JP4283925B2 - Corrosion resistant material - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、腐蝕ガスあるいはそれらのプラズマに対して、高い耐蝕性を有する耐蝕性部材に関する。
【０００２】
【従来の技術】
現在、半導体メモリーの急激な高集積化により、エッチング、不純物拡散、イオン注入工程の繰り返し回数の増加や、細密化によるプラズマの高集積化など半導体製造装置内の環境は、以前と比較して苛酷なものとなっている。特にドライプロセスやプラズマコーティングなど、プラズマの利用が急速に進んでいる。
【０００３】
その中で、パターンの焼き付けのために行われるドライエッチングでは、弗素系腐蝕ガスがその反応性の高さから利用されており、製造装置を構成する部材には、このような活性なガスに対する耐蝕性が要求される。
【０００４】
従来、製造装置を構成する部品として石英ガラスが使用されてきたが、石英ガラスは、ＣＦ４等の弗素系腐蝕ガスからプラズマによって分解して発生したラジカルＦがＳｉと反応して腐蝕され消耗が激しく、苛酷なエッチング環境ではその寿命が極めて短いものになっている。そこで、従来用いられてきた石英ガラスに代わりアルミナ等のセラミックス部材が用いられている。
【０００５】
【発明が解決しようとする課題】
従来半導体製造装置内のプラズマエッチング工程で使用されているアルミナ部材は、石英ガラスと比較すると耐蝕性に優れてはいるものの、それでもＣＦ４等の弗素系腐蝕ガスと反応し、表面の結晶粒子が脱落して装置内を汚染するという問題を生じさせている。
【０００６】
つまり、半導体製造におけるエッチング工程等で使用される部材は、ＣＦ４等の弗素系腐蝕ガスあるいはそれらのプラズマとの反応を抑え、表面の粒子の脱落を少なくしなければならないが、未だそのような部材は得られていない。
【０００７】
本発明はかかる事情に鑑みてなされたものであって、腐蝕ガスあるいはそれらのプラズマ、特に弗素系の腐蝕ガスあるいはそれらのプラズマに対して、高い耐蝕性を有する耐蝕性部材を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、腐蝕ガス特に弗素系腐蝕性ガスとの反応性が低いという点から、気孔率が２％以下の緻密で気孔の少ない弗化物セラミックスを用いることにより腐蝕ガスあるいはそれらのプラズマとの反応を抑え、表面の粒子の脱落を少なくできることを見出した。つまり、耐蝕性を必要とする部分に用いられる部材として、従来のアルミナと比較してＣＦ４等の腐蝕ガスに反応による表面の侵食速度が遅い弗化物セラミックスを少なくとも腐蝕ガスあるいはそれらのプラズマに露呈される部位に用いることにより、腐蝕ガス中でのプラズマエッチングにおいて、優れた耐蝕性を発揮することを見出した。
【００１１】
本発明はこのような知見に基づいてなされたものであり、半導体製造装置内において、腐蝕ガスあるいはそれらのプラズマの雰囲気で用いられる耐蝕部材であって、基体と、その表面で少なくとも腐蝕ガスあるいは腐蝕ガスのプラズマに露呈される面に設けられた溶射で得られた耐蝕層とを有し、前記耐蝕層は、気孔率が２％以下である緻密質の弗化物セラミックスで構成され、前記弗化物セラミックスがＣａＦ２、ＭｇＦ２から選択される少なくとも一種であることを特徴とする耐蝕性部材を提供するものである。
【００１２】
前記基体は、金属またはセラミックスが好ましい。
【００１３】
本発明の耐食性部材が適用される前記半導体製造装置としては、エッチング工程で用いられるものが好適である。
【００１４】
【発明の実施の形態】
以下、本発明について具体的に説明する。
本発明の耐蝕性部材は、腐蝕ガスあるいはそれらのプラズマの雰囲気で用いられ、少なくともその腐蝕ガスあるいはそれらのプラズマに露呈される部位が、気孔率２％以下である緻密質の弗化物セラミックスで構成される。
【００１５】
この場合に、耐蝕部材の全部が弗化物セラミックスであってもよいし、腐蝕ガスあるいはそのプラズマに露呈される表面部分のみが弗化物セラミックスであってもよい。このような弗化物セラミックスとしては、ＣａＦ２、ＭｇＦ２、ＹＦ３、ＡｌＦ３、ＣｅＦ３から選択される少なくとも一種を主体とするものを挙げることができる。弗化物セラミックスは緻密なものであればその形態は問わないが、典型的には焼結体で構成することができる。弗化物セラミックス焼結体を他の部材に接合することにより、腐蝕ガスあるいはそのプラズマに露呈される表面部分のみを弗化物焼結体とすることができる。
【００１６】
この弗化物セラミックス焼結体としては、弗化物から実質的になる主相と、主相を構成する弗化物よりも融点が低い弗化物から実質的になり、主に前記主相の粒界に存在する副相とからなるものであることが好ましい。
【００１７】
この場合に、副相として存在する、主相を構成する弗化物よりも融点が低い弗化物は、主に主相の粒界に存在して焼結助剤として機能し、焼結体の緻密化に寄与する。この副相の存在により緻密化が促進される結果、常圧焼結でも十分に緻密化する。したがって、形状の制限がなく緻密な焼結体を得ることができる。また、主相および副相のいずれもが、腐蝕ガスとの反応性が低い弗化物で構成されているため、耐蝕性が極めて高い。なお、主相および副相は、弗化物の他、微量の不純物や添加物は含まれていてもよい。
【００１８】
ここで、主相を構成する弗化物としては、ＣａＦ２、ＭｇＦ２、ＹＦ３から選択される少なくとも一種を用いることが好ましい。これは、これらの弗化物に毒性がなく、以下に述べるＬｉＦ等を添加して焼結した場合に、最も焼結性が優れているからである。主相を構成する弗化物として、他に、ＡｌＦ３、ＳｒＦ２、ＢａＦ２、ＣｅＦ３等を用いることもできる。
【００１９】
また、副相を構成する弗化物としては、ＬｉＦが好ましい。これは、ＬｉＦの融点が８４２℃と、ＣａＦ２（融点：１３７３℃）やＭｇＦ２（融点：１２６０℃）やＹＦ３（融点：１１５２℃）と比較してかなり低く、焼結助剤としての効果が大きいからである。副相を構成する弗化物として、他に、ＮａＦ等を用いることもできる。
【００２０】
このように、副相は主に焼結助剤としての機能を果たすものであり、その量は焼結体全体の０．５〜５ｍｏｌ％が好ましい。０．５ｍｏｌ％未満であると焼結を促進する効果が小さく、５ｍｏｌ％を超えると副相を構成する弗化物、例えばＬｉＦが粒界に偏析して粒界相を形成し、機械的特性の劣化、特に高温強度の低下をもたらすからである。
【００２１】
また、弗化物セラミックス焼結体の密度は、相対密度で９９％以上であることが好ましい。このような緻密な焼結体とすることにより、腐蝕ガスに対する耐蝕性、耐プラズマ性を一層高いものとすることができる。
【００２２】
本発明の耐蝕性部材としては、基体と、その表面で少なくとも腐蝕ガスあるいはそれらのプラズマに露呈される面に設けられた気孔率が２％以下である緻密質の弗化物セラミックスからなる膜状の耐蝕層とで構成することができる。この耐蝕層は緻密な膜状体であれば、どのようなものであっても良いが、溶射または蒸着により得られる膜であることが好ましい。蒸着には、スパッタ、真空蒸着、イオンプレーティング等が含まれる。また、基体としてはセラミックス、金属等を用いることができる。さらに、耐蝕層を構成する弗化物セラミックスとしては、ＣａＦ２、ＭｇＦ２、ＹＦ３、ＡｌＦ３、ＣｅＦ３から選択される少なくとも一種を主体とするものを用いることが好ましい。前記耐蝕層は、耐久性の観点から、その厚さが１００μｍ以上が好ましく、さらに、２００μｍ以上であれば一層好ましい。その厚さが１００μｍ未満であると、プラズマ等により短期間のうちに損耗してしまうことがあり好ましくない。また、厚すぎてもコストが上昇してまうため、５００μｍ以下であることが好ましい。
【００２３】
上述した耐蝕性部材は、半導体デバイスを製造する際のエッチング工程等で用いられる腐蝕ガスやプラズマに露呈される部材として好適である。このような分野で用いられる腐蝕ガスとしてはＣＦ４、ＳＦ６、ＣＨＦ３などの弗素系ガスが用いられ、これらの使用に際しては、典型的にはこれらのガス雰囲気に高周波電力を印加したりマイクロ波等を導入することによりプラズマ化されるが、本発明の耐蝕性部材は、このような雰囲気下において十分な耐蝕性を有する。
【００２４】
次に、上述した本発明の耐蝕性部材の製造方法を例示する。
耐蝕性部材の全部が弗化物セラミックスであって、弗化物セラミックスが焼結体の場合には、常法に従って、粉末を成形し焼結することにより得られる。弗化物の焼結体として、弗化物から実質的になる主相と、主相を構成する弗化物よりも融点が低い弗化物から実質的になり、主に前記主相の粒界に存在する副相からなる焼結体を用いる場合には、主相となる弗化物原料例えばＣａＦ２、ＭｇＦ２、ＹＦ３等の粉末を用い、副相となる弗化物原料、例えばＬｉＦ粉末を０．５〜５ｍｏｌ％添加して湿式混合し、成形したものを５５０〜１０５０℃で常圧焼結することが好ましい。原料粉末としては、平均粒径が２μｍ以下のものが好ましい。さらに、得られた常温焼結体をＡｒ雰囲気で温度５００〜１０００℃、圧力１０００〜１８００ｋｇ／ｃｍ２の条件でＨＩＰ法にて処理することにより、相対密度１００％の高密度を有する弗化物セラミックス焼結体の耐蝕性部材を得ることができる。
【００２５】
一方、弗化物セラミックスが膜状の耐蝕層を構成する場合には、弗化物原料例えばＣａＦ２、ＭｇＦ２、ＹＦ３、ＡｌＦ３、ＣｅＦ３等の粉末を使用して、基体となるＡｌ２Ｏ３、ＡｌＮ、ＺｒＯ２等のセラミックス、またはＳＵＳ３０４、Ｃｕ、Ａｌ、Ａｌ合金等の金属の表面に例えば従来の溶射または蒸着にて膜を形成することが好ましい。この方法によれば、これらの表面に気孔率が２％以下の緻密で気孔の少ない弗化物セラミックスの膜を有する耐蝕性部材を容易に得ることができる。この際に、上述したような１００〜５００μｍの範囲の膜厚を得る観点からは、成膜方法として溶射を用いることがより好ましい。
【００２６】
上述したように、これらの方法で得られた気孔率が２％以下である緻密質の弗化物セラミックス焼結体または表面が弗化物セラミックスの膜で構成される耐蝕性部材は、従来、半導体製造装置内で用いられる腐蝕ガスやプラズマに露呈される部分に用いられた石英やアルミナに比べて表面の侵食速度が遅く、半導体製造装置内を汚染しない耐蝕性部材として有効である。
【００２７】
【実施例】
以下、本発明の実施例について説明する。
（参考例１〜１９）
純度９８％のＣａＦ２（関東化学製、試薬１級）、ＭｇＦ２（関東化学製、試薬１級）、ＹＦ３（関東化学製、試薬１級）粉末を、ボールミルを用いて６４時間粉砕して、平均粒径を１．６μｍとした。その後、これら粉末にＬｉＦ（試薬１級）粉末を０．５〜５ｍｏｌ％添加し、エタノール中で６４時間、湿式混合を行った。このようにして得られた混合粉末を、一軸加圧により７５ＭＰａで１分間、および冷間静水圧成型法により１５０ＭＰａで１分間の条件で成形した。このようにして得られた成形体について、５５０〜９００℃で１時間の条件で常圧焼結を行った。この常圧焼結体の密度をアルキメデス法により測定した結果、常圧焼結体の相対密度は９０％以上であった。
【００２８】
その後、上記常圧焼結体を、圧力媒体をＡｒとして、５５０〜９００℃の最高温度で、圧力１８００ｋｇ／ｃｍ２で１時間ＨＩＰ法により処理し、このＨＩＰ焼結体を作製した。そのようにして得られた焼結体をアルキメデス法で測定した。その結果、表に示さないが、相対密度が１００％の高密度を有する弗化物セラミックス焼結体が得られたことが確認された。
【００２９】
このようにして得られた弗化物セラミックス焼結体を、周波数が２．４５ＧＨｚで出力が８００Ｗの平行平板電極型プラズマエッチング装置を用いて、ＣＦ４とＯ２の体積比が４：１である雰囲気で約４０分間プラズマエッチングを行った。
【００３０】
そして、エッチング前後の重量変化を測定することにより、エッチングレートを算出した。その結果を製造条件とともに表１に示す。表１に示すように、これら実施例のエッチングレートは０．９〜２．９μｍ／ｈｒであり、高い耐蝕性を有する弗化物セラミックス焼結体が得られることが確認された。また、気孔率を測定した結果、表１に示すように気孔率が０．１〜０．９％であることから、緻密性が極めて優れていることも確認された。
【００３１】
【表１】
（実施例１〜４、参考例２０〜２２）
ＣａＦ２、ＭｇＦ２、ＹＦ３、ＡｌＦ３、ＣｅＦ３（森田化学製、平均粒径１０μｍ）を溶射被膜材とし、プラスト処理して表面を１０〜５０ｍｍの粗さにした５０×５０×１０ｍｍのＳＵＳ３０４、Ａｌ２Ｏ３、ＺｒＯ２、を基体として用いた。この基体上に、上記の溶射被膜材を、メテコ社製のプラズマ溶射装置９ＭＢにより、大気雰囲気で電圧１５０ボルト、電流９０アンペア、粉末供給量１０ｇ／ｍｉｎの条件にてプラズマ溶射して、２００〜３００μｍの厚さで気孔率が１〜２％の溶射被膜を形成した。
【００３３】
このようにして得られた弗化物セラミックスの被膜部材について、実施例１〜１９と同様の方法でプラスマエッチングを行い、エッチング前後の重量変化を測定し、エッチングレートを算出した。その結果、表２に示すようにエッチングレートは２．１〜３．３μｍ／ｈｒであり、高い耐蝕性を有する弗化物セラミックスの膜が得られたことが確認された。また、気孔率を測定した結果、表２に示すように気孔率が１．７〜２．０％であることから、緻密性が優れていることも確認された。
【００３４】
【表２】
（参考例２３〜２６）
ＭｇＦ２、ＣａＦ２、ＹＦ３（森田化学製、平均粒径１０μｍ）を蒸着被膜材とし、５０×５０×１０ｍｍのＳＵＳ３０４、Ａｌ２Ｏ３を基板として用い、この基板上に、真空蒸着装置を用いて、真空度１×１０−４torrでＷバスケットヒーターによる真空蒸着を行って、２〜３μｍの厚さで蒸着被膜を形成した。
【００３６】
このようにして得られた弗化物セラミックスの被膜部材について、前述の実施例と同様の方法でプラスマエッチングを行い、エッチング前後の重量変化を測定し、エッチングレートを算出した。その結果、表３に示すようにエッチングレートは１．７〜２．０μｍ／ｈｒであり、高い耐蝕性を有する弗化物セラミックスの膜が得られたことが確認された。
【００３７】
【表３】
（比較例１〜２）
石英ガラスおよびＡｌ２Ｏ３（日本セラテック製）について、実施例１〜１９と同様の方法でプラズマエッチングを行い、エッチング前後の重量変化を測定し、エッチングレートを算出した。その結果、表４に示すように石英ガラスのエッチングレートは１０．２μｍ／ｈｒであり、また、Ａｌ２Ｏ３のエッチングレートは５．１μｍ／ｈｒとなり、焼結体の耐蝕性が劣っていることが確認された。
【００３９】
【表４】
【発明の効果】
以上説明したように、本発明によれば、少なくとも腐蝕ガスあるいはそのプラズマに露呈される部位が、気孔率２％以下である緻密質の弗化物セラミックスによって構成されるので、従来半導体製造装置内で使用されていた石英ガラスおよびアルミナに比べて、ＣＦ４ガスとの反応による表面の侵食速度が遅く、耐蝕性に極めて優れている。したがって、エッチング、不純物拡散、イオン注入工程などの腐蝕性雰囲気で用いられる半導体製造装置を構成する部材に極めて好適に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a corrosion-resistant member having high corrosion resistance against a corrosive gas or plasma thereof.
[0002]
[Prior art]
Currently, the environment in semiconductor manufacturing equipment, such as the increase in the number of repetitions of etching, impurity diffusion, and ion implantation processes due to the rapid integration of semiconductor memories and the high integration of plasma due to miniaturization, is more severe than before. It has become a thing. In particular, the use of plasma is rapidly progressing in dry processes and plasma coating.
[0003]
Among them, in dry etching performed for pattern baking, a fluorine-based corrosive gas is used because of its high reactivity, and the members constituting the manufacturing apparatus are resistant to such active gas. Sex is required.
[0004]
Conventionally, quartz glass has been used as a component of a manufacturing apparatus. However, quartz glass is consumed by radical F generated by decomposition by plasma from a fluorine-based corrosive gas such as CF 4 , reacting with Si, and is consumed. In a harsh and harsh etching environment, its lifetime is extremely short. Therefore, ceramic members such as alumina are used instead of the conventionally used quartz glass.
[0005]
[Problems to be solved by the invention]
Although the alumina member used in the plasma etching process in the conventional semiconductor manufacturing apparatus is superior in corrosion resistance compared to quartz glass, it still reacts with a fluorine-based corrosive gas such as CF 4 and the surface crystal particles are This causes a problem of dropping and contaminating the inside of the apparatus.
[0006]
That is, a member used in an etching process or the like in semiconductor manufacturing must suppress the reaction with a fluorine-based corrosive gas such as CF 4 or their plasma and reduce the dropout of surface particles. The member is not obtained.
[0007]
The present invention has been made in view of such circumstances, and an object thereof is to provide a corrosion-resistant member having high corrosion resistance against a corrosive gas or a plasma thereof, in particular, a fluorine-based corrosive gas or a plasma thereof. And
[0008]
[Means for Solving the Problems]
As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that fluoride ceramics having a porosity of 2% or less and low porosity are low in reactivity with a corrosive gas, particularly a fluorine-based corrosive gas. It has been found that the reaction of the corrosive gases or their plasma can be suppressed by using the, and the dropout of the surface particles can be reduced. In other words, as a material used in parts that require corrosion resistance, fluoride ceramics whose surface erosion rate is slow due to reaction with a corrosive gas such as CF 4 compared to conventional alumina is exposed to at least the corrosive gas or their plasma. It has been found that by using it in a portion to be applied, excellent corrosion resistance is exhibited in plasma etching in a corrosive gas.
[0011]
The present invention has been made on the basis of such knowledge, and is a corrosion-resistant member used in a semiconductor manufacturing apparatus in an atmosphere of a corrosive gas or a plasma thereof. The base and the surface thereof are at least a corrosive gas or a corrosive material. A corrosion-resistant layer obtained by thermal spraying provided on a surface exposed to gas plasma, wherein the corrosion-resistant layer is made of a dense fluoride ceramic having a porosity of 2% or less, and the fluoride The present invention provides a corrosion-resistant member characterized in that the ceramic is at least one selected from CaF 2 and MgF 2 .
[0012]
Before Symbol substrate, metal or ceramics is not preferred.
[0013]
The semiconductor manufacturing apparatus to which the corrosion-resistant member of the present invention is applied is preferably one used in an etching process.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
The corrosion-resistant member of the present invention is used in an atmosphere of a corrosive gas or their plasma, and is composed of a dense fluoride ceramic having a porosity of 2% or less at least at a portion exposed to the corrosive gas or their plasma. Is done.
[0015]
In this case, all of the corrosion-resistant member may be fluoride ceramics, or only the surface portion exposed to the corrosive gas or its plasma may be fluoride ceramics. Examples of such fluoride ceramics include those mainly composed of at least one selected from CaF 2 , MgF 2 , YF 3 , AlF 3 , and CeF 3 . The form of fluoride ceramics is not particularly limited as long as it is dense, but can typically be composed of a sintered body. By bonding the fluoride ceramic sintered body to another member, only the surface portion exposed to the corrosive gas or its plasma can be made the fluoride sintered body.
[0016]
This fluoride ceramic sintered body is substantially composed of a main phase substantially composed of fluoride and a fluoride having a melting point lower than that of the fluoride constituting the main phase, and mainly at the grain boundary of the main phase. It is preferable that it consists of the subphase which exists.
[0017]
In this case, the fluoride existing as a secondary phase and having a melting point lower than that of the fluoride constituting the main phase is mainly present at the grain boundary of the main phase and functions as a sintering aid. Contributes to As a result of the promotion of densification by the presence of this subphase, the sub-phase is sufficiently densified even under normal pressure sintering. Therefore, it is possible to obtain a dense sintered body without limitation of the shape. Further, since both the main phase and the subphase are made of fluoride having low reactivity with the corrosive gas, the corrosion resistance is extremely high. In addition, the main phase and the subphase may contain a trace amount of impurities and additives in addition to fluoride.
[0018]
Here, it is preferable to use at least one selected from CaF 2 , MgF 2 and YF 3 as the fluoride constituting the main phase. This is because these fluorides are not toxic and have the highest sinterability when sintered by adding LiF or the like described below. In addition, AlF 3 , SrF 2 , BaF 2 , CeF 3 and the like can also be used as the fluoride constituting the main phase.
[0019]
Further, LiF is preferable as the fluoride constituting the subphase. This is because the melting point of LiF is 842 ° C., which is considerably lower than that of CaF 2 (melting point: 1373 ° C.), MgF 2 (melting point: 1260 ° C.) and YF 3 (melting point: 1152 ° C.). This is because the effect is great. In addition, NaF or the like can also be used as the fluoride constituting the subphase.
[0020]
Thus, the subphase mainly functions as a sintering aid, and the amount thereof is preferably 0.5 to 5 mol% of the entire sintered body. If the amount is less than 0.5 mol%, the effect of promoting sintering is small, and if it exceeds 5 mol%, a fluoride constituting the subphase, for example, LiF segregates at the grain boundary to form a grain boundary phase, and the mechanical properties are reduced. This is because the deterioration, particularly the high temperature strength is reduced.
[0021]
The density of the fluoride ceramic sintered body is preferably 99% or more in terms of relative density. By using such a dense sintered body, the corrosion resistance against the corrosive gas and the plasma resistance can be further enhanced.
[0022]
The corrosion-resistant member of the present invention is a film-like film made of a dense fluoride ceramic having a porosity of 2% or less provided on the surface of the substrate and at least the surface exposed to the corrosive gas or plasma thereof. It can be composed of a corrosion resistant layer. The corrosion-resistant layer may be any film as long as it is a dense film, but is preferably a film obtained by thermal spraying or vapor deposition. Deposition includes sputtering, vacuum deposition, ion plating, and the like. Moreover, ceramics, metals, etc. can be used as the substrate. Further, it is preferable to use a ceramic mainly comprising at least one selected from CaF 2 , MgF 2 , YF 3 , AlF 3 , and CeF 3 as the fluoride ceramic constituting the corrosion resistant layer. From the viewpoint of durability, the corrosion resistant layer preferably has a thickness of 100 μm or more, and more preferably 200 μm or more. If the thickness is less than 100 μm, it may be worn out in a short period of time due to plasma or the like. Moreover, since it will raise cost even if it is too thick, it is preferable that it is 500 micrometers or less.
[0023]
The corrosion-resistant member described above is suitable as a member exposed to a corrosive gas or plasma used in an etching process or the like when manufacturing a semiconductor device. As a corrosive gas used in such a field, a fluorine-based gas such as CF 4 , SF 6 , or CHF 3 is used. In using these gases, typically, a high-frequency power is applied to these gas atmospheres or a micro gas is used. Although it is turned into plasma by introducing waves or the like, the corrosion-resistant member of the present invention has sufficient corrosion resistance in such an atmosphere.
[0024]
Next, the manufacturing method of the corrosion-resistant member of this invention mentioned above is illustrated.
In the case where all of the corrosion-resistant members are fluoride ceramics and the fluoride ceramics is a sintered body, it is obtained by molding and sintering the powder according to a conventional method. As a sintered body of fluoride, it consists essentially of a main phase composed of fluoride and a fluoride having a melting point lower than that of the fluoride constituting the main phase, and exists mainly at the grain boundaries of the main phase. In the case of using a sintered body comprising a subphase, a fluoride raw material serving as a main phase, for example, CaF 2 , MgF 2 , YF 3 or the like powder is used, and a fluoride raw material serving as a subphase, such as LiF powder, is 0.5%. It is preferable to add ~ 5 mol%, wet mix, and form the molded article at 550 to 1050 ° C under atmospheric pressure sintering. The raw material powder preferably has an average particle size of 2 μm or less. Furthermore, the obtained normal temperature sintered body is treated by the HIP method in an Ar atmosphere at a temperature of 500 to 1000 ° C. and a pressure of 1000 to 1800 kg / cm 2 , thereby obtaining a fluoride ceramic having a high density of 100% relative density. A corrosion-resistant member of a sintered body can be obtained.
[0025]
On the other hand, when fluoride ceramics constitutes a film-like corrosion-resistant layer, fluoride raw materials such as CaF 2 , MgF 2 , YF 3 , AlF 3 , CeF 3, etc. are used to form a base Al 2 O 3. Preferably, a film is formed on the surface of a ceramic such as AlN or ZrO 2 or a metal such as SUS304, Cu, Al, or an Al alloy by conventional thermal spraying or vapor deposition. According to this method, it is possible to easily obtain a corrosion-resistant member having a fluoride ceramic film with a small porosity of 2% or less on these surfaces. At this time, from the viewpoint of obtaining a film thickness in the range of 100 to 500 μm as described above, it is more preferable to use thermal spraying as a film forming method.
[0026]
As described above, a dense fluoride ceramic sintered body having a porosity of 2% or less obtained by these methods or a corrosion-resistant member having a surface composed of a fluoride ceramic film has been conventionally used in semiconductor manufacturing. It is effective as a corrosion-resistant member that does not contaminate the inside of the semiconductor manufacturing apparatus because the surface erosion rate is lower than that of quartz or alumina used in the portion exposed to the corrosive gas or plasma used in the apparatus.
[0027]
【Example】
Examples of the present invention will be described below.
( Reference Examples 1-19)
98% pure CaF 2 (Kanto Chemical Co., reagent grade 1), MgF 2 (Kanto Chemical Co., reagent grade 1), YF 3 (Kanto Chemical Co., reagent grade 1) powder was pulverized for 64 hours using a ball mill. The average particle size was 1.6 μm. Thereafter, 0.5 to 5 mol% of LiF (reagent grade 1) powder was added to these powders, and wet mixing was performed in ethanol for 64 hours. The mixed powder thus obtained was molded under the conditions of uniaxial pressing at 75 MPa for 1 minute and cold isostatic pressing at 150 MPa for 1 minute. The molded body thus obtained was subjected to atmospheric pressure sintering at 550 to 900 ° C. for 1 hour. As a result of measuring the density of this atmospheric pressure sintered body by the Archimedes method, the relative density of the atmospheric pressure sintered body was 90% or more.
[0028]
Thereafter, the pressureless sintering body, a pressure medium as Ar, at a maximum temperature of 550 to 900 ° C., treated with 1 hour HIP process at a pressure 1800 kg / cm 2, to prepare the HIP sintered bodies. The sintered body thus obtained was measured by the Archimedes method. As a result, although not shown in the table, it was confirmed that a fluoride ceramic sintered body having a relative density of 100% was obtained.
[0029]
The fluoride ceramic sintered body thus obtained has a volume ratio of CF 4 and O 2 of 4: 1 using a parallel plate electrode type plasma etching apparatus having a frequency of 2.45 GHz and an output of 800 W. Plasma etching was performed for about 40 minutes in an atmosphere.
[0030]
And the etching rate was computed by measuring the weight change before and behind etching. The results are shown in Table 1 together with the manufacturing conditions. As shown in Table 1, the etching rate of these examples was 0.9 to 2.9 μm / hr, and it was confirmed that a fluoride ceramic sintered body having high corrosion resistance was obtained. Moreover, as a result of measuring the porosity, as shown in Table 1, the porosity was 0.1 to 0.9%, and it was confirmed that the denseness was extremely excellent.
[0031]
[Table 1]
( Examples 1-4, Reference Examples 20-22 )
CaF 2 , MgF 2 , YF 3 , AlF 3 , CeF 3 (Morita Chemical Co., Ltd., average particle size 10 μm) was used as a thermal spray coating material, and the surface was roughened to 10 to 50 mm by plasting to 50 × 50 × 10 mm SUS304, Al 2 O 3 , ZrO 2 was used as a substrate. On this substrate, the above-mentioned sprayed coating material is plasma sprayed under the conditions of a voltage of 150 volts, a current of 90 amps, and a powder supply amount of 10 g / min in an air atmosphere by a plasma spraying apparatus 9MB manufactured by Meteco Co., Ltd. A sprayed coating having a thickness of 300 μm and a porosity of 1 to 2% was formed.
[0033]
The thus obtained fluoride ceramic coating member was subjected to plasma etching in the same manner as in Examples 1 to 19, the weight change before and after etching was measured, and the etching rate was calculated. As a result, as shown in Table 2, the etching rate was 2.1 to 3.3 μm / hr, and it was confirmed that a fluoride ceramic film having high corrosion resistance was obtained. Moreover, as a result of measuring the porosity, as shown in Table 2, since the porosity was 1.7 to 2.0%, it was confirmed that the denseness was excellent.
[0034]
[Table 2]
( Reference Examples 23 to 26 )
MgF 2 , CaF 2 , YF 3 (Morita Chemical Co., Ltd., average particle size 10 μm) is used as a vapor deposition coating material, 50 × 50 × 10 mm SUS304, Al 2 O 3 is used as a substrate, and a vacuum vapor deposition apparatus is formed on this substrate. Then, vacuum deposition was performed with a W basket heater at a vacuum degree of 1 × 10 −4 torr to form a deposited film with a thickness of 2 to 3 μm.
[0036]
The thus obtained fluoride ceramic coating member was subjected to plasma etching in the same manner as in the previous example, the change in weight before and after etching was measured, and the etching rate was calculated. As a result, as shown in Table 3, the etching rate was 1.7 to 2.0 μm / hr, and it was confirmed that a fluoride ceramic film having high corrosion resistance was obtained.
[0037]
[Table 3]
(Comparative Examples 1-2)
For quartz glass and Al 2 O 3 (manufactured by Nippon Ceratech), plasma etching was performed in the same manner as in Examples 1 to 19, the change in weight before and after etching was measured, and the etching rate was calculated. As a result, as shown in Table 4, the etching rate of quartz glass is 10.2 μm / hr, and the etching rate of Al 2 O 3 is 5.1 μm / hr, so that the sintered body has poor corrosion resistance. It was confirmed.
[0039]
[Table 4]
【The invention's effect】
As described above, according to the present invention, at least the portion exposed to the corrosive gas or the plasma thereof is constituted by dense fluoride ceramics having a porosity of 2% or less. Compared to quartz glass and alumina that have been used, the surface erosion rate due to the reaction with CF 4 gas is slow, and the corrosion resistance is extremely excellent. Therefore, it can be used very suitably for a member constituting a semiconductor manufacturing apparatus used in a corrosive atmosphere such as etching, impurity diffusion, and ion implantation process.
Claims (3)
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| JP01847199A JP4283925B2 (en) | 1999-01-27 | 1999-01-27 | Corrosion resistant material |
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| JP01847199A JP4283925B2 (en) | 1999-01-27 | 1999-01-27 | Corrosion resistant material |
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