above-described embodiment and manufacturing method, a plasma-resistant member capable of achieving excellent plasma resistance and low particle resistance to corrosive gas plasma and realizing a long life can be provided.
[0037]
FIG. 5 shows an etching apparatus to which the plasma resistant member of the present invention is applied. In the chamber 21, a wafer 24 is placed on the lower electrode 23 and held by the clamp ring 22, and a high-frequency coil 25 is provided outside. Among them, the above-described plasma-resistant member of the present invention can be used for the chamber 21.
[0038]
【Example】
Example 1
The embodiment shown in FIG. 1 was manufactured as an example of the present invention. The approximate dimensions of the cylindrical body 1 are as follows: the maximum outer diameter including the projection 4 of the single-sealed cylindrical dome of FIGS. 1 (A) and 1 (B) is 380 mm; the outer diameter of the outer peripheral surface 3 excluding the projection 4 is 350 mm; The inner diameter of the inner peripheral surface 2 is 320 mm, the total height is 65 mm, the depth on the inner diameter side is 50 mm, and the maximum outer diameter including the protrusion 4 of the open-ended tubular ring shown in FIGS. 1 (C) and 1 (D) is 380 mm. The outer diameter of the outer peripheral surface 3 is 350 mm, the inner diameter of the inner peripheral surface 2 is 320 mm, and the total height is 50 mm.
[0039]
The cylindrical body 1 was made of silicon carbide and boron carbide. The silicon carbide sintered body was obtained by adding 0.6% by weight of boron carbide and 2% by weight of a carbon source to α-type silicon carbide powder having a purity of 99.5%, performing CIP molding, and firing at 2060 ° C. in a non-oxidizing atmosphere. . On the other hand, the substrate of the boron carbide sintered body was fired using a hot press. Specifically, a raw material obtained by adding a small amount of boron to boron carbide powder having a purity of 99.9% was placed in a carbon mold and fired at a firing temperature of 2200 ° C. and a molding pressure of 200 kg / cm ² .
[0040]
As the material of the supporting member 5, high-purity carbon having a bending strength of 50 MPa, 40 MPa, 30 MPa, 20 MPa, and 10 MPa was used. On the other hand, a contact member in which the contact state between the actual support portion 6 of the support member 5 and the projection portion 4 was a full-surface contact, a discontinuous surface contact, a discontinuous line contact, and a discontinuous point contact was prepared.
[0041]
The supporting member 5 in contact with the entire peripheral surface has an outer diameter of 380 mm, an inner diameter of 360 mm, a width of the actual supporting portion 6 of 10 mm, and a height of 125 mm for a single-sealed cylindrical dome shape and 100 mm for a circular tube ring shape with both ends open. An opening 8 for smoothing the gas flow is formed in the height direction of the support member 5. The support member 5 having discontinuous surface contact has substantially the same shape as the entire peripheral surface contact, but the width of the actual support portion 6 remains at 10 mm, and the actual support portion 6 having an arc length divided into 16 in the circumferential direction. Are equally arranged in four places in the circumferential direction, and a portion other than the actual support portion 6 is cut into a height of 5 mm in the height direction. The circumferential arrangement of the actual support portion 6 of the support member 5 in the discontinuous line contact is the same as that of the discontinuous surface contact, and the radius R5 is applied in the width direction of the actual support portion 6. The support member 5 at the discontinuous point contact has a hemispherical projection with a radius R5 at a position equally divided into four in the circumferential direction.
[0042]
Based on the combination of the bending strength of the supporting member 5 and the contact state described above, four stages are stacked in a reaction vessel of a CVD apparatus, and the pressure is reduced under a temperature condition of 1200 ° C., and in the case of silicon carbide, CH ₃ SiCl _{3 is used.} In the case of a raw material gas or boron carbide, a mixed raw material gas of BCl ₃ and C ₆ H ₆ is introduced into a reaction vessel, and the above-mentioned heat is applied as an energy source to cause a chemical reaction, thereby forming each film into a cylindrical body. The film was formed on the surface so as to have a thickness of 400 μm.
[0043]
After the completion of the predetermined film formation, the reaction vessel was opened, and the stacked cylindrical bodies 1 and the support members 5 were disassembled. As a result, a silicon carbide film was formed on the silicon carbide sintered body base, and the boron carbide sintered body base was formed. Even when a boron carbide coating is formed thereon, the disassembly, deformation of the actual support portion 6, and damage to the support member 5 are determined by the contact state of the actual support portion 6 and the material strength of the support member 5 regardless of the material. showed that. Table 1 shows the results obtained by summarizing the contact state of the actual support portion 6 and the strength of the support member 5.
[0044]
When using the supporting member 5 that is in contact with the entire peripheral surface, the protrusion 4 and the supporting member 5 cannot be easily dismantled, and a large-scale operation of cutting and disassembling the supporting member 5 side of the supporting member 5 is required. And In the case of the discontinuous surface contact, the cutting operation was easier than in the case of the entire peripheral surface contact, but the large-scale cutting operation was not eliminated. On the other hand, in the case of the support member 5 having the discontinuous line contact and the discontinuous point contact structure, the support member 5 and the protrusion 4 can be separated by applying a slight impact, thereby facilitating dismantling work. Was completed. However, in the case of discontinuous line contact or discontinuous point contact, if the strength of the support member 5 is as low as 10 MPa, deformation of the actual support portion 6 at a high temperature occurs, deterioration of dismantling properties, and support due to impact given during disassembly. The member 5 was damaged, and additional work was required for repeated use of the support member 5.
[0045]
Therefore, by making the actual support portion 6 of the support member 5 on the side of the protrusion 4 a discontinuous line contact or a discontinuous point contact, the disassembly of the protrusion 4 and the support member 5 after CVD film formation can be greatly improved. By setting the bending strength of the support member 5 to 20 MPa or more, it is possible to prevent deformation due to high-temperature creep at the time of stacking and forming the cylindrical body 1, and to achieve good dismantling and repeated use of the support member 5. Can be possible.
[0046]
[Table 1]

[0047]
Example 2
The C-plane and the R-plane of the peripheral edge portion 13 of the plasma atmosphere sealing surface of the cylindrical body made of the single-sealed cylindrical dome-shaped silicon carbide sintered body shown in Example 1 were 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, and 100 μm. Using a carbon support member 5 having a projection 4 at a discontinuous point contact and a bending strength of 50 MPa, five products each having a 400 μm thick silicon carbide film formed by a CVD method were manufactured. Peeling of the film on the peripheral portion 13 after disassembly after film formation and polishing of the sealing surface was confirmed. Table 2 shows the results. When the C surface and the R surface of the peripheral portion 13 are set to 10 μm, peeling of the film is observed on the product. Since the peripheral portion 13 of the silicon carbide sintered body is formed to be thick at the time of film formation, peeling due to the influence of film stress at the time of film formation, peeling due to collision at the time of disassembly after film formation, and grinding wheel at the time of polishing work. Some defects were found due to processing defects generated when the surface to be processed, which is the coating 9 surface, was separated.
[0048]
As described above, when the C surface or the R surface having a thickness of 20 μm or more is formed on the peripheral portion 13, peeling of the film due to film stress, collision, or impact during processing can be prevented.
[0049]
[Table 2]

[0050]
Example 3
A 30 mm square, 3 mm thick test piece having a 400 μm film formed simultaneously with Examples 1 and 2 was prepared, and plasma resistance was evaluated. A corrosion test using Cl ₂ gas plasma was performed while cooling the test piece by cooling the sample stage of the RIE apparatus. For comparison, alumina ceramics conventionally used were also evaluated at the same time. Table 3 shows the ratio of the corrosion rate of the silicon carbide test piece to that of the silicon carbide test piece and the rate of the corrosion rate of the boron carbide CVD film to the boron carbide test piece, based on the corrosion rate of alumina ceramics. The product on which the CVD film is formed has a low corrosion rate of 1/40 to 1/50 as compared with the conventional alumina ceramics.
[0051]
[Table 3]

[0052]
As described above, in this embodiment, the example in which the silicon carbide and boron carbide films are formed on the silicon carbide and boron carbide sintered body base by the CVD method has been described. However, the protrusions 4 of the present invention are provided. The shape of the base and the shape of the support member can be applied to a member formed by coating a base made of an insulating material having excellent plasma resistance, such as silicon nitride, aluminum nitride, YAG, and MgAl ₂ O _4. It is. In the case of silicon carbide or boron carbide, it is possible to use high-purity carbon for the substrate, but in this case, it is necessary to use a material combination in which the carbon on the substrate is stronger than the carbon on the support member. Basically, it should be composed of a substrate and a coating of the same material, but when combining different materials, an intermediate layer having an intermediate coefficient of thermal expansion is formed between the substrate and the coating, and the substrate and the coating are formed. It is also possible to adopt a method of improving the adhesion of the slab.
[0053]
Although the support member of the present invention has shown an integral shape, the important point is to improve the disassembly of the base without damaging the base protrusion, and to improve the disassembly of the base and the base protrusion. The contact surface is constituted by discontinuous line contact and discontinuous point contact, and is not trapped as an integral type.
[0054]
As described above in detail, according to the present invention, a large number of individual products can be formed in a film forming operation, and a product with less peeling of a film can be stably provided.
[Brief description of the drawings]
FIG. 1 shows a plasma-resistant member of the present invention, wherein (A) and (C) are plan views, and (B) and (D) are cross-sectional views.
FIGS. 2A and 2B are arrangement diagrams of respective members when the members are installed in a CVD apparatus in order to form a film on a plasma-resistant member of the present invention.
FIG. 3 shows another embodiment of the present invention, wherein (A) and (C) are plan views, and (B) and (D) are cross-sectional views.
FIGS. 4A and 4B are schematic diagrams when the plasma resistant member of the present invention is installed in a semiconductor manufacturing apparatus.
FIG. 5 is a schematic view of a semiconductor manufacturing apparatus using the plasma-resistant member of the present invention.
[Explanation of symbols]
1: cylindrical body 1a: one-side sealing portion 2: inner peripheral surface 3: outer peripheral surface 4: protrusion 5: support member 6: actual support portion 7: support base 8: opening 9: coating film 10: end surface (sealing surface) )
11: Pressure point 13: Peripheral edge

Claims

The cylindrical body has a single-sided or open-ended cylindrical body, and the inner peripheral surface and the end surface of the cylindrical body have a plasma-resistant coating on the sealing surface, and the outer peripheral surface has a height different from the sealing surface of the cylindrical body. A plasma-resistant member having a projection formed thereon.

2. The plasma-resistant member according to claim 1 , wherein the projection has a surface that is continuously inclined from the outer peripheral side of the sealing surface, and the projection is also provided with a plasma-resistant coating.

The plasma resistance coating, silicon carbide, boron carbide, silicon nitride, aluminum nitride, YAG, plasma resistant member according to claim 1 or 2, characterized in that it is composed of MgAl ₂ O ₄ of one or more such .

A projection is formed on the outer peripheral surface of a cylindrical body which is partially sealed or open at both ends, and the inner peripheral surface and the end surface of the cylindrical body are sealed while the projection is mounted on the upper surface of the cylindrical support member. A method for producing a plasma-resistant member, comprising forming a plasma-resistant film on a surface.

5. The method for manufacturing a plasma-resistant member according to claim 4, wherein a support member and another cylindrical body are further laminated on the protrusion, and a plasma-resistant coating is simultaneously formed on the plurality of cylindrical bodies. .