JP2000154062A - Boron carbide sintered compact and its production - Google Patents
Boron carbide sintered compact and its productionInfo
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- JP2000154062A JP2000154062A JP10327221A JP32722198A JP2000154062A JP 2000154062 A JP2000154062 A JP 2000154062A JP 10327221 A JP10327221 A JP 10327221A JP 32722198 A JP32722198 A JP 32722198A JP 2000154062 A JP2000154062 A JP 2000154062A
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- boron carbide
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体製造装置用
治具、特にハロゲンプラズマ中で使用させる治具などの
精密加工製品などに使用される高純度高強度の炭化ホウ
素焼結体およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-purity and high-strength boron carbide sintered body used for a jig for a semiconductor manufacturing apparatus, in particular, a precision processing product such as a jig used in a halogen plasma, and its production. About the method.
【０００２】[0002]
【従来の技術】従来より、炭化ホウ素焼結体は、その優
れた耐プラズマ特性から、ドライエッチング装置用多孔
質電極に使用することが提案されている（特開平０１−
５９８１８）。この炭化ホウ素焼結体は、純度が９９．
５％、平均粒径１００μｍの炭化ホウ素粉末を黒鉛ダイ
スに充填したのち、ホットプレス焼成にて作製するもの
である。2. Description of the Related Art Hitherto, it has been proposed that a boron carbide sintered body be used for a porous electrode for a dry etching apparatus because of its excellent plasma resistance (Japanese Patent Application Laid-Open No. 01-2001).
59818). This boron carbide sintered body has a purity of 99.
It is prepared by filling a graphite die with 5% boron carbide powder having an average particle diameter of 100 μm and then sintering by hot pressing.
【０００３】一方、緻密な焼結体を作製する手法として
は、１μｍ以下の粒度分布をもつ粉末状炭化ホウ素に遊
離炭素を０．５〜１０％混合した理論密度の９０％以上
の密度を有する焼結体が提案されている（特公昭５８−
３０２６３号公報参照）。On the other hand, as a technique for producing a dense sintered body, a powdered boron carbide having a particle size distribution of 1 μm or less has a density of 90% or more of the theoretical density obtained by mixing 0.5 to 10% of free carbon. A sintered body has been proposed (Japanese Patent Publication No. 58-
No. 30263).
【０００４】また、本発明者らは、高純度で緻密な焼結
体を作製する手法として、ケイ素化合物特に炭化ケイ素
を０．０５〜５重量％および、熱分解で炭素に変化し得
る有機化合物を炭素換算で０．５〜５重量％添加し純化
処理後に焼成させる方法を提案している。The inventors of the present invention have proposed a technique for producing a high-density sintered compact of a silicon compound, particularly 0.05 to 5% by weight of a silicon carbide and an organic compound which can be converted to carbon by thermal decomposition. Is added in an amount of 0.5 to 5% by weight in terms of carbon, followed by baking after the purification treatment.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、添加物
を用いない上記炭化ホウ素焼結体が開気孔率が２０％以
上あり焼結体自体の強度が充分でない。また、助剤とし
て遊離炭素を添加した焼結体は、アルカリ金属、アルカ
リ土類金属、遷移金属を多く含んでおり、それらが製品
を汚すため半導体製造装置用として使用するには問題が
あった。However, the above-mentioned boron carbide sintered body containing no additive has an open porosity of 20% or more and the strength of the sintered body itself is not sufficient. Further, the sintered body to which free carbon is added as an auxiliary agent contains a large amount of alkali metals, alkaline earth metals, and transition metals, and these have a problem in using them for semiconductor manufacturing equipment because they stain products. .
【０００６】また、炭化ホウ素の一次原料中には不純物
としてグラファイト相が含まれているが、このグラファ
イト相が焼結過程で偏析するため、焼結体組織に異相組
織を形成する傾向にある。しかもこのグラファイト相は
ハロゲンガスのプラズマに対する耐食性が低いため、グ
ラファイト相を多量に含有する焼結体を腐食性の高いな
どのハロゲンプラズマ中で使用すると、グラファイト相
の腐食を初期的腐食とするエッチングが促進され、エッ
チングレートが著しく増大するなど、半導体製造装置用
耐プラズマ部材の材料として使用するには問題があっ
た。The primary material of boron carbide contains a graphite phase as an impurity, and since the graphite phase segregates during the sintering process, it tends to form a heterogeneous structure in the structure of the sintered body. In addition, since the graphite phase has low corrosion resistance to halogen gas plasma, if a sintered body containing a large amount of the graphite phase is used in a halogen plasma such as a highly corrosive one, the etching of the graphite phase as an initial corrosion is performed. And the etching rate is remarkably increased. Therefore, there is a problem in using it as a material for a plasma-resistant member for a semiconductor manufacturing apparatus.
【０００７】従って、本発明は、焼結体中のグラファイ
ト相を低減し、且つ緻密で高強度の炭化ホウ素焼結体と
その製造方法を提供することを目的とするものである。[0007] Accordingly, an object of the present invention is to provide a dense and high-strength boron carbide sintered body which reduces the graphite phase in the sintered body and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記目的
に対して検討を重ねた結果、炭化ホウ素に対して、金属
ホウ素を所定量含有せしめるか、または金属シリコンを
添加することにより、金属ホウ素または金属シリコンが
余剰の炭素と反応して、炭化ホウ素または炭化ケイ素に
変換することにより、グラファイト相を低減できること
を見いだした。また、その場合、アルカリ金属、アルカ
リ土類金属および遷移金属を低減し、且つグラファイト
相をＸ線回折測定によるピーク強度において特定の関係
を満足する場合、優れた強度とハロゲンプラズマに対す
る耐久性が得られることを見いだし、本発明に至った。Means for Solving the Problems As a result of repeated studies on the above objects, the present inventors have found that by adding a predetermined amount of metallic boron to boron carbide or adding metallic silicon, It has been found that the graphite phase can be reduced by reacting metallic boron or metallic silicon with excess carbon and converting it to boron carbide or silicon carbide. In this case, when the alkali metal, the alkaline earth metal and the transition metal are reduced and the graphite phase satisfies a specific relationship in peak intensity by X-ray diffraction measurement, excellent strength and durability to halogen plasma are obtained. Have been found, and the present invention has been achieved.
【０００９】即ち、本発明の炭化ホウ素焼結体は、炭化
ホウ素を主成分とし、Ｘ線回折測定において、炭化ホウ
素の（０２１）面に帰属する回折ピークのピーク強度を
Ｉａ、グラファイトの（００２）面に帰属する回折ピー
クのピーク強度をＩｂとした時、Ｉｂ／Ｉａで表される
ピーク強度比が０．０１以下、アルカリ金属、アルカリ
土類金属および遷移金属元素が総量で３００ｐｐｍ以下
であり、且つ相対密度が９６％以上であることを特徴と
するものである。More specifically, the boron carbide sintered body of the present invention contains boron carbide as a main component, and in X-ray diffraction measurement, the peak intensity of a diffraction peak belonging to the (021) plane of boron carbide is Ia, and the peak intensity of graphite is (002). ) When the peak intensity of the diffraction peak attributed to the plane is Ib, the peak intensity ratio represented by Ib / Ia is 0.01 or less, and the total amount of alkali metals, alkaline earth metals and transition metal elements is 300 ppm or less. And a relative density of 96% or more.
【００１０】また、本発明の他の炭化ホウ素焼結体は、
炭化ホウ素を主成分とし、炭化珪素を０．５〜５重量％
含有し、Ｘ線回折測定において、炭化ホウ素に（０２
１）面に帰属する回折ピークのピーク強度をＩａ、グラ
ファイトの（００２）面に帰属する回折ピークのピーク
強度をＩｂとした時、Ｉｂ／Ｉａで表されるピーク強度
比が０．０１以下、アルカリ金属、アルカリ土類金属お
よび遷移金属元素が総量で３００ｐｐｍ以下であり、且
つ相対密度が９６％以上であることを特徴とするもので
ある。Further, another boron carbide sintered body of the present invention comprises:
The main component is boron carbide, and silicon carbide is 0.5 to 5% by weight.
Contained in boron carbide in X-ray diffraction measurement.
1) When the peak intensity of the diffraction peak attributed to the plane is Ia and the peak intensity of the diffraction peak attributed to the (002) plane of graphite is Ib, the peak intensity ratio represented by Ib / Ia is 0.01 or less; The total amount of the alkali metal, alkaline earth metal and transition metal element is 300 ppm or less, and the relative density is 96% or more.
【００１１】また、本発明によれば、上記の焼結体を製
造するにあたって、平均粒径が５μｍ以下の炭化ホウ素
粉末に、平均粒径が３μｍ以下の金属ホウ素粉末を４〜
１２重量％、炭素粉末あるいは熱分解によって炭素に変
化し得る有機化合物を炭素換算で０．５〜５重量％の割
合で混合する工程と、該混合物を所定形状に成形する工
程と、該成形体を１６００℃〜２１００℃の真空中で熱
処理して、アルカリ金属、アルカリ土類金属および遷移
金属元素を総量で３００ｐｐｍ以下となるまで純化する
工程と、純化処理後に１９００〜２２５０℃の温度で焼
成して、相対密度９６％以上に緻密化する工程とを具備
することを特徴とするものである。Further, according to the present invention, in producing the above-described sintered body, a metal boron powder having an average particle diameter of 3 μm or less is added to a boron carbide powder having an average particle diameter of 5 μm or less by 4 to 4 μm.
Mixing 12% by weight of carbon powder or an organic compound which can be converted to carbon by pyrolysis at a ratio of 0.5 to 5% by weight in terms of carbon; forming the mixture into a predetermined shape; Heat treatment in a vacuum of 1600 ° C. to 2100 ° C. to purify the alkali metal, alkaline earth metal and transition metal element to a total amount of 300 ppm or less, and baking at a temperature of 1900 to 2250 ° C. after the purification treatment. Densification to a relative density of 96% or more.
【００１２】さらに、他の製造方法としては、平均粒径
が５μｍ以下の炭化ホウ素粉末に、平均粒径が５μｍ以
下の金属シリコン粉末、あるいは前記金属シリコンと平
均粒径が１μｍ以下の炭化ケイ素粉末あるいは熱分解に
よって炭化ケイ素に変換し得る有機化合物との混合物を
炭化ケイ素換算で０．５〜５重量％、炭素粉末あるいは
熱分解によって炭素に変化し得る有機化合物を炭素換算
で０．５〜５重量％の割合で混合し、その混合物を所定
形状に成形した後、１６００℃〜２１００℃の真空中で
熱処理して、アルカリ金属、アルカリ土類金属および遷
移金属元素を総量で３００ｐｐｍ以下となるまで純化
し、さらに１９００〜２２５０℃の温度で焼成すること
により、相対密度９６％以上に緻密化できることを見い
だした。Further, as another production method, a boron carbide powder having an average particle diameter of 5 μm or less, a metal silicon powder having an average particle diameter of 5 μm or less, or a silicon carbide powder having an average particle diameter of 1 μm or less with the metal silicon Alternatively, a mixture with an organic compound that can be converted to silicon carbide by thermal decomposition is 0.5 to 5% by weight in terms of silicon carbide, and a carbon powder or an organic compound that can be converted to carbon by thermal decomposition is 0.5 to 5% by weight. And then heat-treating in a vacuum at 1600 ° C. to 2100 ° C. until the total amount of alkali metals, alkaline earth metals and transition metal elements becomes 300 ppm or less. It has been found that by purifying and further firing at a temperature of 1900 to 2250 ° C., it is possible to densify to a relative density of 96% or more.
【００１３】[0013]
【発明の実施の形態】本発明の炭化ホウ素焼結体は、ま
ず、第１に、Ｌｉ，Ｎａ、Ｋなどのアルカリ金属、Ｍ
ｇ、Ｃａ、Ｂａなどのアルカリ土類金属、およびＹ、希
土類元素、Ｔｉ、Ｖ、Ｔａ、Ｍｏ、Ｗ、Ｍｎ、Ｃｒ、Ｃ
ｏ、Ｆｅ、Ｎｉなどの遷移金属元素が総量で３００ｐｐ
ｍ以下、特に１５０ｐｐｍ以下、さらには５０ｐｐｍ以
下、また言い換えると、アルカリ金属、アルカリ土類金
属、遷移金属が各々１００ｐｐｍ以下、特に５０ｐｐｍ
以下、さらには１０ｐｐｍ以下であることが重要であ
る。これは、上記の元素量が３００ｐｐｍよりも多い
と、半導体製造装置に使用した場合に、半導体製造時に
半導体製品を汚染して、半導体の特性を劣化させてしま
うためである。BEST MODE FOR CARRYING OUT THE INVENTION First of all, a boron carbide sintered body of the present invention comprises an alkali metal such as Li, Na or K, M
g, alkaline earth metals such as Ca and Ba, and Y, rare earth elements, Ti, V, Ta, Mo, W, Mn, Cr, C
Transition metal elements such as o, Fe, and Ni are 300 pp in total.
m or less, especially 150 ppm or less, furthermore 50 ppm or less, in other words, alkali metal, alkaline earth metal, and transition metal are each 100 ppm or less, particularly 50 ppm or less.
It is important that the content be 10 ppm or less. This is because if the amount of the element is more than 300 ppm, when used in a semiconductor manufacturing apparatus, the semiconductor product is contaminated during semiconductor manufacturing, and the characteristics of the semiconductor are deteriorated.
【００１４】また、本発明の炭化ホウ素焼結体は相対密
度９６％以上であり、好ましくは９８％以上の緻密体か
らなることが重要である。前記相対密度が９６％よりも
小さいと強度が低下してしまい、目的の強度が得られな
いためである。ここで、前記相対密度は理論密度に対す
る百分率で表したものである。It is important that the boron carbide sintered body of the present invention is a dense body having a relative density of 96% or more, preferably 98% or more. If the relative density is less than 96%, the strength decreases, and the desired strength cannot be obtained. Here, the relative density is expressed as a percentage with respect to the theoretical density.
【００１５】さらに、本発明の炭化ホウ素焼結体は、炭
化ホウ素の（０２１）面に帰属する回折ピークのピーク
強度をＩａ、グラファイトの（００２）面に帰属する回
折ピークのピーク強度をＩｂとした時、Ｉｂ／Ｉａで表
されるピーク強度比が０．０１以下、特に０．００２以
下であることが重要である。Further, in the boron carbide sintered body of the present invention, the peak intensity of the diffraction peak belonging to the (021) plane of boron carbide is Ia, and the peak intensity of the diffraction peak belonging to the (002) plane of graphite is Ib. It is important that the peak intensity ratio represented by Ib / Ia is 0.01 or less, particularly 0.002 or less.
【００１６】これは、上記ピーク強度比が０．０１より
も高いと、焼結体粒界中に存在するグラファイト相が偏
析して異相組織を形成し、ここを起点としてプラズマに
よる腐食が進行するため著しく耐プラズマ性が劣化する
ためである。If the peak intensity ratio is higher than 0.01, the graphite phase present in the grain boundaries of the sintered body segregates to form a heterogeneous structure, and the corrosion by plasma proceeds from this point as a starting point. This is because the plasma resistance is significantly deteriorated.
【００１７】なお、本発明によれば、半導体製造時に悪
影響を及ぼすことがなく、しかも真空中から高温まで安
定な炭化ケイ素を０．５〜５重量％の割合で含有するこ
ともできる。この炭化ケイ素は焼結助剤として作用し、
この量が０．５重量％よりも少ないと焼結助剤的な効果
が期待できず、５重量％を越えると炭化ホウ素が粒成長
を来たし、焼結体の強度を低下させてしまう。According to the present invention, it is possible to contain silicon carbide in a ratio of 0.5 to 5% by weight which has no adverse effect on the production of a semiconductor and is stable from a vacuum to a high temperature. This silicon carbide acts as a sintering aid,
If the amount is less than 0.5% by weight, the effect as a sintering aid cannot be expected, and if it exceeds 5% by weight, boron carbide will grow and the strength of the sintered body will be reduced.
【００１８】かかる高純度で高強度な炭化ホウ素焼結体
を作製する方法は、少なくとも以下の（１）〜（４）の
工程から構成される。A method for producing such a high-purity and high-strength sintered boron carbide body includes at least the following steps (1) to (4).
【００１９】（１）まず、出発原料として、ａ）炭化ホ
ウ素粉末、ｂ）平均粒径が３μｍ以下の金属ホウ素粉
末、ｃ）平均粒径が５μｍ以下の金属シリコン粉末、あ
るいは前記金属シリコンと平均粒径が１μｍ以下の炭化
ケイ素粉末あるいは熱分解によって炭化ケイ素に変換し
得る有機化合物との混合物とからなる炭化ケイ素成分、
ｄ）炭素粉末あるいは熱分解によって炭素に変化し得る
有機化合物等の炭素源を用いて、ａ）およびｃ）に対し
て、ｂ）及び／又はｃ）を添加混合する。(1) First, as starting materials, a) boron carbide powder, b) metal boron powder having an average particle size of 3 μm or less, c) metal silicon powder having an average particle size of 5 μm or less, or A silicon carbide component having a particle size of 1 μm or less and a mixture with a silicon carbide powder or an organic compound that can be converted to silicon carbide by thermal decomposition;
d) b) and / or c) are added and mixed to a) and c) using a carbon source such as carbon powder or an organic compound which can be converted to carbon by thermal decomposition.
【００２０】この場合、主成分となるａ）炭化ホウ素粉
末の平均粒径は５μｍ以下、好ましくは２μｍ以下、よ
り好ましくは１μｍ以下であることが必要であり、平均
粒径が５μｍを超えると、緻密化不足を招いて、強度低
下を引き起こしてしまう。In this case, the average particle size of the main component a) boron carbide powder needs to be 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less. If the average particle size exceeds 5 μm, Insufficient densification causes a reduction in strength.
【００２１】また、上記ｂ）の金属ホウ素は４〜１２重
量％、特に７〜９重量％の割合で添加することが望まし
く、この量が４重量％よりも少ないと、グラファイト相
が残存し、１２重量％よりも多いと過剰なホウ素が緻密
化を阻害する。It is desirable that the metallic boron of the above b) is added in a ratio of 4 to 12% by weight, particularly 7 to 9% by weight. If the amount is less than 4% by weight, a graphite phase remains, If it is more than 12% by weight, excess boron inhibits densification.
【００２２】さらに、上記ｃ）炭化ケイ素成分は、炭化
ケイ素に換算して総量で０．５〜５重量％、好ましくは
１〜４重量％、より好ましくは２〜３重量％である。こ
の量が０．５重量％より小さいと緻密化が難しく、５重
量％を超えると炭化ホウ素が粒子成長を起こし、強度を
低下させてしまうためである。The silicon carbide component (c) is 0.5 to 5% by weight, preferably 1 to 4% by weight, more preferably 2 to 3% by weight in terms of silicon carbide. If the amount is less than 0.5% by weight, densification is difficult, and if it exceeds 5% by weight, boron carbide causes grain growth and lowers the strength.
【００２３】また、本発明によれば、平均粒径が５μｍ
以下の金属シリコンを必須成分として含有し、特に炭化
ケイ素換算で０．０５重量％以上、好ましくは１重量％
以上の割合で添加する。この金属シリコンは、後述する
純化処理中に、炭化ホウ素の一次原料中に存在するグラ
ファイト相と反応して炭化ケイ素を生成し、焼結体中に
炭素源がグラファイト相として残存するのを抑制するこ
とができるためである。なお、上記金属シリコンの平均
粒径が５μｍよりも大きいと、グラファイト相との反応
性が低下し、未反応のグラファイト相が残存しやすくな
る。好ましくは２μｍ以下がよい。According to the present invention, the average particle size is 5 μm.
The following metal silicon is contained as an essential component, and particularly 0.05% by weight or more, preferably 1% by weight in terms of silicon carbide.
Add at the above ratio. This metal silicon reacts with the graphite phase present in the primary material of boron carbide during the purification process described later to generate silicon carbide, and suppresses the carbon source from remaining in the sintered body as the graphite phase. This is because you can do it. If the average particle size of the metal silicon is larger than 5 μm, the reactivity with the graphite phase is reduced, and the unreacted graphite phase tends to remain. Preferably it is 2 μm or less.
【００２４】なお、熱分解によって炭化ケイ素を生成し
得る有機化合物としては、ポリカルボシランなどが挙げ
られる。The organic compound capable of forming silicon carbide by thermal decomposition includes polycarbosilane and the like.
【００２５】また上記ｄ）炭素源は、炭素換算で０．５
〜５重量％、好ましくは１〜４重量％の割合で混合す
る。この炭素源は、焼結中に炭化ホウ素主原料等に含ま
れるＢ2 Ｏ3 と反応して酸素分を除去する作用をなす。
Ｂ2 Ｏ3 は焼結性を阻害するためにＢ2 Ｏ3 が還元分解
されることにより焼結性が促進される。従って、この炭
素量が０．５重量％よりも少ないとＢ2 Ｏ3 の還元が充
分に行われず緻密化が難しく、５重量％を超えると逆に
炭化ホウ素の粒子成長を抑制し、緻密化を阻害してしま
うためである。なお、熱分解によって炭素に変化し得る
有機化合物としては、コールタールピッチ、フルフリル
アルコール、コーンスターチ、糖類、フェノール樹脂等
が挙げられる。The d) carbon source is 0.5% in terms of carbon.
５5% by weight, preferably 1-4% by weight. This carbon source reacts with B 2 O 3 contained in the boron carbide main raw material or the like during sintering to remove oxygen.
Since B 2 O 3 impairs sinterability, B 2 O 3 is reductively decomposed to promote sinterability. Therefore, if the carbon content is less than 0.5% by weight, B 2 O 3 is not sufficiently reduced and densification is difficult, and if it exceeds 5% by weight, on the contrary, boron carbide particle growth is suppressed and densification is performed. This is because it hinders. Note that examples of the organic compound that can be converted to carbon by thermal decomposition include coal tar pitch, furfuryl alcohol, corn starch, sugars, phenol resins, and the like.
【００２６】（２）次に、これらの混合物を、公知の所
望の成形手段、例えば、金型プレス、冷間静水圧プレ
ス、射出成形、押出し成形等により任意の形状に成形す
る。(2) Next, the mixture is formed into an arbitrary shape by a known desired forming means, for example, a die press, a cold isostatic press, an injection molding, an extrusion molding or the like.
【００２７】（３）そして、上記成形体を、まず、１６
００℃〜２１００℃の真空中で熱処理することにより、
成形体中のアルカリ金属、アルカリ土類金属および遷移
金属元素が総量で３００ｐｐｍ以下となるように純化処
理を施す。また、この時の真空圧力は、１０Ｐａ以下で
あることが望ましく、１０Ｐａを超えると上記元素を効
率的に除去することが難しくなるためである。(3) Then, the molded body is first
By performing heat treatment in a vacuum of 00 ° C to 2100 ° C,
Purification is performed so that the total amount of alkali metals, alkaline earth metals, and transition metal elements in the molded body is 300 ppm or less. Further, the vacuum pressure at this time is desirably 10 Pa or less, and if it exceeds 10 Pa, it becomes difficult to efficiently remove the above elements.
【００２８】この純化処理の温度は１６００℃〜２１０
０℃であるが、好ましくは１８００℃〜２０００℃であ
り、１６００℃よりも低いと純化処理できず、２１００
℃を超えると添加した炭化ケイ素が飛散し緻密化を阻害
し強度低下を引き起こすためである。The temperature of this purification treatment is from 1600 ° C. to 210
The temperature is 0 ° C., preferably 1800 ° C. to 2000 ° C. If the temperature is lower than 1600 ° C., purification treatment cannot be performed and 2100 ° C.
If the temperature exceeds ℃, the added silicon carbide is scattered to inhibit densification and cause a decrease in strength.
【００２９】（４）上記純化処理後、１９００〜２２５
０℃の温度で焼成して、相対密度９６％以上に緻密化す
る。前記焼成温度は、好ましくは１９００℃〜２１００
℃であり、真空中あるいは不活性雰囲気、特にアルゴン
ガス中で焼成するのが望ましい。この焼成温度が２２５
０℃を超えると炭化ホウ素が粒子成長し、強度低下を招
き、１９００℃よりも低いと相対密度９６％以上に緻密
化することが難しい。(4) After the above purification treatment, 1900 to 225
It is fired at a temperature of 0 ° C. to densify to a relative density of 96% or more. The firing temperature is preferably 1900 ° C. to 2100
C. and preferably fired in a vacuum or in an inert atmosphere, particularly in argon gas. This firing temperature is 225
If the temperature exceeds 0 ° C., boron carbide grows and the strength is reduced. If the temperature is lower than 1900 ° C., it is difficult to make the relative density 96% or more.
【００３０】なお、焼成方法としては、常圧焼成（普通
焼成）の他、ホットプレス焼成によって２００ｋｇ／ｃ
ｍ2 の機械的圧力を付与しながら焼成することもでき
る。上記ホットプレス法においては、（１）の粉末をホ
ットプレス型内に充填して、上記の（３）純化処理を施
した後、５００ｋｇ／ｃｍ2 以上の機械的圧力を付与し
ながら（４）の条件で焼成することにより、（２）成形
工程を（４）焼成工程と同時を行うことができるととも
に、短時間で緻密化できる点で有利である。The firing method includes normal pressure firing (normal firing) and hot press firing at 200 kg / c.
Firing can also be performed while applying a mechanical pressure of m 2 . In the hot press method, after the powder of (1) is filled in a hot press mold and subjected to the above-mentioned (3) purification treatment, while applying a mechanical pressure of 500 kg / cm 2 or more, (4) Firing under the above conditions is advantageous in that the (2) forming step can be performed simultaneously with the (4) firing step, and the densification can be performed in a short time.
【００３１】かくして得られる焼結体は、高純度で緻密
化された高強度でかつ高い耐ハロゲンプラズマ性を有す
る炭化ホウ素焼結体であり、半導体製造装置用の治具や
サセプターに使用した場合においても、アルカリ金属、
アルカリ土類金属及び遷移金属による半導体の汚染がほ
とんど無いという作用効果を有する。The sintered body thus obtained is a boron carbide sintered body having a high purity and a high density and a high strength and a high halogen plasma resistance, and is used for a jig or a susceptor for a semiconductor manufacturing apparatus. Also in alkali metals,
This has the effect that the semiconductor is hardly contaminated by the alkaline earth metal and the transition metal.
【００３２】しかも、本発明の炭化ホウ素焼結体は、導
電性を有する高強度の材料であり、ドライエッチングプ
ロセスやハロゲンプラズマ等のプラズマ雰囲気中での成
膜プロセスで使用される電極、サセプターなどの治具な
どの半導体製造装置用部品、半導体製造装置用チャンバ
ー（壁体）、産業機械用の各種治工具、各種耐磨耗部
品、精密加工用部品として好適に使用できる。Moreover, the boron carbide sintered body of the present invention is a high-strength material having conductivity, and is used for electrodes, susceptors, etc. used in a dry etching process or a film forming process in a plasma atmosphere such as a halogen plasma. Jigs and other parts for semiconductor manufacturing equipment, chambers (walls) for semiconductor manufacturing equipment, various jigs and tools for industrial machinery, various wear-resistant parts, and parts for precision machining.
【００３３】[0033]
【実施例】炭化ホウ素粉末として、Ｎａ、Ｃａ、Ｆｅが
それぞれ８４０ｐｐｍ、１２０ｐｐｍ、３００ｐｐｍ
で、平均粒径が０．８μｍの粉末（試料Ｎo.１〜３２）
と、平均粒径が２０μｍの粉末（試料Ｎo.３３）を用い
た。EXAMPLES As boron carbide powder, Na, Ca, and Fe were 840 ppm, 120 ppm, and 300 ppm, respectively.
And powder having an average particle size of 0.8 μm (Sample Nos. 1 to 32)
And a powder having an average particle diameter of 20 μm (Sample No. 33).
【００３４】また、金属ホウ素粉末として平均粒径が１
μｍのものを使用した。金属Ｓｉ粉末には平均粒径４μ
ｍのものを用いた。炭化ケイ素粉末としては、平均粒子
径０．６μｍのα−炭化ケイ素粉末を用いた。また、炭
素源としては炭化率が２０％のフェノール樹脂を有機溶
媒に溶解させて用いた。The metal boron powder has an average particle size of 1
μm was used. Average particle size 4μ for metal Si powder
m. As the silicon carbide powder, α-silicon carbide powder having an average particle diameter of 0.6 μm was used. As a carbon source, a phenol resin having a carbonization ratio of 20% was used by being dissolved in an organic solvent.
【００３５】そして、上記炭化ホウ素粉末、金属ホウ素
あるいは炭化ケイ素源、炭素源を表１〜３に示す組み合
わせおよび配合量で秤量し、プラスチックボールを用い
て有機溶媒中で混合し、エバポレーターを用いて乾燥粉
末を得た。Then, the above-mentioned boron carbide powder, metallic boron or silicon carbide source, and carbon source are weighed in combinations and amounts shown in Tables 1 to 3, mixed in an organic solvent using a plastic ball, and then mixed with an evaporator. A dry powder was obtained.
【００３６】焼成は、ホットプレス焼成装置（ＨＰ）と
普通焼成（ＰＬＳ）装置を用いた。ホットプレス焼成の
場合は、混合粉末をカーボン型に入れ、表１〜３に示す
温度で５Ｐａの真空中で２時間純化処理をし、その後３
００ｋｇ／ｃｍ2 の圧力下で表に示す焼成温度でアルゴ
ン中２時間保持し、焼成した。普通焼成の場合は、この
粉末を３ｔ／ｃｍ2 の圧力で静水圧処理をして成形体を
作製し、表１〜３に示す温度で、５Ｐａの真空中で２時
間純化処理し、その後、表１〜３に示す焼成温度でアル
ゴンガス中で３時間保持し焼成した。For firing, a hot press firing device (HP) and a normal firing (PLS) device were used. In the case of hot press firing, the mixed powder is put into a carbon mold and subjected to a purification treatment at a temperature shown in Tables 1 to 3 in a vacuum of 5 Pa for 2 hours.
Under the pressure of 00 kg / cm 2 and the firing temperature shown in the table, it was kept in argon for 2 hours and fired. In the case of normal firing, this powder is subjected to hydrostatic pressure treatment at a pressure of 3 t / cm 2 to produce a molded body, and purified at a temperature shown in Tables 1 to 3 in a vacuum of 5 Pa for 2 hours. At the firing temperature shown in Tables 1 to 3, it was held and fired in an argon gas for 3 hours.
【００３７】また、比較のために、炭素粉末を真空雰囲
気中で２５００℃で５時間焼成したグラファイト焼結体
を作製した（試料Ｎo.３４）。For comparison, a graphite sintered body was prepared by firing carbon powder at 2500 ° C. for 5 hours in a vacuum atmosphere (Sample No. 34).
【００３８】得られた焼結体から試験片を切り出し、研
磨加工した。そして比重をＪＩＳＲ２２０５に基づいて
求め相対密度を求めた。強度値はＪＩＳＲ１６０１に基
づく４点曲げ試験より室温強度を求めた。また、試料を
粉砕し、Ｘ線回折測定を行いＢ4 Ｃ相の（０２１）面に
帰属する回折ピークのピーク強度Ｉａ、およびグラファ
イト相の（００２）面に帰属する回折ピークのピーク強
度Ｉｂより、Ｉｂ／Ｉａのピーク強度比を求めた。な
お、表中、試料Ｎo.３（本発明品）および試料Ｎo.１
（比較品）のＸ線回折測定結果を図１および図２に示し
た。さらに、粉砕した粉末をＩＣＰ発光分光分析を行
い、アルカリ金属、アルカリ土類金属、その他遷移金属
量を測定した。A test piece was cut out from the obtained sintered body and polished. Then, the specific gravity was determined based on JISR2205, and the relative density was determined. As the strength value, a room temperature strength was obtained from a four-point bending test based on JISR1601. Further, the sample was pulverized and subjected to X-ray diffraction measurement to determine the peak intensity Ia of the diffraction peak belonging to the (021) plane of the B 4 C phase and the peak intensity Ib of the diffraction peak belonging to the (002) plane of the graphite phase. , Ib / Ia were determined. In the table, sample No. 3 (product of the present invention) and sample No. 1
The X-ray diffraction measurement results of the (comparative product) are shown in FIGS. Furthermore, the pulverized powder was subjected to ICP emission spectroscopy to measure the amounts of alkali metals, alkaline earth metals, and other transition metals.
【００３９】また、この試料をリアクティブイオンエッ
チング装置内に設置して、この装置内に塩素ガスを導入
して装置内圧力を７〜１０Ｐａに保持した。そして、１
３．５６ＭＨｚ、１ｋＷの高周波を導入してプラズマを
発生させ、試料をプラズマに接触させた。なお試料温度
は室温（２５℃）に設定した。上記の条件下で３時間エ
ッチング処理を行った後、試料の重量減少からエッチン
グ速度を算出した。The sample was set in a reactive ion etching apparatus, and chlorine gas was introduced into the apparatus to maintain the pressure in the apparatus at 7 to 10 Pa. And 1
Plasma was generated by introducing a high frequency of 3.56 MHz and 1 kW, and the sample was brought into contact with the plasma. The sample temperature was set at room temperature (25 ° C.). After performing the etching treatment under the above conditions for 3 hours, the etching rate was calculated from the weight loss of the sample.
【００４０】また、得られた焼結体から、炭化ケイ素量
を算出した。炭化ケイ素量は、焼結体中に金属シリコン
が検出されていないことから、焼結体中の総シリコン量
から炭化ケイ素換算して求めた。The amount of silicon carbide was calculated from the obtained sintered body. The amount of silicon carbide was determined in terms of silicon carbide from the total amount of silicon in the sintered body, since no metallic silicon was detected in the sintered body.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【表３】 [Table 3]
【００４４】表１〜３によると本発明の範囲内の試料
は、いずれも高純度であり、２００ＭＰａ以上の高強度
を有し、エッチング速度が４０Å／ｍｉｎ以下の優れた
耐プラズマ性を有するものであり、特に焼結体中に炭化
ケイ素を含む場合、強度の向上が見られた。According to Tables 1 to 3, all the samples within the scope of the present invention have high purity, high strength of 200 MPa or more, and excellent plasma resistance at an etching rate of 40 ° / min or less. In particular, when silicon carbide was contained in the sintered body, improvement in strength was observed.
【００４５】これに対して、グラファイト焼結体は、エ
ッチング速度が著しく高く、耐プラズマ性は低い。一
方、金属ホウ素または金属シリコンを添加しない試料Ｎ
o.１、１９では、ピーク強度比が０．０１より高く、一
次原料中のグラファイト相が偏析する異相組織を形成し
ており耐プラズマ性も低いものであった。On the other hand, the graphite sintered body has a remarkably high etching rate and low plasma resistance. On the other hand, the sample N without addition of metallic boron or metallic silicon
In O. 1 and 19, the peak intensity ratio was higher than 0.01, a heterophase structure in which the graphite phase in the primary raw material segregated was formed, and the plasma resistance was low.
【００４６】また、平均粒径が５μｍを越える粉末を用
いた試料Ｎo.３５では、緻密化不足となり、強度が低下
した。Sample No. 35 using a powder having an average particle size exceeding 5 μm was insufficient in densification, resulting in a decrease in strength.
【００４７】[0047]
【発明の効果】上述の如く、本発明の炭化ホウ素焼結体
は、優れた抗折強度と高純度を有するとともに、優れた
耐プラズマ性を有することから、半導体製造装置用治
具、特にハロゲンプラズマ中で使用される治具などの精
密加工製品に使用できる。As described above, the boron carbide sintered body of the present invention has excellent bending strength and high purity and excellent plasma resistance. It can be used for precision processing products such as jigs used in plasma.
【図１】本発明の炭化ホウ素焼結体（試料Ｎo.３）のＸ
線回折チャートを示す図である。FIG. 1 shows the X of the boron carbide sintered body of the present invention (sample No. 3).
It is a figure showing a line diffraction chart.
【図２】従来の炭化ホウ素焼結体（試料Ｎo.１）のＸ線
回折チャートを示す図である。FIG. 2 is a view showing an X-ray diffraction chart of a conventional boron carbide sintered body (sample No. 1).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高坂 祥二 鹿児島県国分市山下町１番４号 京セラ株 式会社総合研究所内 Ｆターム(参考） 4G001 BA22 BA23 BA60 BA62 BA71 BA78 BB22 BB23 BB60 BB71 BC12 BC13 BC31 BC46 BC47 BC52 BD14 BD37 BD38 BE11 BE33 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Takasaka 1-4-4 Yamashita-cho, Kokubu-shi, Kagoshima F-term in Kyocera Research Institute (reference) 4G001 BA22 BA23 BA60 BA62 BA71 BA78 BB22 BB23 BB60 BB71 BC12 BC13 BC31 BC46 BC47 BC52 BD14 BD37 BD38 BE11 BE33
Claims (4)
おいて、炭化ホウ素の（０２１）面に帰属する回折ピー
クのピーク強度をＩａ、グラファイトの（００２）面に
帰属する回折ピークのピーク強度をＩｂとした時、Ｉｂ
／Ｉａで表されるピーク強度比が０．０１以下、アルカ
リ金属、アルカリ土類金属および遷移金属元素が総量で
３００ｐｐｍ以下であり、且つ相対密度が９６％以上で
あることを特徴とする炭化ホウ素焼結体。1. An X-ray diffraction measurement comprising boron carbide as a main component, wherein the peak intensity of a diffraction peak belonging to the (021) plane of boron carbide is Ia, and the peak intensity of a diffraction peak belonging to the (002) plane of graphite. Is Ib, Ib
/ Ia, wherein the peak intensity ratio is 0.01 or less, the total amount of alkali metals, alkaline earth metals and transition metal elements is 300 ppm or less, and the relative density is 96% or more. Sintered body.
５〜５重量％含有し、Ｘ線回折測定において、炭化ホウ
素の（０２１）面に帰属する回折ピークのピーク強度を
Ｉａ、グラファイトの（００２）面に帰属する回折ピー
クのピーク強度をＩｂとした時、Ｉｂ／Ｉａで表される
ピーク強度比が０．０１以下、アルカリ金属、アルカリ
土類金属および遷移金属元素が総量で３００ｐｐｍ以下
であり、且つ相対密度が９６％以上であることを特徴と
する炭化ホウ素焼結体。2. The method according to claim 1, wherein the main component is boron carbide, and the silicon carbide is 0.1%.
In X-ray diffraction measurement, the peak intensity of the diffraction peak attributed to the (021) plane of boron carbide was Ia, and the peak intensity of the diffraction peak attributed to the (002) plane of graphite was Ib. In this case, the peak intensity ratio represented by Ib / Ia is 0.01 or less, the total amount of alkali metals, alkaline earth metals, and transition metal elements is 300 ppm or less, and the relative density is 96% or more. Boron carbide sintered body.
に、平均粒径が３μｍ以下の金属ホウ素粉末を４〜１２
重量％、炭素粉末あるいは熱分解によって炭素に変化し
得る有機化合物を炭素換算で０．５〜５重量％の割合で
混合する工程と、 該混合物を所定形状に成形する工程と、 該成形体を１６００℃〜２１００℃の真空中で熱処理し
て、アルカリ金属、アルカリ土類金属および遷移金属元
素を総量で３００ｐｐｍ以下となるまで純化する工程
と、 純化処理後に１９００〜２２５０℃の温度で焼成して、
相対密度９６％以上に緻密化する工程とを具備すること
を特徴とする炭化ホウ素焼結体の製造方法。3. A boron carbide powder having an average particle diameter of 5 μm or less, and a metal boron powder having an average particle diameter of 3 μm or less being 4 to 12 μm.
% By weight, a step of mixing 0.5 to 5% by weight of carbon powder or an organic compound which can be converted to carbon by thermal decomposition, a step of forming the mixture into a predetermined shape, Heat-treating in a vacuum of 1600 ° C. to 2100 ° C. to purify the alkali metal, alkaline earth metal and transition metal element to a total amount of 300 ppm or less; and firing at a temperature of 1900 to 2250 ° C. after the purifying treatment. ,
Densifying to a relative density of 96% or more.
に、平均粒径が５μｍ以下の金属シリコン粉末、あるい
は前記金属シリコンと平均粒径が１μｍ以下の炭化ケイ
素粉末あるいは熱分解によって炭化ケイ素に変換し得る
有機化合物との混合物を炭化ケイ素換算で０．５〜５重
量％、炭素粉末あるいは熱分解によって炭素に変化し得
る有機化合物を炭素換算で０．５〜５重量％の割合で混
合する工程と、 該混合物を所定形状に成形する工程と、 該成形体を１６００℃〜２１００℃の真空中で熱処理し
て、アルカリ金属、アルカリ土類金属および遷移金属元
素を総量で３００ｐｐｍ以下となるまで純化する工程
と、 純化処理後に１９００〜２２５０℃の温度で焼成して、
相対密度９６％以上に緻密化する工程とを具備すること
を特徴とする炭化ホウ素焼結体の製造方法。4. A boron carbide powder having an average particle size of 5 μm or less, a metal silicon powder having an average particle size of 5 μm or less, a silicon carbide powder having an average particle size of 1 μm or less, or silicon carbide by thermal decomposition. A mixture with an organic compound that can be converted is mixed at a ratio of 0.5 to 5% by weight in terms of silicon carbide, and a carbon powder or an organic compound that can be converted to carbon by pyrolysis is mixed at a ratio of 0.5 to 5% by weight in terms of carbon. A step of forming the mixture into a predetermined shape; and heat-treating the formed body in a vacuum at 1600 ° C. to 2100 ° C. until the total amount of alkali metals, alkaline earth metals and transition metal elements becomes 300 ppm or less. Purifying, after the purification treatment, firing at a temperature of 1900 to 2250 ° C.,
Densifying to a relative density of 96% or more.
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| JP32722198A JP3667121B2 (en) | 1998-11-17 | 1998-11-17 | Boron carbide sintered body and manufacturing method thereof |
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| JP32722198A JP3667121B2 (en) | 1998-11-17 | 1998-11-17 | Boron carbide sintered body and manufacturing method thereof |
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| JP2000154062A true JP2000154062A (en) | 2000-06-06 |
| JP3667121B2 JP3667121B2 (en) | 2005-07-06 |
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| JP (1) | JP3667121B2 (en) |
Cited By (9)
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| JP2007322010A (en) * | 2006-05-30 | 2007-12-13 | Kyocera Corp | Protective member |
| US7592279B1 (en) * | 2003-06-12 | 2009-09-22 | Georgia Tech Research Corporation | Boron carbide and boron carbide components |
| US7854190B2 (en) | 2005-04-11 | 2010-12-21 | Georgia Tech Research Corporation | Boron carbide component and methods for the manufacture thereof |
| WO2012060442A1 (en) | 2010-11-04 | 2012-05-10 | 黒崎播磨株式会社 | High rigidity ceramic material and method for producing same |
| US8377369B2 (en) | 2004-12-20 | 2013-02-19 | Georgia Tech Research Corporation | Density and hardness pressureless sintered and post-HIPed B4C |
| CN103613389A (en) * | 2013-11-29 | 2014-03-05 | 宁波伏尔肯机械密封件制造有限公司 | Sintering preparation method of boron carbide ceramic |
| KR102262340B1 (en) * | 2020-07-02 | 2021-06-09 | 주식회사 티씨케이 | Boron carbide material |
| KR20220114929A (en) * | 2021-02-09 | 2022-08-17 | 주식회사 티씨케이 | Semiconductor manufacturing parts including boron carbide resistant plasma members |
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| CN110204337B (en) * | 2019-06-04 | 2021-04-30 | 中南大学 | Preparation method of boron carbide ceramic material for aerospace gyroscope bearing and boron carbide ceramic material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7592279B1 (en) * | 2003-06-12 | 2009-09-22 | Georgia Tech Research Corporation | Boron carbide and boron carbide components |
| US8377369B2 (en) | 2004-12-20 | 2013-02-19 | Georgia Tech Research Corporation | Density and hardness pressureless sintered and post-HIPed B4C |
| US7854190B2 (en) | 2005-04-11 | 2010-12-21 | Georgia Tech Research Corporation | Boron carbide component and methods for the manufacture thereof |
| JP2007322010A (en) * | 2006-05-30 | 2007-12-13 | Kyocera Corp | Protective member |
| WO2012060442A1 (en) | 2010-11-04 | 2012-05-10 | 黒崎播磨株式会社 | High rigidity ceramic material and method for producing same |
| US8937029B2 (en) | 2010-11-04 | 2015-01-20 | Krosakiharima Corporation | High-rigidity ceramic material and production method therefor |
| CN103613389A (en) * | 2013-11-29 | 2014-03-05 | 宁波伏尔肯机械密封件制造有限公司 | Sintering preparation method of boron carbide ceramic |
| CN115210197A (en) * | 2020-02-12 | 2022-10-18 | Skc索密思株式会社 | Ceramic member and plasma etching apparatus including the same |
| KR102262340B1 (en) * | 2020-07-02 | 2021-06-09 | 주식회사 티씨케이 | Boron carbide material |
| KR20220114929A (en) * | 2021-02-09 | 2022-08-17 | 주식회사 티씨케이 | Semiconductor manufacturing parts including boron carbide resistant plasma members |
| KR102513077B1 (en) | 2021-02-09 | 2023-03-24 | 주식회사 티씨케이 | Semiconductor manufacturing parts including boron carbide resistant plasma members |
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|---|---|
| JP3667121B2 (en) | 2005-07-06 |
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