JP5876259B2 - Method for manufacturing member covered with aluminum nitride film - Google Patents
Method for manufacturing member covered with aluminum nitride film Download PDFInfo
- Publication number
- JP5876259B2 JP5876259B2 JP2011220004A JP2011220004A JP5876259B2 JP 5876259 B2 JP5876259 B2 JP 5876259B2 JP 2011220004 A JP2011220004 A JP 2011220004A JP 2011220004 A JP2011220004 A JP 2011220004A JP 5876259 B2 JP5876259 B2 JP 5876259B2
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- aluminum nitride
- fluorine
- film
- vapor deposition
- 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
Links
Description
本発明は、フッ素系の腐食性ガスに対する耐性に優れた部材に関し、特に、放熱用基板や半導体デバイスの製造工程に好適に使用される静電チャック、ウエハを加熱するセラミックスヒーター、半導体製造装置内で使用される円板、シャワープレート及びリング形状の部材等の、フッ素系腐食性ガスに対する耐性に優れた部材の製造方法に関する。 The present invention relates to a member excellent in resistance to a fluorine-based corrosive gas, and in particular, an electrostatic chuck, a ceramic heater for heating a wafer, and a semiconductor manufacturing apparatus that are preferably used in a manufacturing process of a heat dissipation substrate or a semiconductor device. The present invention relates to a method for producing a member excellent in resistance to a fluorine-based corrosive gas , such as a disc, a shower plate, and a ring-shaped member used in the above.
半導体製造工程において、ＣＶＤ装置を用いてシリコンウエハ上に酸化膜や配線のメタル膜等を形成させる場合、ウエハ以外の余分な箇所にも膜成分が付着する。この余分に付着した膜成分を除去するために行われる定期的なセルフクリーニングのために、或いは、エッチング装置を用いて熱エッチングやプラズマエッチングにより形成した膜を除去する際に、腐蝕性の高い、ＮＦ3、ＣＦ4、ＣｌＦ3 等のフッ素系ガスが用いられている。 In a semiconductor manufacturing process, when a CVD apparatus is used to form an oxide film, a metal film of wiring, or the like on a silicon wafer, film components adhere to extra portions other than the wafer. Highly corrosive for periodic self-cleaning performed to remove this excessively adhered film component, or when removing a film formed by thermal etching or plasma etching using an etching apparatus, A fluorine-based gas such as NF 3 , CF 4 , or ClF 3 is used.
このような高腐蝕性ガス中という厳しい条件下で使用する、ウエハを載置するサセプタやクランプリング、フォーカスリング等の、半導体装置を構成する部材としては、従来、シリコン（Ｓｉ）や石英ガラス、炭化珪素等が、用途に応じて選択され適用されてきた。しかしながら、従来用いられているこれらの材料には、以下のような種々の問題があった。 As a member constituting a semiconductor device, such as a susceptor, a clamp ring, and a focus ring for mounting a wafer, which are used under such severe conditions as highly corrosive gas, conventionally, silicon (Si), quartz glass, Silicon carbide or the like has been selected and applied depending on the application. However, these conventionally used materials have the following various problems.
例えば、石英ガラスの場合には、反応性の高いフッ素系ガスの存在下においては、フッ化珪素等の反応生成物の蒸気圧が高く、気体となって揮散するため、腐蝕が連続的に進行し部材の消失が生じるという欠点があった。 For example, in the case of quartz glass, in the presence of a highly reactive fluorine-based gas, the vapor pressure of reaction products such as silicon fluoride is high and vaporizes as a gas, so that corrosion proceeds continuously. However, there has been a drawback that the disappearance of the members occurs.
また炭化珪素の場合には、基本的には石英ガラスよりも耐蝕性が優れているものの、半導体製造装置用として使用する炭化珪素は、主にシリコン含浸炭化珪素であるため、シリコン部がフッ素系ガスとの反応により消失する。このため、構造組織が緻密化された基材から炭化珪素が離脱し易く、半導体不良の原因となるパーティクルを発生し易くなるという欠点があった。 In addition, in the case of silicon carbide, although the corrosion resistance is basically better than that of quartz glass, silicon carbide used for semiconductor manufacturing equipment is mainly silicon-impregnated silicon carbide. Disappears upon reaction with gas. For this reason, there is a drawback in that silicon carbide is easily detached from a substrate having a dense structure, and particles that cause a semiconductor defect are easily generated.
一方、窒化アルミニウム焼結体の場合には、上記材料に比べて耐蝕性に優れているので、最近は、窒化アルミニウム焼結体部材が、特に半導体製造工程で使用される耐蝕部材として多く採用されるようになった。しかしながら、窒化アルミニウム焼結体を成型体とした場合には、微量の焼結助剤を含有すると共に、製法特有の粒界が存在する。したがって、長時間フッ素系ガスに曝されると、助剤部分や粒界部分付近が選択的にエッチングされ、上記石英や炭化珪素の場合ほどではないものの、徐々に劣化するため、長時間使用すると前記パーティクルを発生し易くなると言う欠点があった。 On the other hand, in the case of an aluminum nitride sintered body, since it is superior in corrosion resistance compared to the above materials, recently, an aluminum nitride sintered body member has been widely adopted as a corrosion resistant member used particularly in a semiconductor manufacturing process. It became so. However, when the aluminum nitride sintered body is formed into a molded body, it contains a trace amount of a sintering aid and has grain boundaries peculiar to the manufacturing method. Therefore, when exposed to fluorine-based gas for a long time, the auxiliary part and the vicinity of the grain boundary part are selectively etched, and although it is not as much as in the case of the above-mentioned quartz or silicon carbide, it gradually deteriorates. There is a drawback that the particles are easily generated.
近年、前記したような従来の欠点を改善するために、窒化アルミニウム焼結体の表面にフッ化アルミニウム膜を設けて、フッ素系腐蝕性ガスに対する耐蝕性を改善することが提案された（特許文献１）。しかしながらこの場合には、窒化アルミニウム焼結体（セラミックス）基材の熱膨張率が4×10-6/℃であるのに対し、フッ化アルミニウムの熱膨張率は1.9×10-5/℃と５倍程度の差があるために、フッ化アルミニウム膜にクラックが発生し、ヒートサイクルを伴う使用においては、酷い場合には、フッ化アルミニウム膜が剥がれるという欠点があった。 In recent years, in order to improve the conventional defects as described above, it has been proposed to provide an aluminum fluoride film on the surface of an aluminum nitride sintered body to improve the corrosion resistance against a fluorine-based corrosive gas (Patent Literature). 1). However, in this case, the thermal expansion coefficient of the aluminum nitride sintered body (ceramics) substrate is 4 × 10 −6 / ° C., whereas the thermal expansion coefficient of aluminum fluoride is 1.9 × 10 −5 / ° C. Since there is a difference of about 5 times, cracks occur in the aluminum fluoride film, and there is a drawback that the aluminum fluoride film is peeled off in severe cases when used with a heat cycle.
したがって本発明の第１の目的は、フッ素系腐蝕性ガスに対する耐蝕性に優れる部材の製造方法を提供することにある。
本発明の第２の目的は、フッ素系腐蝕性ガスに対する耐蝕性に優れる部材だけでなく、ヒートサイクルを伴う使用にも十分耐え、熱膨張差によるクラックの発生や剥離が生じ難い、基材との密着性に優れた被覆膜を有する部材を提供することにある。
Accordingly, a first object of the present invention is to provide a method for producing a member having excellent corrosion resistance against a fluorine-based corrosive gas .
The second object of the present invention is not only a member excellent in corrosion resistance against fluorine-based corrosive gas , but also sufficiently withstands use with a heat cycle, and is less likely to cause cracking or peeling due to a difference in thermal expansion. An object of the present invention is to provide a member having a coating film having excellent adhesion.
本発明者らは、上記の目的を達成するために鋭意検討した結果、基材を被覆する膜として、被覆膜表面から内部に向けて熱膨張率が徐々に変化する耐蝕性の窒化アルミニウム膜を使用した場合には、該膜にクラック等が発生し難く、被覆膜の基材への密着性が良好となることを見出し、本発明に到達した。
即ち本発明は、（１）窒化アルミニウム、熱分解窒化硼素、窒化硼素と窒化アルミニウムの混合焼結体、熱分解窒化硼素コートグラファイト、希土類酸化物、酸化アルミニウム、酸化珪素、ジルコニア、サイアロン、グラファイト、シリコン、タングステン及びニッケル並びにインコネルからなる群の中から選択される１種を主成分としてなる基材の少なくとも一部表面に、化学気相成長法によって、相対密度が７０〜９８％で厚みが５〜５００μｍの窒化アルミニウムからなる被覆膜を設ける工程、
（２）前記窒化アルミニウム被覆膜の表面を１００℃〜５００℃のフッ素系腐食性ガス雰囲気中で処理する工程、及び、
（３）前記被覆膜が、その最表面に１原子％以上40原子％以下のフッ素を含有するように、前記処理工程（２）における処理時間及びアルミニウム被覆膜の表面温度の管理・調整を行う工程、
を含むことを特徴とする、フッ素系腐食性ガスに対する耐性に優れた部材の製造方法である。
本発明においては、前記化学気相成長法の工程における加熱温度が８００℃〜１２００℃であることが好ましく、該工程が特に、前記被覆膜中の相対密度が８０〜９５％となるように調整された工程であることが好ましく、更に、被腹膜の厚みが１０〜３００μｍとなるように調整された工程であることが好ましい。
As a result of intensive studies to achieve the above-mentioned object, the present inventors have determined that a corrosion-resistant aluminum nitride film whose coefficient of thermal expansion gradually changes from the surface of the coating film toward the inside as a film for coating the substrate. It was found that when the film was used, cracks and the like were hardly generated in the film, and the adhesion of the coating film to the base material was improved, and the present invention was achieved.
That is, the present invention provides: (1) Aluminum nitride, pyrolytic boron nitride, mixed sintered body of boron nitride and aluminum nitride, pyrolytic boron nitride coated graphite, rare earth oxide, aluminum oxide, silicon oxide, zirconia, sialon, graphite, A relative density of 70 to 98% and a thickness of 5 are formed on at least a part of the surface of a base material mainly composed of one selected from the group consisting of silicon, tungsten, nickel and inconel by chemical vapor deposition. Providing a coating film made of aluminum nitride of ~ 500 μm;
(2) a step of treating the surface of the aluminum nitride coating film in a fluorine corrosive gas atmosphere at 100 ° C. to 500 ° C., and
(3) Management and adjustment of the treatment time in the treatment step (2) and the surface temperature of the aluminum coating film so that the coating film contains 1 atomic% to 40 atomic% of fluorine on the outermost surface. The process of performing,
It is a manufacturing method of the member excellent in the tolerance with respect to fluorine type corrosive gas characterized by including .
In the present invention, it is preferable that the heating temperature in the chemical vapor deposition step is 800 ° C. to 1200 ° C., the process is particularly, such that the relative density in the coating film becomes 80% to 95% it is rather preferably be adjusted step further is preferably a step of thickness of the peritoneum has been adjusted to be 10 to 300 [mu] m.
本発明の方法によって製造された部材においては、被覆膜の基材への密着性が優れているので、ヒートサイクルに曝されてもクラックや膜剥がれ等が発生し難い上、フッ素プラズマガスに対する耐蝕性にも優れるという効果も奏する。 In the member manufactured by the method of the present invention, the adhesion of the coating film to the base material is excellent, so that cracks and film peeling do not easily occur even when exposed to a heat cycle, and against the fluorine plasma gas. There is also an effect of excellent corrosion resistance.
以下本発明を、図面を参照しつつ詳細に説明する。
図１は、基材１０１の表面をフッ素含有窒化アルミニウム被覆膜１０３で保護した、本発明の方法で製造された部材（以下、単に「本発明の部材」とする。）の断面概念図である。
Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a conceptual cross-sectional view of a member manufactured by the method of the present invention (hereinafter, simply referred to as “member of the present invention”) in which the surface of the substrate 101 is protected by a fluorine-containing aluminum nitride coating film 103. is there.
前記フッ素含有窒化アルミニウムによって被覆される基材は、通常、高温で腐蝕性の高い、ＮＦ3、ＣＦ4、ＣｌＦ3 等のフッ素系ガスに曝される環境に使用される部材である。したがって、これらの部材は、上記腐食性ガスに対する耐性が比較的高い材質であることが好ましい。このような基材は、通常、シリコン、タングステン及びニッケル等の高融点金属、窒化アルミニウム、熱分解窒化硼素、窒化硼素と窒化アルミニウムの混合焼結体、熱分解窒化硼素コートグラファイト、希土類酸化物、酸化アルミニウム、酸化珪素、ジルコニア、サイアロン、及びグラファイト等のセラミックス、並びにインコネル等の高融点合金からなる群の中から選択される何れかを主成分とすれば良い。このようにすることにより、半導体製造装置内における８０0℃程度の高温成膜プロセスにも十分に対応することができる。 The base material coated with the fluorine-containing aluminum nitride is a member used in an environment exposed to a fluorine-based gas such as NF 3 , CF 4 , or ClF 3 that is usually highly corrosive at high temperatures. Therefore, these members are preferably made of a material having a relatively high resistance to the corrosive gas. Such base materials are usually refractory metals such as silicon, tungsten and nickel, aluminum nitride, pyrolytic boron nitride, mixed sintered body of boron nitride and aluminum nitride, pyrolytic boron nitride coated graphite, rare earth oxide, The main component may be selected from the group consisting of ceramics such as aluminum oxide, silicon oxide, zirconia, sialon, and graphite, and a high melting point alloy such as inconel. By doing so, it is possible to sufficiently cope with a high-temperature film forming process of about 800 ° C. in the semiconductor manufacturing apparatus.
図２〜図４は、本発明の部材を応用した具体例であり、図２は静電チャックの断面概念図、図３はウエハホルダの断面概念図、図４はリング部品の断面概念図である。図５は、基材１０１の表面をフッ素含有窒化アルミニウム被覆膜１０３で保護した本発明の部材における、前記基材と被覆膜の間の密着強度を測定する方法を説明するための概念図である。 2 to 4 are specific examples in which the member of the present invention is applied. FIG. 2 is a conceptual sectional view of an electrostatic chuck, FIG. 3 is a conceptual sectional view of a wafer holder, and FIG. 4 is a conceptual sectional view of a ring component. . FIG. 5 is a conceptual diagram for explaining a method of measuring the adhesion strength between the base material and the coating film in the member of the present invention in which the surface of the base material 101 is protected by the fluorine-containing aluminum nitride coating film 103. It is.
本発明においては、上記基材表面の少なくとも一部を覆うように、基材表面に窒化アルミニウム被覆膜等の保護膜を形成させる。これによって、基材に、フッ素系ガスのような高腐蝕性ガスに対する耐性を付与する。この場合、上記窒化アルミニウム被覆膜を、表面におけるフッ素含有量が1原子％〜40原子％である窒化アルミニウム被覆膜とすることが必要である。これによって、基材と窒化アルミニウム被覆膜との密着強度を高め、部材としての機械的特性を向上させることができるので、ヒートサイクルに曝しても、クラックや膜剥離が発生することを抑制することができ、したがって膜厚を十分厚くしても割れることが無く、半導体の不良率を高めるパーティクルの発生を抑えることができる。 In the present invention, a protective film such as an aluminum nitride coating film is formed on the substrate surface so as to cover at least a part of the substrate surface. This gives the substrate resistance to a highly corrosive gas such as a fluorine-based gas. In this case, the aluminum nitride coating film needs to be an aluminum nitride coating film having a fluorine content of 1 atomic% to 40 atomic% on the surface. As a result, the adhesion strength between the base material and the aluminum nitride coating film can be increased and the mechanical properties as a member can be improved, so that the occurrence of cracks and film peeling is suppressed even when exposed to a heat cycle. Therefore, even if the film thickness is sufficiently thick, it is not cracked, and generation of particles that increase the defect rate of the semiconductor can be suppressed.
前記フッ素含有量が1原子％未満では被覆膜の十分な密着強度が得られず、フッ素系ガスに対する耐蝕性が不十分となり、４０原子％以上となると膜が脆くなりクラックが発生し易く、密着強度も低下する。本発明においては、前記フッ素含有量を２原子％以上３０原子％以下とすることが好ましい。 When the fluorine content is less than 1 atomic%, sufficient adhesion strength of the coating film cannot be obtained, and the corrosion resistance against the fluorine-based gas becomes insufficient. When the fluorine content is 40 atomic% or more, the film becomes brittle and cracks easily occur. The adhesion strength also decreases. In the present invention, the fluorine content is preferably 2 atom% or more and 30 atom% or less.
本発明においては、前記フッ素含有窒化アルミニウム被覆膜中のフッ素含有量が、被覆膜表面から膜内部に向かって漸次減少することが好ましい。このようにすることにより、密着強度を飛躍的に向上させることができる。 In the present invention, it is preferable that the fluorine content in the fluorine-containing aluminum nitride coating film gradually decreases from the coating film surface toward the inside of the film. By doing in this way, contact | adhesion intensity | strength can be improved significantly.
上記のようなフッ素含有量の勾配は、化学気相成長法（ＣＶＤ）によって相対密度７０〜９８％に調整した窒化アルミニウム被覆膜を基材表面に成膜した後に、該窒化アルミニウム被覆膜の表面をフッ素系腐食性ガス雰囲気中で１００℃以上５００℃未満の温度で加熱する本発明の製造方法によって容易に形成することができる（図６及び図７参照）。 The gradient of fluorine content as described above is obtained by depositing an aluminum nitride coating film adjusted to a relative density of 70 to 98% by chemical vapor deposition (CVD) on the surface of the substrate, and then the aluminum nitride coating film. Can be easily formed by the production method of the present invention in which the surface is heated in a fluorine-based corrosive gas atmosphere at a temperature of 100 ° C. or higher and lower than 500 ° C. (see FIGS. 6 and 7).
上記被覆膜の相対密度が70％以下であると、フッ素系腐食性ガスによる処理によって導入されるフッ素含有量が多くなり、膜が膨張して割れが生じる。一方相対密度が98％以上であるとフッ素系腐食性ガスによる処理によって導入されるフッ素含有量が少なく、期待する効果が得られない。本発明においては、特に、相対密度が80％以上95％以下となるように調節することが好ましい。
When the relative density of the coating film is 70% or less, the fluorine content introduced by the treatment with the fluorine-based corrosive gas increases, and the film expands to cause cracks. On the other hand, if the relative density is 98% or more, the fluorine content introduced by the treatment with the fluorine-based corrosive gas is small, and the expected effect cannot be obtained. In the present invention, in particular, Rukoto be adjusted so that the relative density is 95% 80% or less is preferable.
前記ＣＶＤ法とは、具体的には、アルミニウムの有機金属化合物又は塩化アルミニウムとアンモニアを原料とした化学気相成長法であり、その反応温度は８００℃〜１２００℃の間であることが好ましい。これにより、結晶性に優れた高純度の窒化アルミニウム被覆膜が得られる。このように化学気相成長法を利用することは、金属不純物が５０ｐｐｍ以下と非常に少ない窒化アルミニウム被覆膜とすることができるので、高純度を要求される半導体製造装置の部材、ヒーター、静電チャック等に、特に好都合である。 Specifically, the CVD method is a chemical vapor deposition method using an organometallic compound of aluminum or aluminum chloride and ammonia as raw materials, and the reaction temperature is preferably between 800 ° C and 1200 ° C. Thereby, a high purity aluminum nitride coating film having excellent crystallinity is obtained. By using the chemical vapor deposition method in this way, an aluminum nitride coating film having a very low metal impurity of 50 ppm or less can be obtained. Therefore, a member of a semiconductor manufacturing apparatus, a heater, It is particularly convenient for an electric chuck or the like.
これに対し、窒化アルミニウム焼結体の表面を単純にフッ素で置換する表面処理を施した場合には、焼結体中の金属不純物（焼結助剤やＣａ、Ｎａ、重金属等）がフッ素で置換される箇所にも存在するので、金属汚染が懸念される。金属不純物の少ない被覆膜であれば、金属不純物のコンタミネーションによる半導体への影響が少ないという優位性も付与される。 On the other hand, when the surface treatment for simply replacing the surface of the aluminum nitride sintered body with fluorine is performed, metal impurities (sintering aid, Ca, Na, heavy metal, etc.) in the sintered body are fluorine. Since it is also present at the place where it is replaced, metal contamination is a concern. If the coating film has few metal impurities, the advantage that there is little influence on the semiconductor due to contamination of metal impurities is given.
本発明においては、前記窒化アルミニウム被覆膜の厚さを５μm以上５００μm以下とすることにより、使用条件によって多少異なるものの、十分に所望する耐蝕性が得られる。
被覆膜の厚さが５μm未満であると、部分的に欠陥があった場合に下地の母材が腐蝕され、半導体の不良率を高めるパーティクルが発生するという危険性がある。また、そこから金属不純物が飛散するという可能性もある。一方、５００μmを超えると、膜の内部応力により基材との境界部分から分離する危険性があるだけでなく、製造するのに膨大な時間がかかってコスト的に見合わない。したがって本発明においては、窒化アルミニウム被覆膜の厚さを１０μm以上３００μm以下とすることが特に好ましい。
以下、実施例及び比較例によって更に本発明を説明するが、本発明はこれらによって限定されるものではない。
In the present invention, by setting the thickness of the aluminum nitride coating film to 5 μm or more and 500 μm or less, sufficiently desired corrosion resistance can be obtained although it varies slightly depending on the use conditions.
If the thickness of the coating film is less than 5 μm, there is a risk that if there is a partial defect, the base material of the base is corroded and particles that increase the defective rate of the semiconductor are generated. There is also the possibility that metal impurities will scatter from there. On the other hand, if it exceeds 500 μm, there is not only a risk of separation from the boundary portion with the base material due to internal stress of the film, but also it takes an enormous amount of time to manufacture and it is not cost effective. Therefore, in the present invention, the thickness of the aluminum nitride coating film is particularly preferably 10 μm or more and 300 μm or less.
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited by these.
[実施例及び比較例]
長さ50mm、幅15mm、厚さ0.5mmの窒化アルミ焼結体基材の表面全体に、熱CVD法によって被覆膜を設けた。
上記被覆膜を成膜するに際しては、原料であるアルミニウムの有機金属化合物としてトリメチルアルミニウムをバブラー法によって供給し、バブリング用のガスとしてArガスを用いた。なお、Arガスの代わりにN2、H2、He等を用いても同様の結果が得られる。
[Examples and Comparative Examples]
A coating film was provided on the entire surface of the aluminum nitride sintered base having a length of 50 mm, a width of 15 mm, and a thickness of 0.5 mm by a thermal CVD method.
When forming the coating film, trimethylaluminum was supplied by a bubbler method as an organometallic compound of aluminum as a raw material, and Ar gas was used as a bubbling gas. Similar results can be obtained by using N 2 , H 2 , He or the like instead of Ar gas.
トリメチルアルミニウムを、２５℃の温度で一定になるように恒温槽に入れ、バブリング用のArガス流量を１〜4L/分とし、シリンダ内の圧力をゲージ圧で10kPaとなるように制御した。成膜に際するトリメチルアルミニウムの供給量を0.1〜0.4mol/hrの間で変え、種々の相対密度の被覆膜を形成させた。
一方、アンモニア原料については、直接加熱気化させて供給量が1.7mol/hrとなるようにMFC（マスフローコントローラー）で調整して供給した。反応炉内を真空状態となるように真空ポンプでガスを排気しながら、圧力が絶対圧で50Pa程度になるように調整し、厚さ95μm、相対密度65％〜99％の被覆膜を形成させた。
Trimethylaluminum was placed in a thermostatic bath so as to be constant at a temperature of 25 ° C., the Ar gas flow rate for bubbling was set to 1 to 4 L / min, and the pressure in the cylinder was controlled to be 10 kPa as a gauge pressure. The supply amount of trimethylaluminum during film formation was changed between 0.1 to 0.4 mol / hr to form coating films having various relative densities.
On the other hand, the ammonia raw material was directly heated and vaporized and adjusted and supplied with an MFC (mass flow controller) so that the supply amount became 1.7 mol / hr. While exhausting the gas with a vacuum pump so that the inside of the reactor is in a vacuum state, the pressure is adjusted to about 50 Pa in absolute pressure to form a coating film with a thickness of 95 μm and a relative density of 65% to 99% I let you.
被覆膜が形成された基材を、室温から550℃まで種々変更して、フッ素気流中（50sccm）で４時間加熱処理を行った。比較例として、加熱処理を行わない基材も準備した。
各条件で作製された被覆膜について、表面のフッ素量と膜の密着強度を調べた。相対密度が90％の被覆膜を形成させた後に、フッ素気流中で加熱処理温度を変えて、フッ素含有量を変化させた部材に関する結果を表１に示し、相対密度が65％〜99％の被覆膜を形成させた後に、400℃のフッ素気流中で加熱処理した部材に関する結果を表２に示した。
The base material on which the coating film was formed was variously changed from room temperature to 550 ° C., and was subjected to heat treatment in a fluorine gas flow (50 sccm) for 4 hours. As a comparative example, a base material not subjected to heat treatment was also prepared.
The coating film prepared under each condition was examined for the amount of fluorine on the surface and the adhesion strength of the film. Table 1 shows the results for members in which the fluorine content was changed by changing the heat treatment temperature in a fluorine stream after forming a coating film having a relative density of 90%. The relative density was 65% to 99%. Table 2 shows the results regarding the members heat-treated in a fluorine stream at 400 ° C. after forming the coating film.
被覆膜中のフッ素量は、サンプルの断面をSEM-EDX（EDAX社）を用いて測定し、Al,N,O,Fの総和を100％として、定量分析によって決定した。一方、被覆膜の密着強度は、薄膜密着強度測定機Romulus（QUAD GROUP社）を用い、エポキシ接着剤付Al製のスタットピン（先端φ2.7mm）を加熱して被覆膜に接着し、室温まで十分に冷却した後に該スタットピンをロードセルで引張り、剥がれる強度を測定した。 The amount of fluorine in the coating film was determined by quantitative analysis by measuring the cross section of the sample using SEM-EDX (EDAX) and setting the total of Al, N, O, and F as 100%. On the other hand, the adhesion strength of the coating film is adhered to the coating film by heating an Al stat pin (tip φ2.7 mm) with an epoxy adhesive using a thin film adhesion strength measuring device Romulus (QUAD GROUP) After sufficiently cooling to room temperature, the stat pin was pulled with a load cell, and the peel strength was measured.
フッ素気流中25℃の加熱処理温度で処理した被覆膜の密着強度は925kgf/cm2、90℃の加熱処理温度では955kg/cm2の密着強度を有していたが、何れも被覆膜と基材との界面で剥がれた。一方、100℃以上500℃以下で処理した被覆膜においては、エポキシ接着材部が1200kgf／cm2の負荷時に剥がれ、被覆膜側は全く剥がれずに、基材に密着したまま完全に残っていた。
又、500℃を超える高温で加熱処理した場合には、被覆膜と基材との界面で膜剥がれが生じた。
The adhesion strength of the coating film treated at a heat treatment temperature of 25 ° C. in a fluorine gas stream was 925 kgf / cm 2 and the adhesion strength of 955 kg / cm 2 at the heat treatment temperature of 90 ° C. And peeled off at the interface between the substrate and the substrate. On the other hand, in the coating film treated at 100 ° C. or more and 500 ° C. or less, the epoxy adhesive part peeled off under a load of 1200 kgf / cm 2 , and the coating film side did not peel at all and remained completely adhered to the substrate. It was.
In addition, when heat treatment was performed at a high temperature exceeding 500 ° C., film peeling occurred at the interface between the coating film and the substrate.
表１及び表２の結果は、本発明の有効性を実証するものである。 The results in Tables 1 and 2 demonstrate the effectiveness of the present invention.
本発明の部材は、被覆膜表面がフッ素系腐蝕性ガスに対する耐蝕性に優れるだけでなく、基材と被覆膜との密着性が優れており、ヒートサイクルを伴う使用にも十分耐え、熱膨張差によるクラックの発生や剥離が生じ難いので、産業上極めて有意義である。 The member of the present invention is not only excellent in corrosion resistance against the fluorine-based corrosive gas on the surface of the coating film, but also excellent in adhesion between the base material and the coating film, sufficiently withstands use with a heat cycle, Since it is difficult for cracks and peeling due to the difference in thermal expansion to occur, it is extremely significant in industry.
１００ 静電チャック
１０１、１０２ 基材
１０３ フッ素含有窒化アルミニウム被覆膜
１０４ａ、１０４ｂ 電極
１０５ ヒーター
１０６ 冷却用ガス孔
１０７ スタッドピン
１０８ エポキシ接着剤
１０９ 密着強度測定用基材固定部品
１１０ ロードセル加重
DESCRIPTION OF SYMBOLS 100 Electrostatic chuck 101,102 Base material 103 Fluorine-containing aluminum nitride coating film 104a, 104b Electrode 105 Heater 106 Cooling gas hole 107 Stud pin 108 Epoxy adhesive 109 Base material fixing part for adhesion strength measurement 110 Load cell load
Claims (4)
（２）前記窒化アルミニウム被覆膜の表面を１００℃〜５００℃のフッ素系腐食性ガス雰囲気中で処理する工程、及び、
（３）前記被覆膜が、その最表面に１原子％以上40原子％以下のフッ素を含有するように、前記処理工程（２）における処理時間及び窒化アルミニウム被覆膜の表面温度の管理・調整を行う工程、
を含むことを特徴とする、フッ素系腐食性ガスに対する耐性に優れた部材の製造方法。 (1) Aluminum nitride, pyrolytic boron nitride, mixed sintered body of boron nitride and aluminum nitride, pyrolytic boron nitride coated graphite, rare earth oxide, aluminum oxide, silicon oxide, zirconia, sialon, graphite, silicon, tungsten and nickel In addition, aluminum nitride having a relative density of 70 to 98% and a thickness of 5 to 500 μm is formed on at least a part of the surface of a substrate mainly composed of one selected from the group consisting of inconel by chemical vapor deposition. Providing a coating film comprising:
(2) a step of treating the surface of the aluminum nitride coating film in a fluorine corrosive gas atmosphere at 100 ° C. to 500 ° C., and
(3) Management of the treatment time in the treatment step (2) and the surface temperature of the aluminum nitride coating film so that the coating film contains 1 atomic% to 40 atomic% of fluorine on the outermost surface. Adjustment process,
Method for producing a member having excellent resistance to, wherein, fluorine-based corrosive gas comprises a.
The method for producing a member according to claim 1, wherein the chemical vapor deposition method is a step in which the thickness of the coating film is adjusted to be 10 to 300 μm .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011220004A JP5876259B2 (en) | 2011-04-14 | 2011-10-04 | Method for manufacturing member covered with aluminum nitride film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011089783 | 2011-04-14 | ||
| JP2011089783 | 2011-04-14 | ||
| JP2011220004A JP5876259B2 (en) | 2011-04-14 | 2011-10-04 | Method for manufacturing member covered with aluminum nitride film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012229149A JP2012229149A (en) | 2012-11-22 |
| JP5876259B2 true JP5876259B2 (en) | 2016-03-02 |
Family
ID=47431061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011220004A Expired - Fee Related JP5876259B2 (en) | 2011-04-14 | 2011-10-04 | Method for manufacturing member covered with aluminum nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5876259B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641489B (en) * | 2013-12-16 | 2014-12-03 | 黑龙江省科学院高技术研究院 | Preparation method of rare earth surface modified aluminum nitride powder |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3078671B2 (en) * | 1992-11-26 | 2000-08-21 | 日本碍子株式会社 | Corrosion resistant member, method of using the same and method of manufacturing the same |
| JPH09328382A (en) * | 1996-06-04 | 1997-12-22 | Mitsubishi Materials Corp | Aluminum nitride base material for semiconductor production unit and its production |
| JP3949268B2 (en) * | 1998-04-20 | 2007-07-25 | 日本碍子株式会社 | Corrosion resistant ceramic material |
| JP4054148B2 (en) * | 1999-02-01 | 2008-02-27 | 日本碍子株式会社 | Corrosion-resistant member manufacturing method and corrosion-resistant member |
| JP4166386B2 (en) * | 1999-09-30 | 2008-10-15 | 日本碍子株式会社 | Corrosion resistant member and manufacturing method thereof |
| JP2010228965A (en) * | 2009-03-27 | 2010-10-14 | Shin-Etsu Chemical Co Ltd | Corrosion resistant member |
-
2011
- 2011-10-04 JP JP2011220004A patent/JP5876259B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012229149A (en) | 2012-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8017062B2 (en) | Semiconductor processing components and semiconductor processing utilizing same | |
| US20060008676A1 (en) | Protective coating on a substrate and method of making thereof | |
| JPH104083A (en) | Anticorrosive material for semiconductor fabrication | |
| JP2010228965A (en) | Corrosion resistant member | |
| JP2009054984A (en) | Component for film forming apparatus and its manufacturing method | |
| TW202113135A (en) | Substrate support cover for high-temperature corrosive environment | |
| JP5876259B2 (en) | Method for manufacturing member covered with aluminum nitride film | |
| JP2012237024A (en) | Alminum nitride film and member covered therewith | |
| JP2008001562A (en) | Yttrium-based ceramic covering material and its production method | |
| JP3929140B2 (en) | Corrosion resistant member and manufacturing method thereof | |
| WO2021117498A1 (en) | Tantalum carbonate-coated graphite member and method for producing same | |
| JP4373487B2 (en) | Corrosion resistant CVD-SiC coating material and jig for CVD equipment | |
| JP2008007350A (en) | Yttria ceramic sintered compact | |
| JP3500278B2 (en) | Corrosion resistant materials for semiconductor manufacturing | |
| JP3784180B2 (en) | Corrosion resistant material | |
| JP2010258276A (en) | Anti-corrosion member | |
| KR20120046007A (en) | A corrosion-resistant article coated with aluminum nitride and method for producing the same | |
| JP2011093772A (en) | Graphite member provided with plasma resistance characteristic | |
| JP4570372B2 (en) | Materials for plasma-resistant semiconductor manufacturing equipment | |
| JPH1067584A (en) | Reaction vessel | |
| US20220181124A1 (en) | Erosion resistant metal fluoride coatings, methods of preparation and methods of use thereof | |
| JP2007073823A (en) | Ceramic covering material and method of manufacturing same | |
| JP2006097114A (en) | Corrosion-resistant spray deposit member | |
| US20220228260A1 (en) | A chemical vapor deposition chamber article | |
| KR20070032050A (en) | Protective coating on a substrate and method of making thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131029 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140718 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140808 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141006 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150421 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150609 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150918 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151023 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160119 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160121 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5876259 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |