JPH11217268A - Silicon carbide sintered compact for plasma apparatus and its production - Google Patents
Silicon carbide sintered compact for plasma apparatus and its productionInfo
- Publication number
- JPH11217268A JPH11217268A JP10032253A JP3225398A JPH11217268A JP H11217268 A JPH11217268 A JP H11217268A JP 10032253 A JP10032253 A JP 10032253A JP 3225398 A JP3225398 A JP 3225398A JP H11217268 A JPH11217268 A JP H11217268A
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- weight
- sintered body
- aluminum
- boron
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プラズマ装置用炭化珪
素焼結体に関し、特に耐プラズマ性に優れ、粒子脱落に
よるパーティクル汚染の少ないプラズマ装置用炭化珪素
焼結体及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 silicon carbide sintered body for a plasma device, and more particularly to a silicon carbide sintered body for a plasma device having excellent plasma resistance and less particle contamination due to falling off of particles, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、電極、シールドリング、緩衝板等
のプラズマ装置用素材としては、アルマイト処理された
アルミニウム金属、ガラス状カーボン、シリコン単結晶
等が知られている。2. Description of the Related Art Conventionally, as a material for a plasma device such as an electrode, a shield ring, and a buffer plate, anodized aluminum metal, glassy carbon, silicon single crystal, and the like are known.
【０００３】しかしながら、これらの材料のうち、アル
ミニウム金属、ガラス状カーボンはいずれも、プラズマ
処理中にプラズマ装置用素材から粒子が脱落することに
起因するパーティクル汚染が発生し易いという問題点を
有しており、またシリコン単結晶はプラズマ装置内に供
給されるガスと反応し、耐久性に乏しいという問題点を
有している。However, among these materials, aluminum metal and glassy carbon all have a problem that particles are easily contaminated due to particles falling off from the material for plasma devices during plasma processing. In addition, the silicon single crystal has a problem that it reacts with a gas supplied into the plasma apparatus and has poor durability.
【０００４】[0004]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、上述のごとき問題点を解決することのでき
る耐プラズマ性に優れたプラズマ装置用素材、即ち粒子
脱落によるパーティクル汚染の発生が少なく、耐久性に
優れたプラズマ装置用炭化珪素焼結体及びプラズマ装置
用炭化珪素焼結体の製造方法を提供することである。The problem to be solved by the present invention is that a material for a plasma apparatus having excellent plasma resistance capable of solving the above-mentioned problems, that is, the generation of particle contamination due to falling off of particles. An object of the present invention is to provide a method for producing a silicon carbide sintered body for a plasma device and a silicon carbide sintered body for a plasma device, which is excellent in durability.
【０００５】[0005]
【課題を解決するための手段】上述のごとき課題は、密
度が２．７ｇ／ｃｍ3 以上、好ましくは３．０ｇ／ｃｍ
3 以上、結晶粒径の平均値が２０μｍ以上、熱伝導率が
８０Ｗ／ｍＫ以上、電気抵抗率が１０-2〜１０2 Ωｃｍ
であることを特徴とするプラズマ装置用炭化珪素焼結体
を使用することにより解決することができ、なかでもホ
ウ素を０．１５〜１．０重量％、またはアルミニウムを
０．５〜１０重量％、さらに遊離炭素を０．５〜１０重
量％含有してなるプラズマ装置用炭化珪素焼結体により
好適に解決することができる。ここで結晶粒径とは、焼
結体の任意の切断面において観察される結晶粒の長手方
向寸法をａとし、長手方向に対し垂直方向をｂとした場
合、（ａ＋ｂ）／２なる式で表される値である。Means for Solving the Problems] such problems described above, the density of 2.7 g / cm 3 or higher, preferably 3.0 g / cm
3 or more, average crystal grain size is 20 μm or more, thermal conductivity is 80 W / mK or more, and electric resistivity is 10 −2 to 10 2 Ωcm.
It can be solved by using a silicon carbide sintered body for a plasma device, wherein boron is 0.15 to 1.0% by weight or aluminum is 0.5 to 10% by weight. Further, the problem can be suitably solved by a silicon carbide sintered body for a plasma device further containing 0.5 to 10% by weight of free carbon. Here, the crystal grain size is expressed by (a + b) / 2, where a is a longitudinal dimension of a crystal grain observed on an arbitrary cut surface of the sintered body, and b is a direction perpendicular to the longitudinal direction. The value to be represented.
【０００６】[0006]
【作用】次に本発明を詳細に説明する。本発明の炭化珪
素焼結体は、密度が２．７ｇ／ｃｍ3 以上、さらに好ま
しくは３．０ｇ／ｃｍ3 以上、結晶粒径の平均値が２０
μｍ以上、熱伝導率が８０Ｗ／ｍＫ以上、電気抵抗率が
１０-2〜１０2 Ωｃｍであることが必要である。Next, the present invention will be described in detail. The silicon carbide sintered body of the present invention has a density of 2.7 g / cm 3 or more, more preferably 3.0 g / cm 3 or more, and an average crystal grain size of 20 g / cm 3 or more.
It is necessary that the thermal conductivity is not less than μm, the thermal conductivity is not less than 80 W / mK, and the electric resistivity is 10 −2 to 10 2 Ωcm.
【０００７】炭化珪素焼結体の密度が２．７ｇ／ｃｍ3
以上であることが必要である理由は、密度が２．７ｇ／
ｃｍ3 より低い焼結体は結晶粒子間の結合が弱いため、
耐プラズマ性に劣るからである。特に密度が３．０ｇ／
ｃｍ3 以上の炭化珪素焼結体は、焼結体内の気孔が極め
て少なく、粒子間結合が強固であるため耐プラズマ製に
優れている。The density of the silicon carbide sintered body is 2.7 g / cm 3
The reason why it is necessary that the density be 2.7 g /
Since the sintered body lower than 3 cm3 has weak bonding between crystal grains,
This is because it has poor plasma resistance. In particular, the density is 3.0 g /
A silicon carbide sintered body of cm 3 or more has very few pores in the sintered body and strong bonding between particles, so that it is excellent in plasma resistance.
【０００８】炭化珪素焼結体の結晶粒径の平均値が２０
μｍ以上であることが必要である理由は、結晶粒径の平
均値が２０μｍより小さいと結晶粒ごとに電荷がチャー
ジされるためプラズマによるアタックを受けやすく粒子
が脱落し易いからである。The average value of the crystal grain size of the silicon carbide sintered body is 20
The reason why it is necessary to be not less than μm is that if the average value of the crystal grain size is smaller than 20 μm, the charge is charged for each crystal grain, so that the particles are easily attacked by the plasma and the particles are easily dropped.
【０００９】炭化珪素焼結体の熱伝導率が８０Ｗ／ｍＫ
以上であることが必要である理由は、炭化珪素焼結体の
熱伝導率が８０Ｗ／ｍＫより低いと炭化珪素焼結体内で
温度のばらつきが生じ易くプラズマ電荷の均一性が損な
われ、装置の熱的定常状態を得にくいからであり、１０
０〜３００Ｗ／ｍＫの範囲の炭化珪素焼結体が好適であ
る。なお、プラズマ装置用の炭化珪素としては熱伝導率
は高ければ高い程好ましく、３００Ｗ／ｍＫより高いも
のとしては単結晶炭化珪素が知られているが、これは工
業的な材料にはなっていない。The thermal conductivity of the silicon carbide sintered body is 80 W / mK
The reason for the above requirement is that if the thermal conductivity of the silicon carbide sintered body is lower than 80 W / mK, temperature variation easily occurs in the silicon carbide sintered body, and the uniformity of the plasma charge is impaired. This is because it is difficult to obtain a thermal steady state.
A silicon carbide sintered body in the range of 0 to 300 W / mK is suitable. In addition, as silicon carbide for a plasma device, the higher the thermal conductivity is, the more preferable it is. As a material higher than 300 W / mK, single crystal silicon carbide is known, but this is not an industrial material. .
【００１０】電気抵抗率は、１０-2〜１０2 Ωｃｍの範
囲であることが好ましい。その理由は、電気抵抗率が１
０2 Ωｃｍより高いと局部的に電荷がチャージされるた
めプラズマによりアタックを受けやすくプラズマにより
粒子が脱落し易いからであり、一方１０-2Ωｃｍより低
い炭化珪素焼結体は、電荷の局部的なチャージを防ぐ上
からはなるべく低いほうが好ましく、炭化珪素焼結体の
電気抵抗率を低くする手段としては、炭化珪素の粒界に
導電材を多く入れる手段が考えられるが、この手段で
は、不純物増加により粒界が弱くなるという問題点があ
る。The electric resistivity is preferably in the range of 10 -2 to 10 2 Ωcm. The reason is that the electrical resistivity is 1
If it is higher than 0 2 Ωcm, the electric charge is locally charged, so that it is easily attacked by the plasma and the particles are easily dropped off by the plasma. On the other hand, the silicon carbide sintered body lower than 10 −2 Ωcm has a low local electric charge. It is preferable to lower the electrical resistivity of the silicon carbide sintered body as much as possible from the viewpoint of preventing excessive charge. As a means for lowering the electrical resistivity of the silicon carbide sintered body, a means of adding a large amount of a conductive material to a grain boundary of silicon carbide can be considered. There is a problem that the grain boundary is weakened by the increase.
【００１１】本発明の結晶粒径が大きく、熱伝導性およ
び電気伝導性の高い炭化珪素焼結体がプラズマ装置用と
して優れている理由は、耐プラズマ性においてプラズマ
にエッチングされ粒子が脱落し易いというウィークポイ
ントが、粒界を減らすために結晶粒径を大きく制御する
と同時に、プラズマ装置のプラズマ均一性を確保するた
めである。The reason that the silicon carbide sintered body of the present invention having a large crystal grain size and high thermal conductivity and electric conductivity is excellent for a plasma device is that the particles are easily etched by plasma in plasma resistance and fall off easily. The weak point is to control the crystal grain size to a large extent in order to reduce the grain boundaries, and at the same time, to secure the plasma uniformity of the plasma device.
【００１２】本発明の炭化珪素焼結体によれば、ホウ素
を０．１５〜１．０重量％、またはアルミニウムを０．
５〜１０重量％、さらに遊離炭素を０．５〜１０重量％
含有していることにより、粒成長を促進させ、粒界が少
なくすることにより、緻密なプラズマ装置用炭化珪素焼
結体を得ることができる。According to the silicon carbide sintered body of the present invention, 0.15 to 1.0% by weight of boron or 0.1% by weight of aluminum is used.
5 to 10% by weight, further free carbon is 0.5 to 10% by weight
The inclusion promotes grain growth and reduces the number of grain boundaries, so that a dense silicon carbide sintered body for a plasma device can be obtained.
【００１３】また、上記組成の炭化珪素焼結体は、本発
明によれば以下の工程により得ることができる。 第１工程 平均粒径が２．０μｍ以下の炭化珪素であ
って、この粉末はα型、β型および／または非晶質炭化
珪素と不可避的不純物とからなる炭化珪素粉末である出
発原料であって、この粉末１００重量部に対し、アルミ
ニウム、二ホウ化アルミニウム、炭化アルミニウム、窒
化アルミニウム、酸化アルミニウム、ホウ素、炭化ホウ
素、窒化ホウ素、酸化ホウ素、炭素のなかから選ばれる
いずれか１種または２種以上を０．３〜２０重量部を均
一に混合する工程； 第２工程 前記第１工程により得られた混合物を成形
する工程；および 第３工程 前記第２工程により得られた成形体を２０
００〜２４００℃の温度範囲内で焼成する工程。According to the present invention, a silicon carbide sintered body having the above composition can be obtained by the following steps. First Step Silicon carbide having an average particle size of 2.0 μm or less, and this powder is a starting material that is a silicon carbide powder composed of α-type, β-type and / or amorphous silicon carbide and unavoidable impurities. And with respect to 100 parts by weight of this powder, any one or two selected from aluminum, aluminum diboride, aluminum carbide, aluminum nitride, aluminum oxide, boron, boron carbide, boron nitride, boron oxide, and carbon A step of uniformly mixing 0.3 to 20 parts by weight of the above; a second step, a step of molding the mixture obtained in the first step; and a third step, the molding obtained in the second step is 20
Baking in the temperature range of 00 to 2400 ° C.
【００１４】上記工程で出発原料の炭化珪素粉末の平均
粒径が２．０μｍ以上であると、焼結用助剤を添加して
も炭化珪素焼結体の緻密質化は起き難く，成長粒子の間
に気孔が残り、そこからプラズマのアタックを受けやす
いからである。また、焼成温度は２０００〜２４００℃
が好適であり、該焼成温度が２０００℃より低いと構成
粒子の粒径を、２０μｍより大きくすることは困難であ
るばかりでなく気孔も残る。また、２４００℃より高い
と、炭化珪素の分解が発生し構造体としての最低必要な
強度の劣化が発生するという問題点がある。If the average particle size of the silicon carbide powder as the starting material in the above step is 2.0 μm or more, the densification of the silicon carbide sintered body hardly occurs even when a sintering aid is added, and This is because pores remain between them and plasma attack is apt to occur therefrom. The firing temperature is 2000-2400 ° C.
If the firing temperature is lower than 2000 ° C., it is difficult not only to make the particle diameter of the constituent particles larger than 20 μm, but also pores remain. On the other hand, when the temperature is higher than 2400 ° C., there is a problem that silicon carbide is decomposed and the minimum required strength of the structure is deteriorated.
【００１５】[0015]
【発明の実施の形態】次に本発明を実施例および比較例
について説明する。Next, the present invention will be described with reference to examples and comparative examples.
【００１６】実施例１ 出発原料として使用した炭化珪素微粉末には９４．６重
量％がβ型結晶よりなるイビデン株式会社製ベ−タラン
ダム、１．５重量％のホウ素、３．６重量％の遊離炭素
を主として含有し、１．３μｍの平均粒径を有してい
た。Example 1 A silicon carbide fine powder used as a starting material was composed of 94.6% by weight of beta-type crystals, beta random, manufactured by Ibiden Co., Ltd., 1.5% by weight of boron, 3.6% by weight. Of free carbon, and had an average particle size of 1.3 μm.
【００１７】前記炭化珪素微粉末１００重量部に対し、
ポリビニルアルコ−ル５重量部、水３００重量部を配合
し、ボ−ルミル中で５時間混合した後乾燥した。この乾
燥混合物を適量採取し、顆粒化した後金属製押し型を用
いて５０ｋｇ／ｃｍ2 の圧力で成形した。この生成形体
の密度は１．２ｇ／ｃｍ3 であった。前記生成形体を外
気を遮断することのできる黒鉛製ルツボに装入し、タン
マン型焼成炉を使用して１気圧のアルゴンガス雰囲気中
で焼成した。なお、焼成は１０℃／分で２３００℃まで
昇温し、最高温度２３００℃で２時間保持した。得られ
た焼結体の結晶構造は、結晶粒径の平均値（ａ＋ｂ）／
２が５０μｍの板状結晶が多方向に絡み合った三次元構
造を有しており、結晶粒径の平均値が２０〜８０μｍの
板状結晶の含有率は全重量の６２％であった。With respect to 100 parts by weight of the silicon carbide fine powder,
5 parts by weight of polyvinyl alcohol and 300 parts by weight of water were mixed, mixed in a ball mill for 5 hours, and dried. An appropriate amount of the dried mixture was collected, granulated, and then molded at a pressure of 50 kg / cm 2 using a metal mold. The density of this green compact was 1.2 g / cm 3 . The green compact was placed in a graphite crucible capable of shutting off outside air, and was fired in a 1-atmosphere argon gas atmosphere using a Tamman-type firing furnace. In the firing, the temperature was raised to 2300 ° C. at a rate of 10 ° C./min and kept at a maximum temperature of 2300 ° C. for 2 hours. The crystal structure of the obtained sintered body is represented by the average value of the crystal grain size (a + b) /
2 had a three-dimensional structure in which plate crystals of 50 μm were entangled in multiple directions, and the content of the plate crystals having an average crystal grain size of 20 to 80 μm was 62% of the total weight.
【００１８】また、得られた焼結体の密度を測定したと
ころ、３．１ｇ／ｃｍ2 であり、熱伝導率は１５０Ｗ／
ｍＫ、電気抵抗率は６０Ωｃｍであった。焼結体に含有
されるホウ素は０．４重量％、遊離炭素は１．８重量％
であった。得られた焼結体表面をラップ研磨した後，超
純水にて洗浄乾燥され、パーティクルカウンターにて
０．５μｍ以上のパーティクルが０個／ｃｍ2 であるこ
とが確認された単結晶シリコンウエハー上に乗せ，３０
０Ｗのアルゴンプラズマ装置にてアルゴンガス：：酸素
ガス：フッ化炭素ガス＝１：０．６：０．３５の混合プ
ラズマガスを１２時間焼結体に照射した。その後、シリ
コンウエハー上の０．５μｍ以上のパーティクルをカウ
ンターにて測定したところ０．３個／ｃｍ2 であった。When the density of the obtained sintered body was measured, it was 3.1 g / cm 2 and the thermal conductivity was 150 W / cm 2.
mK and electric resistivity were 60 Ωcm. 0.4% by weight of boron contained in the sintered body and 1.8% by weight of free carbon
Met. The surface of the obtained sintered body was lapped and polished, washed and dried with ultrapure water, and measured on a single crystal silicon wafer having a particle counter of 0.5 μm or more particles of 0 / cm 2. And put on 30
The sintered body was irradiated with a mixed plasma gas of argon gas :: oxygen gas: carbon fluoride gas = 1: 0.6: 0.35 for 12 hours using a 0 W argon plasma apparatus. Thereafter, when particles of 0.5 μm or more on the silicon wafer were measured by a counter, it was 0.3 particles / cm 2 .
【００１９】実施例２ 出発原料として使用した炭化珪素微粉末は９４．６重量
％がβ型結晶よりなり、１０重量％のアルミニウム、
５．５重量％の遊離炭素を主として含有し、０．４μｍ
の平均粒径を有していた。Example 2 The silicon carbide fine powder used as a starting material was composed of 94.6% by weight of β-type crystal, 10% by weight of aluminum,
Containing mainly 5.5% by weight of free carbon,
Average particle size.
【００２０】前記炭化珪素微粉末１００重量部に対し、
ポリビニルアルコ−ル５重量部、水３００重量部を配合
し、ボ−ルミル中で５時間混合した後乾燥した。この乾
燥混合物を適量採取し、実施例１と同様の方法で生成形
し、該生成形体を黒鉛製ルツボに装入し、タンマン型焼
成炉を使用して１気圧のアルゴンガス雰囲気中で焼成し
た。なお、焼成は１５ ℃／分で２２００℃まで昇温
し、最高温度２２００℃で５時間保持した。得られた焼
結体の結晶構造は、結晶粒径の平均値（ａ＋ｂ）／２が
５０μｍの板状結晶が多方向に絡み合った三次元構造を
有しており、結晶粒径の平均値が２０〜８０μｍの板状
結晶の含有率は全重量の７８％であった。With respect to 100 parts by weight of the silicon carbide fine powder,
5 parts by weight of polyvinyl alcohol and 300 parts by weight of water were mixed, mixed in a ball mill for 5 hours, and dried. An appropriate amount of the dried mixture was sampled, formed in the same manner as in Example 1, charged into a graphite crucible, and fired in a 1-atmosphere argon gas atmosphere using a tanman type firing furnace. . In the firing, the temperature was raised to 2200 ° C. at a rate of 15 ° C./min and maintained at a maximum temperature of 2200 ° C. for 5 hours. The crystal structure of the obtained sintered body has a three-dimensional structure in which plate-like crystals having an average value of crystal grain size (a + b) / 2 of 50 μm are entangled in multiple directions. The content of the plate-like crystals of 20 to 80 μm was 78% of the total weight.
【００２１】また、得られた焼結体の密度を測定したと
ころ、３．１ｇ／ｃｍ2 であり、熱伝導率は１７０Ｗ／
ｍＫ、電気抵抗率は０．１Ωｃｍであった。焼結体に含
有されるアルミニウムは２．６重量％、遊離炭素は３．
２ 重量％であった。さらに得られた焼結体を実施例１
と同様に研磨し，同様に、３００Ｗのアルゴンプラズマ
装置にて混合プラズマガスを１２時間焼結体に照射し
た。その後、シリコンウエハー上の０．５μｍ以上のパ
ーティクルをカウンターにて測定したところ０．２個／
ｃｍ2 であった。When the density of the obtained sintered body was measured, it was 3.1 g / cm 2 and the thermal conductivity was 170 W / cm 2.
mK and electrical resistivity were 0.1 Ωcm. 2.6% by weight of aluminum contained in the sintered body and 3.
2% by weight. Further, the obtained sintered body was used in Example 1
Similarly, the sintered body was irradiated with a mixed plasma gas for 12 hours using a 300 W argon plasma apparatus. After that, particles having a size of 0.5 μm or more on the silicon wafer were measured by a counter to find that 0.2 particles /
cm 2 .
【００２２】比較例１ 出発原料として使用した炭化珪素微粉末は９４．６重量
％がβ型結晶よりなり、０．１重量％のホウ素、１．２
重量％の遊離炭素を主として含有し、２．７μｍの平均
粒径を有していた。Comparative Example 1 The silicon carbide fine powder used as a starting material was composed of 94.6% by weight of β-type crystal, 0.1% by weight of boron and 1.2% by weight.
It mainly contained free carbon by weight and had an average particle size of 2.7 μm.
【００２３】前記炭化珪素微粉末１００重量部に対し、
ポリビニルアルコ−ル５重量部、水３００重量部を配合
し、ボ−ルミル中で５時間混合した後乾燥した。この乾
燥混合物を適量採取し、実施例１と同様の方法で生成形
し、該生成形体を黒鉛製ルツボに装入し、タンマン型焼
成炉を使用して１気圧のアルゴンガス雰囲気中で焼成し
た。なお、焼成は５℃／分で２１００℃まで昇温し、最
高温度２３００℃で５時間保持した。得られた焼結体の
結晶構造は、結晶粒径の平均値（ａ＋ｂ）／２が５０μ
ｍの板状結晶が多方向に絡み合った三次元構造を有して
おり、結晶粒径の平均値が２０〜８０μｍの板状結晶の
含有率は全重量の２５％であった。With respect to 100 parts by weight of the silicon carbide fine powder,
5 parts by weight of polyvinyl alcohol and 300 parts by weight of water were mixed, mixed in a ball mill for 5 hours, and dried. An appropriate amount of the dried mixture was sampled, formed in the same manner as in Example 1, charged into a graphite crucible, and fired in a 1-atmosphere argon gas atmosphere using a tanman type firing furnace. . In the firing, the temperature was raised to 2100 ° C. at a rate of 5 ° C./min and maintained at a maximum temperature of 2300 ° C. for 5 hours. The crystal structure of the obtained sintered body is such that the average (a + b) / 2 of the crystal grain size is 50 μm.
m had a three-dimensional structure in which plate-shaped crystals were intertwined in multiple directions, and the content of plate-shaped crystals having an average crystal grain size of 20 to 80 μm was 25% of the total weight.
【００２４】また、得られた焼結体の密度を測定したと
ころ、２．３ｇ／ｃｍ2 であり、熱伝導率は３５Ｗ／ｍ
Ｋ、電気抵抗率は４２０００Ωｃｍであった。焼結体に
含有されるホウ素は０．０５重量％、遊離炭素は１．０
重量％であった。さらに得られた焼結体を実施例１と同
様に研磨し，同様に、３００Ｗのアルゴンプラズマ装置
にて混合プラズマガスを１２時間焼結体に照射した。そ
の後、シリコンウエハー上の０．５μｍ以上のパーティ
クルをカウンターにて測定したところ６１．８個／ｃｍ
2 であった。When the density of the obtained sintered body was measured, it was 2.3 g / cm 2 and the thermal conductivity was 35 W / m 2.
K, the electrical resistivity was 42000 Ωcm. The sintered body contains 0.05% by weight of boron and 1.0% of free carbon.
% By weight. Further, the obtained sintered body was polished in the same manner as in Example 1, and similarly, the sintered body was irradiated with a mixed plasma gas for 12 hours using a 300 W argon plasma apparatus. Thereafter, when particles of 0.5 μm or more on the silicon wafer were measured by a counter, it was 61.8 particles / cm.
Was 2 .
【００２５】比較例２ 出発原料として使用した炭化珪素微粉末は９４．６重量
％がβ型結晶よりなり、０．３重量％のアルミニウム、
３．０重量％の遊離炭素を主として含有し、１．７μｍ
の平均粒径を有していた。Comparative Example 2 The silicon carbide fine powder used as a starting material was composed of 94.6% by weight of β-type crystal, 0.3% by weight of aluminum,
Mainly containing 3.0% by weight of free carbon, 1.7 μm
Average particle size.
【００２６】前記炭化珪素微粉末１００重量部に対し、
ポリビニルアルコ−ル５重量部、水３００重量部を配合
し、ボ−ルミル中で５時間混合した後乾燥した。この乾
燥混合物を適量採取し、実施例１と同様の方法で生成形
し、該生成形体を黒鉛製ルツボに装入し、タンマン型焼
成炉を使用して１気圧のアルゴンガス雰囲気中で焼成し
た。なお、焼成は２０℃／分で１８００℃まで昇温し、
最高温度１８００℃で１時間保持した。得られた焼結体
の結晶構造は、結晶粒径の平均値（ａ＋ｂ）／２が５０
μｍの板状結晶が多方向に絡み合った三次元構造を有し
ており、結晶粒径の平均値が２０〜８０μｍの板状結晶
の含有率は全重量の３０％であった。With respect to 100 parts by weight of the silicon carbide fine powder,
5 parts by weight of polyvinyl alcohol and 300 parts by weight of water were mixed, mixed in a ball mill for 5 hours, and dried. An appropriate amount of the dried mixture was sampled, formed in the same manner as in Example 1, charged into a graphite crucible, and fired in a 1-atmosphere argon gas atmosphere using a tanman type firing furnace. . In addition, baking raises temperature to 1800 degreeC at 20 degreeC / min,
The temperature was kept at a maximum temperature of 1800 ° C. for 1 hour. The crystal structure of the obtained sintered body is such that the average value of the crystal grain size (a + b) / 2 is 50.
It had a three-dimensional structure in which plate-like crystals of μm were entangled in multiple directions, and the content of plate-like crystals having an average crystal grain size of 20 to 80 μm was 30% of the total weight.
【００２７】また、得られた焼結体の密度を測定したと
ころ、２．０ｇ／ｃｍ2 であり、熱伝導率は３０Ｗ／ｍ
Ｋ、電気抵抗率は１８０００ Ωｃｍであった。焼結体
に含有されるアルミニウムは０．０９重量％、遊離炭素
は２．８重量％であった。さらに得られた焼結体を実施
例１と同様に研磨し、３００Ｗのアルゴンガスプラズマ
装置にて混合プラズマガスを１２時間焼結体に照射し
た。その後、シリコンウエハー上の０．５μｍ以上のパ
ーティクルをカウンターにて測定したところ２９．８個
／ｃｍ2 であった。実施例１及び２、比較例１及び２の
実施条件及び結果を表１に示す。When the density of the obtained sintered body was measured, it was 2.0 g / cm 2 and the thermal conductivity was 30 W / m 2.
K, the electrical resistivity was 18000 Ωcm. Aluminum contained in the sintered body was 0.09% by weight, and free carbon was 2.8% by weight. Further, the obtained sintered body was polished in the same manner as in Example 1, and the sintered body was irradiated with a mixed plasma gas for 12 hours using a 300 W argon gas plasma apparatus. After that, particles of 0.5 μm or more on the silicon wafer were measured by a counter to find that they were 29.8 particles / cm 2 . Table 1 shows the conditions and results of Examples 1 and 2 and Comparative Examples 1 and 2.
【００２８】実施例３〜７ 実施例１と同様であるが、表１に示した如き出発原料お
よび焼温速度でもって炭化珪素焼結体を製造した。な
お、実施例３及び実施例５において用いたα型炭化珪素
粉末には屋久島電工（株）製ＯＹ１５を使用した。Examples 3 to 7 The procedure of Example 1 was repeated, except that a sintered silicon carbide body was produced using the starting materials and the sintering temperature shown in Table 1. In addition, OY15 manufactured by Yakushima Electric Works, Ltd. was used for the α-type silicon carbide powder used in Examples 3 and 5.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】以上説明したように本発明のプラズマ装
置用炭化珪素焼結体及びプラズマ装置用炭化珪素焼結体
の製造方法によれば、密度が２．７ｇ／ｃｍ3 以上、結
晶粒径の平均値が２０μｍ以上、熱伝導率が８０ｗ／ｍ
Ｋ以上、電気抵抗率が１０-2〜１０2 Ωｃｍであるた
め、耐プラズマ性に優れた、即ち粒子脱落によるパーテ
ィクル汚染の発生が少なく、耐久性に優れたプラズマ装
置用炭化珪素焼結体を得ることができる。As described above, according to the silicon carbide sintered body for a plasma apparatus and the method for manufacturing a silicon carbide sintered body for a plasma apparatus of the present invention, the density is 2.7 g / cm 3 or more and the crystal grain size is Has an average value of 20 μm or more and a thermal conductivity of 80 w / m.
K or more, the electrical resistivity is 10 −2 to 10 2 Ωcm, so that a silicon carbide sintered body for a plasma device having excellent plasma resistance, that is, less occurrence of particle contamination due to particle detachment, and excellent durability can be obtained. Obtainable.
Claims (5)
の平均値が２０μｍ以上、熱伝導率が８０ｗ／ｍＫ以
上、電気抵抗率が１０-2〜１０2 Ωｃｍであることを特
徴とするプラズマ装置用炭化珪素焼結体。1. A material having a density of 2.7 g / cm 3 or more, an average crystal grain size of 20 μm or more, a thermal conductivity of 80 w / mK or more, and an electric resistivity of 10 −2 to 10 2 Ωcm. A silicon carbide sintered body for a plasma device.
炭素を０．５〜１０重量％含有してなる請求項１記載の
プラズマ装置用炭化珪素焼結体。2. The silicon carbide sintered body for a plasma device according to claim 1, comprising 0.15 to 1.0% by weight of boron and 0.5 to 10% by weight of free carbon.
離炭素を０．５〜１０重量％含有してなる請求項１記載
のプラズマ装置用炭化珪素焼結体。3. The silicon carbide sintered body for a plasma device according to claim 1, comprising 0.5 to 10% by weight of aluminum and 0.5 to 10% by weight of free carbon.
不純物含有率が０．０１重量％以下である請求項１記載
のプラズマ装置用炭化珪素焼結体。4. The silicon carbide sintered body for a plasma device according to claim 1, wherein the content of impurities other than boron, aluminum and free carbon is 0.01% by weight or less.
からなる密度が２．７ｇ／ｃｍ3 以上、結晶粒径の平均
値が２０μｍ以上、熱伝導率が８０ｗ／ｍＫ以上、電気
抵抗率が１０-2〜１０2 Ωｃｍであるプラズマ装置用炭
化珪素焼結体の製造方法。 第１工程 平均粒径が２．０μｍ以下の炭化珪素であ
って、この粉末はα型、β型および／または非晶質炭化
珪素であって不可避的不純物の含有量が０．０１重量％
以下の炭化珪素粉末１００重量部に対し、アルミニウ
ム、二ホウ化アルミニウム、炭化アルミニウム、窒化ア
ルミニウム、酸化アルミニウム、ホウ素、炭化ホウ素、
窒化ホウ素、酸化ホウ素、炭素のなかから選ばれるいず
れか１種または２種以上を０．３〜２０重量部を均一に
混合する工程； 第２工程 前記第１工程により得られた混合物を成形
する工程；および 第３工程 前記第２工程により得られた成形体を２０
００〜２４００℃の温度範囲内で焼成する工程。5. The following first to third steps have a density of 2.7 g / cm 3 or more, an average crystal grain size of 20 μm or more, a thermal conductivity of 80 w / mK or more, A method for producing a silicon carbide sintered body for a plasma device having a resistivity of 10 -2 to 10 2 Ωcm. First Step: Silicon carbide having an average particle size of 2.0 μm or less, and this powder is α-type, β-type and / or amorphous silicon carbide, and has an unavoidable impurity content of 0.01% by weight.
For the following silicon carbide powder 100 parts by weight, aluminum, aluminum diboride, aluminum carbide, aluminum nitride, aluminum oxide, boron, boron carbide,
A step of uniformly mixing 0.3 to 20 parts by weight of one or more selected from boron nitride, boron oxide, and carbon; second step; molding the mixture obtained in the first step. And a third step. The molded body obtained in the second step is
Baking in the temperature range of 00 to 2400 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10032253A JPH11217268A (en) | 1998-01-28 | 1998-01-28 | Silicon carbide sintered compact for plasma apparatus and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10032253A JPH11217268A (en) | 1998-01-28 | 1998-01-28 | Silicon carbide sintered compact for plasma apparatus and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11217268A true JPH11217268A (en) | 1999-08-10 |
Family
ID=12353863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10032253A Pending JPH11217268A (en) | 1998-01-28 | 1998-01-28 | Silicon carbide sintered compact for plasma apparatus and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11217268A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10280121B2 (en) | 2015-03-31 | 2019-05-07 | Hokuriku Seikei Industrial Co., Ltd. | Silicon carbide member for plasma processing apparatus |
| KR102124766B1 (en) * | 2019-12-31 | 2020-06-19 | (주)삼양컴텍 | Plasma processing apparatus and manufacturing method of the same |
| US11264214B2 (en) | 2016-09-27 | 2022-03-01 | Hokuriku Seikei Industrial Co., Ltd. | Silicon carbide member for plasma processing apparatus, and production method therefor |
-
1998
- 1998-01-28 JP JP10032253A patent/JPH11217268A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10280121B2 (en) | 2015-03-31 | 2019-05-07 | Hokuriku Seikei Industrial Co., Ltd. | Silicon carbide member for plasma processing apparatus |
| US11264214B2 (en) | 2016-09-27 | 2022-03-01 | Hokuriku Seikei Industrial Co., Ltd. | Silicon carbide member for plasma processing apparatus, and production method therefor |
| KR102124766B1 (en) * | 2019-12-31 | 2020-06-19 | (주)삼양컴텍 | Plasma processing apparatus and manufacturing method of the same |
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