JP3141280B2 - Method for producing glassy carbon member for silicon wafer plasma processing - Google Patents
Method for producing glassy carbon member for silicon wafer plasma processingInfo
- Publication number
- JP3141280B2 JP3141280B2 JP09038587A JP3858797A JP3141280B2 JP 3141280 B2 JP3141280 B2 JP 3141280B2 JP 09038587 A JP09038587 A JP 09038587A JP 3858797 A JP3858797 A JP 3858797A JP 3141280 B2 JP3141280 B2 JP 3141280B2
- Authority
- JP
- Japan
- Prior art keywords
- glassy carbon
- silicon wafer
- plasma processing
- carbon member
- electrode plate
- 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.)
- Expired - Fee Related
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シリコンウエハプ
ラズマ処理用ガラス状カーボン部材の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a glassy carbon member for plasma processing a silicon wafer.
【０００２】[0002]
【従来の技術】一般に、不溶不融の性質を持つ液状熱硬
化性樹脂の硬化物を不活性雰囲気中で炭化すると、ガラ
ス状カーボン材料が得られる。このガラス状カーボン材
料はガス不透過性に優れ、高硬度で、等方性の組織を有
する。さらに、このガラス状カーボン材料は、一般の炭
素材料が有する軽量、耐熱性、高電気伝導度、耐蝕性、
高熱伝導度を有し、すぐれた機械的強度や潤滑性の特性
に加えて、均質の特性や、摺動的に用いたとき切り粉等
の炭素粉末を生じない特性をも備えている。2. Description of the Related Art In general, when a cured product of a liquid thermosetting resin having insoluble and infusible properties is carbonized in an inert atmosphere, a glassy carbon material is obtained. This glassy carbon material has excellent gas impermeability, high hardness, and an isotropic structure. Furthermore, this glassy carbon material has the light weight, heat resistance, high electrical conductivity, corrosion resistance,
It has high thermal conductivity, excellent mechanical strength and lubricating properties, as well as uniform properties and properties that do not generate carbon powder such as cutting powder when used in a sliding manner.
【０００３】最近、このようなガラス状カーボン材料の
特性に着目して、ガラス状カーボン材料をプラズマエッ
チング用電極板として利用することが検討されている。Recently, attention has been paid to the use of the glassy carbon material as an electrode plate for plasma etching, paying attention to the characteristics of such a glassy carbon material.
【０００４】現在製品化されているガラス状カーボン
は、主として次の方法で製造されている。[0004] The glassy carbon currently produced is mainly manufactured by the following method.
【０００５】熱硬化性樹脂を原料とし、所定の形状を
した基盤上に、筆、噴霧、遠心法等により樹脂を薄く塗
布してから硬化させる操作を繰り返すことによって成形
した後、焼成を行う。[0005] A thermosetting resin is used as a raw material, and a resin is thinly applied on a base having a predetermined shape by a brush, spray, centrifugal method or the like, and then cured.
【０００６】骨材そのものを樹脂粉末とし、それを成
形した後に焼成を行い、ガラス状カーボンを得る。The aggregate itself is made into a resin powder, which is molded and then fired to obtain glassy carbon.
【０００７】従来、ピッチ等を原料とする易黒鉛化性カ
ーボン材料は、コークスを粉砕して粉末状のカーボン材
料を製造し、その粉末状のカーボン材料に適宜のバイン
ダーを添加して混練し、その混練した材料を成形して成
形素体を形成し、その成形素体を焼成し、更に焼成素体
を熱処理によって黒鉛化することにより製造されてい
た。Conventionally, a graphitizable carbon material using pitch or the like as a raw material is prepared by pulverizing coke to produce a powdery carbon material, adding an appropriate binder to the powdery carbon material, and kneading the mixture. The kneaded material is molded to form a green body, the green body is fired, and the fired body is graphitized by heat treatment.
【０００８】特開昭６２−２５２９４２号公報には、高
純度のガラス状カーボンからなるプラズマエッチング用
電極板が開示されている。その製法をのべると、液状の
フラン系樹脂、フェノール系樹脂、又はこれらの混合樹
脂、もしくは、これらに同一種類の硬化性樹脂粉末を添
加混合したものを平板状に形成してから硬化させて樹脂
板をつくり、ついでその樹脂板を不活性雰囲気下に８０
０℃で焼成炭化し、さらに必要に応じて３０００℃で黒
鉛化し、そのあと脱灰高純度処理をする。このようにし
て製造された電極板に、直径０．８ｍｍの貫通孔を数多
く２ｍｍ等の間隔で形成する。電極板の厚さは３ｍｍで
ある。電極板の物理特性は、かさ比重が１．４５ｇ／ｃ
ｍ3 、気孔率が３％、ショア硬さが７５、曲げ強さが５
８０ｋｇｆ／ｃｍ2 、弾性率が２４３０ｋｇｆ／ｃｍ2
である。Japanese Patent Application Laid-Open No. 62-252942 discloses an electrode plate for plasma etching made of high-purity glassy carbon. The production method is described as follows. A liquid furan-based resin, a phenol-based resin, or a mixed resin thereof, or a mixture obtained by adding and mixing the same kind of curable resin powder to a plate is formed and then cured to form a resin. Make a board and then put the resin board under inert atmosphere
It is calcined and carbonized at 0 ° C., and if necessary, graphitized at 3000 ° C., and then subjected to a demineralized high-purity treatment. A large number of through holes having a diameter of 0.8 mm are formed at intervals of 2 mm or the like in the electrode plate manufactured as described above. The thickness of the electrode plate is 3 mm. The physical properties of the electrode plate are as follows: bulk specific gravity is 1.45 g / c.
m 3 , porosity 3%, Shore hardness 75, bending strength 5
80 kgf / cm 2 , elastic modulus 2430 kgf / cm 2
It is.
【０００９】[0009]
【発明が解決しようとする課題】上述の製造法によれ
ば、成形時の空隙や、熱処理時の揮発成分の散逸等によ
り比較的大きな径（約２μｍ）の多数の気孔が発生す
る。According to the above-mentioned manufacturing method, a large number of pores having a relatively large diameter (about 2 μm) are generated due to voids during molding and dissipation of volatile components during heat treatment.
【００１０】また、骨材粒子の大きさやバインダーの種
類、製造工程等によって気孔の大きさや分布が異なる。
そのため、気孔が関与した物性は非常に複雑なものにな
る。The size and distribution of pores vary depending on the size of the aggregate particles, the type of binder, the manufacturing process, and the like.
Therefore, physical properties involving pores become extremely complicated.
【００１１】従来のガラス状カーボン製のプラズマエッ
チング用電極板を電子顕微鏡で観察すると、第７図に示
されているように、表面に大きな径（約２μｍ）の開気
孔がある。なお電極板の内部にも大きな径（約２μｍ）
の閉気孔が存在している。When a conventional glass etching electrode plate made of glassy carbon is observed with an electron microscope, as shown in FIG. 7, there are large open pores (about 2 μm) on the surface as shown in FIG. The inside of the electrode plate has a large diameter (about 2μm)
Closed pores exist.
【００１２】このようにガラス状カーボンに特有の開気
孔により、比表面積が増大し、酸化特性と強度が低下す
る現象が派生する。[0012] As described above, due to the open pores specific to glassy carbon, the specific surface area is increased, and a phenomenon in which the oxidation characteristics and strength are reduced is induced.
【００１３】また、開気孔のみならず電極板に閉気孔が
存在すると、研磨したとき内部の閉気孔が表面に現れて
開気孔となり、上記問題点と同様の現象が派生する。Further, if closed pores exist not only in the open pores but also in the electrode plate, the internal closed pores appear on the surface when polished and become open pores, and the same phenomenon as the above-mentioned problem occurs.
【００１４】従来の技術として詳述したの方法は、こ
の開気孔および閉気孔が焼成後の樹脂の積層部分に多数
存在する不都合があり、の方法は、樹脂粉体を使用す
るため、粒子間に粒界が存在し、機械的強度および気孔
率等の特性が通常のガラス状カーボンより劣り、使用中
又口洗浄中にカーボン粒子が脱落し易いという欠点があ
る。The method described in detail as the prior art has the disadvantage that a large number of open pores and closed pores are present in the laminated portion of the fired resin. There are disadvantages in that there are grain boundaries, the properties such as mechanical strength and porosity are inferior to those of ordinary glassy carbon, and carbon particles easily fall off during use and mouth washing.
【００１５】このカーボン粒子脱落現象を防止するため
に、電極板の表面にガラス状カーボン膜や熱分解炭素膜
を形成する方法が提案されているが、被膜自体の機械的
強度が弱く、被膜の剥離の問題点があった。In order to prevent the carbon particle falling-off phenomenon, a method of forming a glassy carbon film or a pyrolytic carbon film on the surface of an electrode plate has been proposed. However, the mechanical strength of the coating itself is weak, and the There was a problem of peeling.
【００１６】本発明の目的は、プラズマの安定性がよ
く、耐用性にすぐれたシリコンウエハプラズマ処理用ガ
ラス状カーボン部材の製造方法を提供することである。An object of the present invention is to provide a method for producing a glass-like carbon member for silicon wafer plasma processing, which has excellent plasma stability and excellent durability.
【００１７】[0017]
【課題を解決するための手段】本発明の要旨は特許請求
の範囲の請求項１〜６のいずれか１項に記載したシリコ
ンウエハプラズマ処理用ガラス状カーボン部材の製造方
法にある。The gist of the present invention resides in a method of manufacturing a glassy carbon member for silicon wafer plasma processing according to any one of claims 1 to 6 of the present invention.
【００１８】[0018]
【発明の実施の形態】本発明の方法によって製造される
カーボン部材の典型例は、プラズマエッチング用電極板
である。それは高純度のガラス状カーボンからなる厚さ
２ｍｍ以上の板状体であり、表面及び内部組織に粒界が
実質的に存在せず、最大気孔径が１μｍ以下である。DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical example of a carbon member manufactured by the method of the present invention is an electrode plate for plasma etching. It is a plate-like body made of high-purity glassy carbon and having a thickness of 2 mm or more, having substantially no grain boundaries on its surface and internal structure, and having a maximum pore diameter of 1 μm or less.
【００１９】好ましくは、ガラス状カーボンの不純物含
有率は５ｐｐｍ以下にし、開気孔率は０．２％以下に
し、最大気孔径は０．５μｍ以下にする。さらに開気孔
率は０．０１％、最大気孔径０．１μｍ以下にするのが
最善である。Preferably, the glassy carbon has an impurity content of 5 ppm or less, an open porosity of 0.2% or less, and a maximum pore size of 0.5 μm or less. Further, it is best that the open porosity is 0.01% and the maximum pore diameter is 0.1 μm or less.
【００２０】[0020]
【実施例】第１〜２図は本発明により製造されるガラス
状カーボン製のプラズマエッチング用電極板の一例を示
している。電極板１０は全体が円板になっていて、中心
の円形の開孔部１１に多数の小さな貫通孔１３（第３
図）が形成されており、周辺には一定間隔に８個の大き
な貫通孔１４が形成されている。1 and 2 show an example of an electrode plate for plasma etching made of glassy carbon manufactured according to the present invention. The electrode plate 10 is a disk as a whole, and a large number of small through holes 13 (third holes) are formed in a central circular opening 11.
) Are formed, and eight large through holes 14 are formed at regular intervals in the periphery.
【００２１】貫通孔１４はプラズマエッチング装置への
取付けを目的としたもので、小径部と大径部からなり、
２段形状になっている。The through hole 14 is intended to be attached to a plasma etching apparatus, and has a small diameter portion and a large diameter portion.
It has a two-stage shape.
【００２２】第２図にごく一部が例示されているが、開
孔部１１の全体には多数の貫通孔１３が密に形成されて
いる。これらの貫通孔１３はエッチングガスを均一に流
すことによりウエハを均一にエッチングすることを目的
としたものであり、第３図に示されているように、上下
左右にわたって一定間隔毎に配置されており、互いに隣
接する３つの貫通孔１３が正三角形の頂点に位置するよ
うになっている。Although only a part is illustrated in FIG. 2, a large number of through holes 13 are densely formed in the entire opening portion 11. These through-holes 13 are intended to uniformly etch the wafer by uniformly flowing an etching gas, and are arranged at regular intervals vertically and horizontally as shown in FIG. The three through holes 13 adjacent to each other are located at the vertices of an equilateral triangle.
【００２３】電極板１０の外径は１０インチであり、開
孔部１１の直径は処理ウエハ（図示せず）の直径に対応
させて８インチに設定されている。もちろん、この他の
態様を採用してもよい。例えば、電極板１０の外径を１
２インチにし、開孔部１１の直径を１０インチにしても
よい。開孔部１１の直径は処理するウエハの直径と同じ
かそれよりも大きくするのが好ましい。The outer diameter of the electrode plate 10 is 10 inches, and the diameter of the opening 11 is set to 8 inches corresponding to the diameter of a processing wafer (not shown). Of course, other modes may be adopted. For example, if the outer diameter of the electrode plate 10 is 1
The diameter of the opening 11 may be 10 inches. The diameter of the opening 11 is preferably equal to or larger than the diameter of the wafer to be processed.
【００２４】開孔部１１内の貫通孔１３の配置密度は第
３図の例で約９８個／ｃｍ2 にするのが好ましい。この
図示例においては、直径８インチの開孔部１１の中に貫
通孔１３が１７３３個形成されている。各貫通孔１３の
直径は０．５〜１ｍｍにするのが好ましい。The arrangement density of the through holes 13 in the opening 11 is preferably about 98 holes / cm 2 in the example of FIG. In the illustrated example, 1733 through holes 13 are formed in the opening 11 having a diameter of 8 inches. The diameter of each through hole 13 is preferably set to 0.5 to 1 mm.
【００２５】なお、図示例における貫通孔１３の配置密
度は開孔部１１全体で均一な分布になっているが、本発
明はその例に限られない。例えば、配置密度は開孔部１
１の中心部を密にし、外周部を疎にしてもよい。Although the arrangement density of the through holes 13 in the illustrated example has a uniform distribution over the entire opening portion 11, the present invention is not limited to this example. For example, the arrangement density is
1 may be made denser at the center and sparse at the outer periphery.
【００２６】電極板１０の厚みは２ｍｍ以上にする。そ
の理由は機械的強度を増大させ、耐用寿命を向上させる
ためである。図示例の電極板１０は３ｍｍの厚みになっ
ている。The thickness of the electrode plate 10 is 2 mm or more. The reason is to increase the mechanical strength and improve the service life. The electrode plate 10 in the illustrated example has a thickness of 3 mm.
【００２７】電極板１０は、従来の不純物含有量の十分
の一から百分の一以下（たとえば５ｐｐｍ以下）に抑制
したガラス状カーボンからなる。The electrode plate 10 is made of glassy carbon in which the impurity content is reduced to one tenth to one hundredth or less (for example, 5 ppm or less) in the related art.
【００２８】本発明の好ましい製造法の概略を以下に説
明する。An outline of a preferred production method of the present invention will be described below.
【００２９】液状熱硬化性樹脂に有機スルホン酸を少量
添加して常温で重合させる工程をくり返す。しかるの
ち、重合させた樹脂を型に注入して円板状に成形し、ゆ
っくり昇温させていって硬化させる。そのように硬化さ
せた円板の中心部に直径０．８ｍｍの多数の貫通孔を設
ける。そのあと、円板を徐々に緩やかに昇温していって
８００〜１２００℃で炭化焼成する。それを表面加工し
て、さらに２０００〜２５００℃で純化処理する。The step of adding a small amount of organic sulfonic acid to the liquid thermosetting resin and polymerizing at room temperature is repeated. Thereafter, the polymerized resin is poured into a mold, molded into a disk shape, and slowly heated to cure. A large number of through-holes having a diameter of 0.8 mm are provided in the center of the disk thus hardened. Thereafter, the temperature of the disk is gradually and gradually increased, and carbonization and firing are performed at 800 to 1200 ° C. It is subjected to a surface treatment and further purified at 2000 to 2500 ° C.
【００３０】本発明の方法により製造される電極板を構
成するガラス状カーボンは、出発原料として流動性のあ
る液体状熱硬化性樹脂を使用して作るのが好ましい。そ
うすることにより、１μｍ以上の気孔を含まず、開気孔
率が０．２％以下であるガラス状カーボン材料を得やす
くなるからである。The glassy carbon constituting the electrode plate produced by the method of the present invention is preferably produced using a liquid, liquid thermosetting resin as a starting material. By doing so, it becomes easy to obtain a glassy carbon material containing no pores of 1 μm or more and having an open porosity of 0.2% or less.
【００３１】第４〜８図は電子顕微鏡により観察された
電極板の表面組織を示すものである。FIGS. 4 to 8 show the surface texture of the electrode plate observed by an electron microscope.
【００３２】第４図の電子顕微鏡写真に示されている電
極板には約０．２μｍ以下の開気孔がごく少し存在する
だけである。この例の開気孔率は０．１％である。 出
発原料として流動性のある熱硬化性樹脂を使用すると、
粒界が生じない。骨材そのものを樹脂粉末状とし、成形
後に焼成した場合、粒子間に粒界が存在し易く、機械的
強度および気孔率等の特性が劣化する。The electrode plate shown in the electron micrograph of FIG. 4 has only a few open pores of about 0.2 μm or less. The open porosity of this example is 0.1%. When a fluid thermosetting resin is used as a starting material,
No grain boundaries occur. When the aggregate itself is formed into a resin powder and fired after molding, grain boundaries are likely to exist between particles, and properties such as mechanical strength and porosity are deteriorated.
【００３３】液状熱硬化性樹脂は、硬化させてから、不
活性雰囲気（酸素を含まず、通常、ヘリウム、アルゴ
ン、窒素、水素、ハロゲン等の不活性ガスの中の少なく
とも一種の気体よりなる雰囲気下、あるいは減圧または
真空下、または大気を遮断した状態の雰囲気）中で緩や
かな昇温速度で炭化焼成する。After the liquid thermosetting resin is cured, it is cured in an inert atmosphere (an atmosphere containing no oxygen and usually made of at least one kind of inert gas such as helium, argon, nitrogen, hydrogen, halogen, etc.). Under a reduced pressure, in a vacuum, or in an atmosphere in which the atmosphere is shut off) at a moderate heating rate.
【００３４】ガラス状カーボンの開気孔率は０．２％以
下にするのが好ましい。開気孔率が０．２ｗｔ％を超え
ると、ガラス状カーボンをプラズマエッチング用の電極
板として用いた場合、電極板がエッチングにより消耗
し、閉気孔が露出し、表面積が大きくなって、エッチン
グとカーボン粒子の脱落が加速される。その結果、ライ
フが短くなる。さらに、カーボン粒子が脱落すると、そ
れが半導体デバイス用シリコンウエハに付着し、ウエハ
の物理特性を劣化させる。それにより、歩留が低下す
る。The open porosity of the glassy carbon is preferably set to 0.2% or less. When the open porosity exceeds 0.2 wt%, when glassy carbon is used as an electrode plate for plasma etching, the electrode plate is consumed by etching, closed pores are exposed, the surface area increases, and etching and carbon Particle shedding is accelerated. As a result, the life is shortened. Furthermore, when the carbon particles fall off, they adhere to the silicon wafer for semiconductor devices, and deteriorate the physical properties of the wafer. Thereby, the yield decreases.
【００３５】液状熱硬化性樹脂としては、フラン樹脂、
フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹
脂、ユリア樹脂、メラミン樹脂、アルキッド樹脂、キシ
レン樹脂等を挙げることができる。このような樹脂を単
独またはブレンドまたは変成することによって使用す
る。その中でも変成フラン樹脂が良い。As the liquid thermosetting resin, furan resin,
Phenol resins, epoxy resins, unsaturated polyester resins, urea resins, melamine resins, alkyd resins, xylene resins and the like can be mentioned. Such resins are used alone or by blending or modifying. Among them, modified furan resin is preferable.
【００３６】実験例１〜３ フリフリルアルコールにｐ−トルエンスルホン酸を０．
４重量部の爆発限界まで攪拌混合して重合し、１０００
〜４０００ｃｐ（センチポイズ）の粘性を有する流動性
ポリマーを得た。 Experimental Examples 1 to 3 p-toluenesulfonic acid was added to furfuryl alcohol in 0.1 ml.
Polymerized by stirring and mixing to the explosion limit of 4 parts by weight, 1000
A flowable polymer having a viscosity of ~ 4000 cp (centipoise) was obtained.
【００３７】生成フリフリルアルコール重合液を脱泡処
理した後、成形型中で直径３００ｍｍ、厚み１０ｍｍの
円板に成形し、乾燥器中で１℃／ｈｒの昇温速度で硬化
させた。After defoaming the produced furfuryl alcohol polymer solution, it was molded into a disk having a diameter of 300 mm and a thickness of 10 mm in a molding die, and was cured in a dryer at a heating rate of 1 ° C./hr.
【００３８】得られた硬化体を窒素雰囲気中で２℃／ｈ
の昇温速度で１０００℃まで昇温して焼成し、最後に２
３００℃で純化処理を行い、ガラス状カーボンとした。The obtained cured product is heated at 2 ° C./h in a nitrogen atmosphere.
The temperature is raised to 1000 ° C. at a heating rate of
Purification was performed at 300 ° C. to obtain glassy carbon.
【００３９】比較例１〜３ フラン樹脂にｐ−トルエンスルホン酸の酸触媒を添加し
た後に脱泡処理し、それを成形した後に２００℃まで緩
やかに昇温して硬化させた。こうして得られた硬化体を
粉砕し、平均粒径３０〜５０μｍの樹脂粉末を得た。こ
の樹脂粉末に同種のフラン樹脂を混合し、その混合物を
脱泡処理した後に直径２００ｍｍ、厚み３ｍｍの円板の
形状に成形し、しかるのち硬化させた。得られた硬化体
を窒素雰囲気中で２℃／ｈの昇温速度で１０００℃まで
昇温させて焼成し、最後に２３００℃で純化処理を行
い、ガラス状カーボンとした。 Comparative Examples 1 to 3 An acid catalyst of p-toluenesulfonic acid was added to a furan resin, followed by defoaming treatment. After molding, the mixture was cured by slowly raising the temperature to 200 ° C. The cured product thus obtained was pulverized to obtain a resin powder having an average particle size of 30 to 50 μm. The same type of furan resin was mixed with this resin powder, and the mixture was defoamed, molded into a disk having a diameter of 200 mm and a thickness of 3 mm, and then cured. The obtained cured body was heated to 1000 ° C. at a rate of 2 ° C./h in a nitrogen atmosphere and calcined. Finally, a purification treatment was performed at 2300 ° C. to obtain glassy carbon.
【００４０】表１は、実験例１〜３および比較例１〜３
のガラス状カーボンについて、開気孔率、ライフおよび
ガス放出量を示す。Table 1 shows Experimental Examples 1 to 3 and Comparative Examples 1 to 3.
The open porosity, life, and amount of released gas are shown for the glassy carbon.
【００４１】円板形のガラス状カーボン電極板にシリコ
ンウエハを載置し、ＣＦ4 、Ａｒ、Ｏ2 の混合ガスを流
し、プラズマを発生させてシリコンウエハをエッチング
した。そのとき、流した酸化性ガスと発生したプラズマ
によりガラス状カーボンもエッチングされ消耗した。ガ
ラス状カーボン電極板の初期厚みを加工して３ｍｍに統
一し、残留厚みが０．８ｍｍとなる時点をライフエンド
とした。A silicon wafer was placed on a disk-shaped glassy carbon electrode plate, a mixed gas of CF 4 , Ar, and O 2 was flowed to generate plasma, and the silicon wafer was etched. At this time, the glassy carbon was also etched and consumed by the flowing oxidizing gas and the generated plasma. The initial thickness of the glassy carbon electrode plate was processed and unified to 3 mm, and the time when the residual thickness became 0.8 mm was defined as the life end.
【００４２】また、表１において、ガス放出量は、９５
０℃に加熱したときにガラス状カーボンの表面に吸着し
ていたＣＯ2 、Ｈ2 、ＣＯ等のガスが放出された量を示
す。In Table 1, the amount of gas released was 95
It indicates the amount of released gas such as CO 2 , H 2 , CO adsorbed on the surface of the glassy carbon when heated to 0 ° C.
【００４３】表１に示すように、本発明のガラス状カー
ボン電極板は比較例と比べて酸素含有条件下でライフが
格段に向上した。As shown in Table 1, the life of the glassy carbon electrode plate of the present invention was remarkably improved under the oxygen-containing condition as compared with the comparative example.
【００４４】本実験においては、電極板の厚みが３ｍｍ
から０．８ｍｍになったところでライフエンドとした
が、実際には比較例のガラス状カーボン電極板には開気
孔が多く存在するため、ガラス状カーボン電極板のエッ
チングのされ方が均一ではなく、電子顕微鏡で観察する
と、第８図に示すように著しく凹凸が生じる。そのた
め、シリコンウエハをエッチングするために発生させる
プラズマが不安定となり、シリコンウエハのエッチング
速度がシリコンウエハの各部で異なる。それゆえ、実際
にはエッチング用ガラス状カーボン電極板として用いた
時のライフは、表１に示したライフよりもさらに短いも
のになると思われる。In this experiment, the thickness of the electrode plate was 3 mm.
Was 0.8 mm from the end, but in reality, the glassy carbon electrode plate of the comparative example has many open pores, so the way the glassy carbon electrode plate is etched is not uniform, Observation with an electron microscope reveals significant irregularities as shown in FIG. For this reason, the plasma generated for etching the silicon wafer becomes unstable, and the etching rate of the silicon wafer differs in each part of the silicon wafer. Therefore, it is considered that the life when actually used as a glassy carbon electrode plate for etching is shorter than the life shown in Table 1.
【００４５】また、現在の小さな口径のシリコンウエハ
では、エッチング速度のバラツキが規定内に入っている
が、今後の大きな口径のシリコンウエハのエッチンング
プロセスを考えた場合、比較例に生じるエッチング速度
のバラツキは非常に大きな問題になると思われる。In addition, the variation in the etching rate of the current silicon wafer having a small diameter is within the specified range. However, considering the etching process of a silicon wafer having a large diameter in the future, the etching rate generated in the comparative example is considered. Variations are likely to be a huge problem.
【００４６】さらに、電極板が第８図に示すように凹凸
状にエッチングされると、パーティクルが発生し易い。
現在の半導体産業では集積度が４Ｍから１６Ｍへと移
り、パターンのエッチングの線幅がサブミクロンへと進
んだ。そのためシリコンウエハの歩留りに一番影響を与
えているのは０．１〜０．３μｍのパーティクルであ
る。このようなパーティクルを減少させることがシリコ
ンウエハの歩留りに大きく寄与することになる。このこ
とから比較例のガラス状カーボンでは使用初期では問題
があまり生じないが、使用時間が経過するに伴い、表面
が凹凸状にエッチングされ、それにより表面が荒れ、パ
ーティクルを発生する。Further, when the electrode plate is etched into an uneven shape as shown in FIG. 8, particles are easily generated.
In the current semiconductor industry, the degree of integration has moved from 4M to 16M, and the line width of pattern etching has advanced to submicron. Therefore, the particles that most affect the yield of the silicon wafer are particles of 0.1 to 0.3 μm. Reducing such particles will greatly contribute to the yield of silicon wafers. For this reason, the glassy carbon of the comparative example does not cause much problem in the early stage of use, but the surface is etched into an uneven shape as the use time elapses, thereby roughening the surface and generating particles.
【００４７】また、ガス放出量が多いことから、使用時
に吸着ガスが放出され、発生しているプラズマとともに
高純度のシリコンウエハが悪影響を受ける。Further, since the amount of gas released is large, the adsorbed gas is released during use, and the high-purity silicon wafer is adversely affected together with the generated plasma.
【００４８】第５〜６図の電子顕微鏡写真に示されてい
るように、本発明の電極板は、エッチングのされ方が均
一で、比較例のようにエッチング後に大きな凹凸が生じ
ない。As shown in the electron micrographs of FIGS. 5 and 6, the electrode plate of the present invention is uniformly etched and does not have large irregularities after the etching as in the comparative example.
【図１】この発明により製造されるプラズマエッチング
用電極板の概略図。FIG. 1 is a schematic view of an electrode plate for plasma etching manufactured according to the present invention.
【図２】第１図の２−２線に沿った概略断面図。FIG. 2 is a schematic sectional view taken along line 2-2 of FIG. 1;
【図３】第１図の開孔部の一部分を拡大して示した平面
図。FIG. 3 is an enlarged plan view showing a part of the opening shown in FIG. 1;
【図４】本発明により製造されるプラズマエッチング用
電極板の一例の表面のセラミック組織を１０００倍の倍
率で示す電子顕微鏡写真。FIG. 4 is an electron micrograph showing the ceramic structure on the surface of an example of the electrode plate for plasma etching manufactured by the present invention at a magnification of 1000 times.
【図５】本発明方法により製造されるプラズマエッチン
グ用電極板のプラズマエッチング後の表面のセラミック
組織を１０００倍の倍率で示す電子顕微鏡写真。FIG. 5 is an electron micrograph showing the ceramic structure of the surface of the electrode plate for plasma etching manufactured by the method of the present invention after plasma etching at a magnification of 1000 times.
【図６】本発明方法により製造されるプラズマエッチン
グ後の表面のセラミック組織を１５０００倍の倍率で示
す電子顕微鏡写真。FIG. 6 is an electron micrograph showing the ceramic structure of the surface after plasma etching manufactured by the method of the present invention at a magnification of 15,000.
【図７】従来のプラズマエッチング用電極板の使用前の
表面のセラミック組織を１０００倍の倍率で示す電子顕
微鏡写真。FIG. 7 is an electron micrograph showing a ceramic structure of a surface of a conventional electrode plate for plasma etching before use at a magnification of 1000 times.
【図８】従来のプラズマエッチング用電極板の使用後の
表面のセラミック組織を１０００倍の倍率で示す電子顕
微鏡写真。FIG. 8 is an electron micrograph showing the ceramic structure of the surface of the conventional electrode plate for plasma etching after use at a magnification of 1000 times.
１０ 電極板 １１ 開孔部 １３ 貫通孔 １４ 貫通孔 DESCRIPTION OF SYMBOLS 10 Electrode plate 11 Opening part 13 Through hole 14 Through hole
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 外谷 栄一 山形県西置賜郡小国町大字小国町378番 地 東芝セラミックス株式会社 小国製 造所内 (72)発明者 佐々木 泰実 山形県西置賜郡小国町大字小国町378番 地 東芝セラミックス株式会社 小国製 造所内 (72)発明者 伊藤 和男 神奈川県秦野市曽屋30 東芝セラミック ス株式会社 中央研究所内 (72)発明者 目黒 和教 山形県西置賜郡小国町大字小国町378番 地 東芝セラミックス株式会社 小国製 造所内 (56)参考文献 特開 平３−119723（ＪＰ，Ａ) 特開 昭60−171206（ＪＰ，Ａ) 特開 昭62−36011（ＪＰ，Ａ) 特開 昭63−76959（ＪＰ，Ａ) 特公 昭64−321（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/52 H01L 21/3065 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Eiichi Toya 378 Oguni-cho, Oguni-machi, Nishiokitama-gun, Yamagata Prefecture Inside the Oguni Plant, Toshiba Ceramics Co., Ltd. (72) Inventor Yasumi Sasaki Ogunimachi, Nishiokitama-gun, Yamagata Prefecture 378 Oguni-machi Toshiba Ceramics Co., Ltd.Oguni Factory (72) Inventor Kazuo Ito 30 Soya, Hadano-shi, Kanagawa Toshiba Ceramics Co., Ltd.Central Research Laboratory (72) Inventor Kazunori Meguro Ogunimachi, Ogunimachi, Nishiokitama-gun, Yamagata Prefecture 378, Toshiba Ceramics Co., Ltd. Oguni Works (56) References JP-A-3-119723 (JP, A) JP-A-60-171206 (JP, A) JP-A-62-36011 (JP, A) JP-A-63-76959 (JP, A) JP-B-64-321 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) C04B 35/52 H01L 21/3065
Claims (6)
量づつ添加して重合させる工程を繰り返すことで、前記
有機スルホン酸を混合して１０００〜４０００センチポ
イズの粘性を有する流動体ポリマーを形成し、脱泡処理
後、所望形状に成形し、硬化後、焼成、純化処理を順次
行うことを特徴とするシリコンウエハプラズマ処理用ガ
ラス状カーボン部材の製造方法。1. A liquid polymer having a viscosity of 1,000 to 4,000 centipoise is formed by mixing the organic sulfonic acid by repeating a process of adding an organic sulfonic acid little by little to a liquid thermosetting resin and polymerizing the same. A method for producing a glassy carbon member for silicon wafer plasma processing, comprising: performing defoaming, forming into a desired shape, curing, firing, and purifying sequentially.
ン酸を合計で爆発限界まで混合することを特徴とする請
求項１に記載のシリコンウエハプラズマ処理用ガラス状
カーボン部材の製造方法。2. The method for producing a glassy carbon member for silicon wafer plasma processing according to claim 1, wherein the organic sulfonic acid is mixed with the liquid thermosetting resin in total up to an explosion limit.
コールであり、かつ上記有機スルホン酸がｐ−トリエン
スルホン酸であることを特徴とする請求項１または２に
記載のシリコンウエハプラズマ処理用ガラス状カーボン
部材の製造方法。3. The glass for processing a silicon wafer plasma according to claim 1, wherein the liquid thermosetting resin is furfuryl alcohol, and the organic sulfonic acid is p-trienesulfonic acid. Of manufacturing a carbon member.
ス状カーボン部材がプラズマエッチング用ガラス状カー
ボン電極板であることを特徴とする請求項１〜３のいず
れか１項に記載のシリコンウエハプラズマ処理用ガラス
状カーボン部材の製造方法。4. The glass for silicon wafer plasma processing according to claim 1, wherein the glassy carbon member for silicon wafer plasma processing is a glassy carbon electrode plate for plasma etching. Of manufacturing a carbon member.
われることを特徴とする請求項１〜４のいずれか１項に
記載のシリコンウエハプラズマ処理用ガラス状カーボン
部材の製造方法。5. The method for producing a glassy carbon member for silicon wafer plasma processing according to claim 1, wherein the curing is performed at a temperature increasing rate of 1 ° C./hr.
昇温速度で行なわれることを特徴とする請求項１〜５の
いずれか１項に記載のシリコンウエハプラズマ処理用ガ
ラス状カーボン部材の製造方法。6. The glassy carbon member for silicon wafer plasma processing according to claim 1, wherein the firing is performed at a temperature increase rate of 2 ° C./hr up to 1000 ° C. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09038587A JP3141280B2 (en) | 1997-02-07 | 1997-02-07 | Method for producing glassy carbon member for silicon wafer plasma processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09038587A JP3141280B2 (en) | 1997-02-07 | 1997-02-07 | Method for producing glassy carbon member for silicon wafer plasma processing |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8502890A Division JPH0814033B2 (en) | 1990-04-02 | 1990-04-02 | Electrode plate for plasma etching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09188566A JPH09188566A (en) | 1997-07-22 |
| JP3141280B2 true JP3141280B2 (en) | 2001-03-05 |
Family
ID=12529440
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014159696A (en) * | 2013-02-20 | 2014-09-04 | Clion Co Ltd | Fitting structure of alc panel and fitting method of alc panel |
-
1997
- 1997-02-07 JP JP09038587A patent/JP3141280B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014159696A (en) * | 2013-02-20 | 2014-09-04 | Clion Co Ltd | Fitting structure of alc panel and fitting method of alc panel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09188566A (en) | 1997-07-22 |
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