JP5122593B2 - MoSi2 powder, method for producing the powder, heating element using the powder, and method for producing the heating element - Google Patents
MoSi2 powder, method for producing the powder, heating element using the powder, and method for producing the heating element Download PDFInfo
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Description
本発明は、５７３°Ｋ〜８７３°Ｋの範囲で、ＭｏとＳｉの同時酸化が起こり、さらにＭｏ酸化物の蒸発減少が伴うという、ペスト（粉化現象）防止できるＭｏＳｉ２粉末、同粉末の製造方法、同粉末を用いた発熱体及び発熱体の製造方法に関する。
なお、本明細書で使用するＭｏＳｉ２を主成分として８０ｗｔ％以上含む基材は、ＭｏＳｉ２基材に絶縁性酸化物であるＳｉＯ２を含有させて電気抵抗を増加させたＭｏＳｉ２を主成分とする発熱体に適用できるものであり、該発熱体に供することのできるＭｏＳｉ２粉末及び方法である。
The present invention is in the range of 573 ° K~873 ° K, occurs simultaneous oxidation of Mo and Si, that further involves evaporation reduction of Mo oxide, plague (powdering phenomenon) preventing it MoSi 2 powder, the same powder The present invention relates to a manufacturing method, a heating element using the same powder, and a manufacturing method of the heating element.
Incidentally, 80 wt% or more comprises a base material MoSi 2 to be used herein as the main component is composed mainly of a MoSi 2 substrate contain a SiO 2 which is an insulating oxide MoSi 2 having an increased electrical resistance This is a MoSi 2 powder and method that can be applied to the heating element.
最近、半導体デバイスの微細化及びデバイス製造時間の短縮化と省エネルギー化のために、従来の金属発熱体に替えて、ＣＶＤ装置や拡散炉等の半導体製造装置に、ＭｏＳｉ２を主成分とする高出力性能の発熱体が利用されるようになってきた。
一般に、半導体製造装置に使用される熱処理炉は炉内の温度分布を厳密に制御するなど、非常に高精度な温度特性が要求されるが、ＭｏＳｉ２を主成分とする発熱体は優れた耐熱特性を有し、金属発熱体の約１０倍の表面負荷が可能であり、また急速加熱昇温することができるという大きな特長を有するので、好適な材料と言える。
Recently, in order to miniaturize semiconductor devices, shorten device manufacturing time, and save energy, instead of conventional metal heating elements, semiconductor manufacturing equipment such as CVD equipment and diffusion furnaces have high MoSi 2 content. Output performance heating elements have come to be used.
Generally, heat treatment furnaces used in semiconductor manufacturing equipment require extremely high-precision temperature characteristics such as strictly controlling the temperature distribution in the furnace, but heating elements based on MoSi 2 have excellent heat resistance. It is a suitable material because it has such characteristics as being capable of surface loading about 10 times that of a metal heating element and capable of rapid heating and heating.
ところが、ＭｏＳｉ２を主成分とする発熱体は５７３°Ｋ〜８７３°Ｋの範囲で、ＭｏとＳｉの同時酸化が起こり、さらにＭｏ酸化物の蒸発減少が伴う、ペスト（粉化現象）という低温酸化が起こるという問題がある。
通常、これを防止するために１５００°Ｋ以上で酸化処理して緻密なシリカ保護被膜を形成する等、発熱体自体の材料開発がなされている。
However, a heating element mainly composed of MoSi 2 has a low temperature called pest (powdering phenomenon) in which the simultaneous oxidation of Mo and Si occurs in the range of 573 ° K to 873 ° K and evaporation of Mo oxide further decreases. There is a problem that oxidation occurs.
Usually, in order to prevent this, materials for the heating element itself have been developed, such as forming a dense silica protective film by oxidizing at 1500 ° K. or higher.
例えば、ペスト（粉化現象）対策として、二珪化モリブデン系セラミックス発熱体において、ＭｏＳｉ２で表せる組成を有する発熱体の不純物としてＦｅ、Ｃｕ、Ａｕ、Ｃａ、Ａｌがそれぞれ０．０５ｍａｓｓ％以下であり、かつ不純物総量が０．１ｍａｓｓ％以下であり、さらに導電性金属をコーティングした給電部を除いた部分で、膜厚が１０〜１００μｍのシリカ保護皮膜がＭｏＳｉ２セラミックス表面を被覆しているという低温加熱寿命が長い二珪化モリブデン系セラミックス発熱体が提案されている（特許文献１参照）。 For example, as a countermeasure against pest (powdering phenomenon), in a molybdenum disilicide ceramic heating element, Fe, Cu, Au, Ca and Al are 0.05 mass% or less as impurities of the heating element having a composition expressed by MoSi 2 . And the total amount of impurities is 0.1 mass% or less, and the silica protective film having a film thickness of 10 to 100 μm covers the surface of the MoSi 2 ceramic except the power supply portion coated with the conductive metal. A molybdenum disilicide ceramic heating element having a long heating life has been proposed (see Patent Document 1).
また、同ペスト（粉化現象）対策として、酸化保護皮膜を一旦形成した二珪化モリブデン系発熱値による加熱中に該酸化保護皮膜が破壊した際に、雰囲気の酸素濃度０．１〜７．０容量％、温度８５０〜１２００°Ｃの条件で二珪化モリブデン系発熱体を熱処理することにより酸化保護皮膜が破壊した発熱体表面に、厚さ０．５μｍ以上の緻密な酸化保護皮膜を生成させる二珪化モリブデン系発熱体の保護皮膜再生方法が開示されている（特許文献２参照）。 Further, as a countermeasure against the plague (powdering phenomenon), when the oxidation protective film is destroyed during heating by the molybdenum disilicide heat generation value once the oxidation protective film is formed, the oxygen concentration of the atmosphere is 0.1 to 7.0. A dense oxidation protective film having a thickness of 0.5 μm or more is formed on the surface of the heating element where the oxidation protection film is destroyed by heat-treating the molybdenum disilicide heating element under the conditions of volume% and temperature of 850 to 1200 ° C. A method for regenerating a protective film of a molybdenum silicide heating element is disclosed (see Patent Document 2).
また、同ペスト（粉化現象）対策として、二珪化モリブデン系複合セラミックス発熱体において、網目状構造を持つＭｏＳｉ２マトリックス中にＭｏＳｉ２に比べて比較的低融点のシリカ系酸化物相またはガラス相がＭｏＳｉ２結晶粒界に網状に分布している低温加熱寿命が長い二珪化モリブデン系複合セラミックス発熱体が開示されている（特許文献３参照）。
以上のペスト（粉化現象）対策としては、いずれもＭｏＳｉ２セラミックス表面シリカ保護皮膜を形成することが必要であり、そのための特別な熱処理工程が必須となる。しかし、このような保護皮膜を形成しても、ペスト（粉化現象）を十分に防止できないという問題があった。
As a countermeasure against the plague (powdering phenomenon), in a molybdenum disilicide-based composite ceramic heating element, a silica-based oxide phase or glass phase having a relatively low melting point compared to MoSi 2 in a MoSi 2 matrix having a network structure. Has disclosed a molybdenum disilicide-based composite ceramic heating element having a low temperature heating life and distributed in a mesh form at the MoSi 2 grain boundaries (see Patent Document 3).
As a countermeasure against the above plague (powdering phenomenon), it is necessary to form a MoSi 2 ceramic surface silica protective film, and a special heat treatment step for that purpose is essential. However, there is a problem that even if such a protective film is formed, the plague (powdering phenomenon) cannot be sufficiently prevented.
本発明は、５７３°Ｋ〜８７３°Ｋの範囲で、ＭｏとＳｉの同時酸化が起こり、さらにＭｏ酸化物の蒸発減少が伴うという、ペスト（粉化現象）を効果的に防止できるＭｏＳｉ２粉末、同粉末の製造方法、同粉末を用いた発熱体及び発熱体の製造方法に関する。特に、半導体製造装置用熱処理炉（酸化・拡散炉を含む）に有用である発熱体及びその製造方法を提供する。 The present invention is a MoSi 2 powder that can effectively prevent the pest (powdering phenomenon) that simultaneous oxidation of Mo and Si occurs in the range of 573 ° K to 873 ° K and further evaporation of the Mo oxide is accompanied. The present invention relates to a method for producing the powder, a heating element using the powder, and a method for producing the heating element. In particular, a heating element useful for a heat treatment furnace for semiconductor manufacturing equipment (including an oxidation / diffusion furnace) and a method for manufacturing the same are provided.
上記の課題を解決するために、本発明者らは、原料であるＭｏＳｉ２粉末を改善することにより、ＭｏＳｉ２を主成分とする発熱体のペスト（粉化現象）を効果的に防止でき、特に半導体製造装置用熱処理炉（酸化・拡散炉を含む）に有用であるＭｏＳｉ２を主成分として８０ｗｔ％以上含む発熱体を低コストで提供できるとの知見を得た。 In order to solve the above problems, the present inventors can effectively prevent the pest (powdering phenomenon) of a heating element mainly composed of MoSi 2 by improving the MoSi 2 powder as a raw material, In particular, the inventors have found that a heating element containing 80 wt% or more of MoSi 2 as a main component, which is useful for a heat treatment furnace for semiconductor manufacturing equipment (including an oxidation / diffusion furnace), can be provided at low cost.
本発明はこの知見に基づき、
１．ＭｏＳｉ２粉末の比表面積が０．２ｍ２／ｇ以上であり、かつ表面に酸化皮膜を備えることを特徴とするＭｏＳｉ２粉末
２．ＭｏＳｉ２粉末の酸素含有量が２０００ｐｐｍ以上であることを特徴とする発熱体用ＭｏＳｉ２粉末
３．ＭｏＳｉ２粉末の酸素含有量が１０００ｐｐｍ以上であることを特徴とする上記１記載の発熱体用ＭｏＳｉ２粉末
４．ＭｏＳｉ２を主成分として８０ｗｔ％以上含み、残余ＳｉＯ２と不純物からなることを特徴する上記１〜３のいずれかに記載のＭｏＳｉ２粉末を用いた発熱体、を提供する。
The present invention is based on this finding,
1. MoSi 2 specific surface area of the powder is not less 0.2 m 2 / g or more, and MoSi 2 powder 2, characterized in that it comprises an oxide film on the surface. Heating element MoSi 2 powder 3 MoSi 2 oxygen content of the powder is characterized in that at 2000ppm or more. Heating element of claim 1, wherein the the MoSi 2 oxygen content of the powder is characterized in that at 1000ppm or more MoSi 2 powder 4. A heating element using the MoSi 2 powder according to any one of the above 1 to 3, characterized by comprising 80 wt% or more of MoSi 2 as a main component and comprising residual SiO 2 and impurities.
また、本発明は、
５．ＭｏＳｉ２粉末を酸化性の酸又は酸化剤を含む酸で洗浄することを特徴とする発熱体用ＭｏＳｉ２粉末の製造方法
６．ＭｏＳｉ２粉末の表面に酸化皮膜を備えることを特徴とする上記５記載の発熱体用ＭｏＳｉ２粉末の製造方法
７．ＭｏＳｉ２粉末の比表面積が０．２ｍ２／ｇ以上であることを特徴とする上記５又は６記載の発熱体用ＭｏＳｉ２粉末の製造方法
８．ＭｏＳｉ２粉末の酸素含有量が２０００ｐｐｍ以上であることを特徴とする上記５〜７のいずれかに記載の発熱体用ＭｏＳｉ２粉末の製造方法
９．比表面積が０．２ｍ２／ｇ以上であるＭｏＳｉ２原料粉末を酸化性の酸又は酸化剤を含む酸で洗浄し乾燥する工程、ＳｉＯ２と混合粉砕する工程、バインダーと混合し脱脂する工程、通電焼結する工程からなることを特徴とするＭｏＳｉ２を主成分とする発熱体の製造方法
１０．脱脂後一次焼結する工程を含むことを特徴とする上記９記載のＭｏＳｉ２を主成分とする発熱体の製造方法、を提供する。
The present invention also provides:
5). Heating element MoSi 2 powder production method 6, characterized in that washing the MoSi 2 powder with an acid containing an oxidizing acid or oxidizing agent. Heating element MoSi 2 powder manufacturing method 7 above 5, wherein further comprising an oxide film on the surface of the MoSi 2 powder. 7. The method for producing MoSi 2 powder for a heating element as described in 5 or 6 above, wherein the specific surface area of the MoSi 2 powder is 0.2 m 2 / g or more. 8. The method for producing MoSi 2 powder for a heating element according to any one of 5 to 7 above, wherein the oxygen content of the MoSi 2 powder is 2000 ppm or more. A step of washing and drying MoSi 2 raw material powder having a specific surface area of 0.2 m 2 / g or more with an oxidizing acid or an acid containing an oxidizing agent, a step of mixing and grinding with SiO 2 , a step of mixing and degreasing with a binder, 9. A method of manufacturing a heating element mainly composed of MoSi 2 , comprising a step of conducting current sintering. The method for producing a heating element mainly comprising MoSi 2 as described in 9 above, comprising a step of primary sintering after degreasing.
本発明は原料であるＭｏＳｉ２粉末を酸化性の酸で洗浄し、同粉末を酸化膜で覆うことにより、ＭｏＳｉ２を主成分とする発熱体のペスト（粉化現象）を効果的に防止できるという優れた効果、すなわち、酸洗浄という比較的簡単な操作により、低コストで発熱体のペスト（粉化現象）を抑制し、発熱体の寿命を大幅に向上させることができるという著しい効果を有する。
また、同時にＭｏＳｉ２粉末内、すなわち同粉末を用いた発熱体内の不純物を低減することが可能であり、特に半導体ウエハの不純物による汚染を防止できるという効果を有する。
In the present invention, the MoSi 2 powder as a raw material is washed with an oxidizing acid, and the powder is covered with an oxide film, thereby effectively preventing the pest (powdering phenomenon) of the heating element mainly composed of MoSi 2. It has a remarkable effect that it can suppress the pest (powdering phenomenon) of the heating element at a low cost and can greatly improve the life of the heating element by a relatively simple operation such as acid cleaning. .
At the same time, it is possible to reduce impurities in the MoSi 2 powder, that is, the heat generating body using the powder, and in particular, it has an effect of preventing contamination of the semiconductor wafer by impurities.
本発明の発熱体は、ＭｏＳｉ２粉末の比表面積が０．２ｍ２／ｇ以上であり、かつ表面に酸化皮膜を有するＭｏＳｉ２粉末を使用する。この酸化皮膜は、硝酸又は過酸化水素等の酸化力が強い酸又は酸化剤を含む酸で洗浄することによって得ることができる。酸化力が強い酸であれば、例えば次亜塩素酸ナトリウム等を使用することもできる。
この酸化膜を形成したＭｏＳｉ２粉末は、そのトータルの酸素含有量を３０００ｐｐｍ以上とするのが望ましい。これによってＭｏＳｉ２粉末に十分な酸化膜を形成することができる。
Heating elements of the invention has a specific surface area of the MoSi 2 powder 0.2 m 2 / g or more, and use the MoSi 2 powder having an oxide film on the surface. This oxide film can be obtained by washing with an acid having strong oxidizing power such as nitric acid or hydrogen peroxide or an acid containing an oxidizing agent. For example, sodium hypochlorite may be used as long as it has strong oxidizing power.
The MoSi 2 powder on which this oxide film is formed preferably has a total oxygen content of 3000 ppm or more. As a result, a sufficient oxide film can be formed on the MoSi 2 powder.
本発明の発熱体は、ＭｏＳｉ２を主成分として８０ｗｔ％以上、好ましくは９０ｗｔ％以上含む基材であり、このＭｏＳｉ２基材に絶縁性酸化物であるＳｉＯ２を含有させて電気抵抗を増加させたＭｏＳｉ２を主成分とする発熱体に適用できる。
さらに、高純度シリカはガラス質形成材料として２０ｗｔ％以下、好ましくは１０ｗｔ％以下含有させる。これは、ＳｉＯ２の体積変化を伴う相転移を考慮したもので、ＳｉＯ２の含有量が多くなり過ぎるとその影響が大きくなり、発熱体の強度に支障をきたす可能性があるためである。
The heating element of the present invention is a base material containing MoSi 2 as a main component and containing 80 wt% or more, preferably 90 wt% or more, and the electric resistance is increased by adding SiO 2 as an insulating oxide to the MoSi 2 base material. It can be applied to a heating element mainly composed of MoSi 2 .
Further, high-purity silica is contained as a vitreous forming material in an amount of 20 wt% or less, preferably 10 wt% or less. This is because the phase transition accompanied by the volume change of SiO 2 is taken into account, and when the SiO 2 content is excessively large, the influence becomes large, which may hinder the strength of the heating element.
このＭｏＳｉ２製発熱体は、ＭｏＳｉ２原料粉を酸化性の酸又は酸化剤を含む酸で洗浄した後これを乾燥し、次にＳｉＯ２と混合粉砕した後、バインダーと混合し、さらに例えば押出しによって棒状又は平板状に成形する。
このようにして得た成形体を脱脂、一次焼結及び通電加熱焼結することによって、密度の高いＭｏＳｉ２製発熱体を製造する。
This MoSi 2 heating element is obtained by washing MoSi 2 raw material powder with an oxidizing acid or an acid containing an oxidizing agent, drying it, then mixing and grinding with SiO 2 , mixing with a binder, and further extruding, for example, To form a rod or flat plate.
The molded body thus obtained is degreased, primary sintered, and energized and heated to produce a MoSi 2 heating element having a high density.
さらに、このようにして作製した棒状又は平板状の発熱体を接合し、例えば円弧状又はＵ字形状等に製造する。このように、ＭｏＳｉ２製発熱体を各種の形状に成形した後、例えば半導体製造装置用熱処理炉に設置する。
上記のＭｏＳｉ２原料粉の酸による洗浄は、さほどの労力や費用を必要としない。それにもかかわらず、発熱体のペスト（粉化現象）を効果的に防止できる。
Furthermore, the rod-shaped or flat plate-shaped heating elements thus manufactured are joined and manufactured into, for example, an arc shape or a U-shape. Thus, after forming the MoSi 2 made heating element to various shapes, placed for example in a heat treatment furnace for semiconductor manufacturing equipment.
Cleaning of the MoSi 2 raw material powder with an acid does not require much labor and cost. Nevertheless, the plague (powdering phenomenon) of the heating element can be effectively prevented.
以下に実施例及び比較例を説明するが、本実施例は理解を容易にするためのものであり、本発明を制限するものではない。すなわち、本発明の技術思想の範囲内での他の変形あるいは他の実施例は、当然本発明に含まれる。 EXAMPLES Examples and comparative examples will be described below, but these examples are for ease of understanding and do not limit the present invention. That is, other modifications or other embodiments within the scope of the technical idea of the present invention are naturally included in the present invention.
（実施例１）
発熱体原料として純度３ＮレベルのＭｏＳｉ２粉末を用いた。これを硝酸で洗浄した。原料粉末及び酸による洗浄後の粉末の比表面積（ｍ２／ｇ）、酸素含有量（ｐｐｍ）、酸化膜の有無を表１に示す。表１に示すように、不純物量は酸による洗浄で著しく減少した。一方、酸化膜の形成により、酸素は９００ｐｐｍから３０００ｐｐｍに上昇した。また、ＭｏＳｉ２粉末の比表面積が０．１３ｍ２／ｇから２．５ｍ２／ｇとなった。
Example 1
MoSi 2 powder having a purity level of 3N was used as a heating element material. This was washed with nitric acid. Table 1 shows the specific surface area (m 2 / g), oxygen content (ppm), and presence / absence of an oxide film of the raw material powder and the powder after washing with an acid. As shown in Table 1, the amount of impurities was significantly reduced by washing with acid. On the other hand, oxygen rose from 900 ppm to 3000 ppm due to the formation of the oxide film. The specific surface area of the MoSi 2 powder became 2.5 m 2 / g from 0.13 m 2 / g.
上記ＭｏＳｉ２粉９５ｗｔ％とＳｉＯ２粉末５ｗｔ％とをバインダーと混合、（なお、バインダーは混合比率には計算しない。以下、同様とする。）、この混合物を型から押出して棒状の成形体とした。
この棒状の成形体（グリーン）を脱脂、一次焼結及び通電加熱焼結することによって、ＭｏＳｉ２製棒状発熱体を得た。
この発熱体について熱サイクル特性試験を実施した。この実施条件は、例えば１サイクル４８０°Ｃで１０時間保持する条件で行った。この結果、５００サイクル後でも粉状化（ペスト）せず、抗折試験でも３００ＭＰａ以上であった。
The above-mentioned MoSi 2 powder 95 wt% and SiO 2 powder 5 wt% are mixed with a binder (note that the binder is not calculated as a mixing ratio. The same shall apply hereinafter), and this mixture is extruded from a mold to form a rod-shaped molded body. did.
This rod-shaped molded body (green) was degreased, primary sintered and energized and heated to obtain a MoSi 2 rod-shaped heating element.
A heat cycle characteristic test was conducted on this heating element. This implementation condition was performed, for example, under the condition of holding one cycle at 480 ° C. for 10 hours. As a result, it was not pulverized (pested) even after 500 cycles, and was 300 MPa or more in the bending test.
（実施例２）
発熱体原料として純度３ＮレベルのＭｏＳｉ２粉末を用いた。この発熱体原料を塩酸と過酸化水素水で洗浄した。酸による洗浄後の粉末の比表面積（ｍ２／ｇ）、酸素含有量（ｐｐｍ）、酸化膜の有無を実施例１と同様に、表１に示す。酸化膜の形成により、酸素は９００ｐｐｍから４５００ｐｐｍの上昇し、また、ＭｏＳｉ２粉末の比表面積が０．１３ｍ２／ｇから３．０ｍ２／ｇとなった。
(Example 2)
MoSi 2 powder having a purity level of 3N was used as a heating element material. The heating element material was washed with hydrochloric acid and hydrogen peroxide. Table 1 shows the specific surface area (m 2 / g), oxygen content (ppm), and presence / absence of an oxide film after washing with acid in the same manner as in Example 1. The formation of the oxide film, oxygen is increased from 900ppm of 4500 ppm, a specific surface area of the MoSi 2 powder became 3.0 m 2 / g from 0.13 m 2 / g.
一方、ＳｉＯ２粉末は市販品を用いた。この市販品から不純物を選別除去した後、さらに１６５０°Ｃ以上の高温で長時間熱処理することにより、含有する金属成分を蒸発させて精製した材料を使用した。なお、ＳｉＯ２の高温熱処理は、実施例１と同様にＳｉＯ２の結晶構造を石英から高温で安定なクリストバライトに相転移させるために必要である。 On the other hand, a commercially available product was used as the SiO 2 powder. After selecting and removing impurities from this commercial product, a material purified by evaporating the metal component contained by further heat treatment at a high temperature of 1650 ° C. or higher was used. Incidentally, the high-temperature heat treatment of SiO 2 is required to phase transition to a stable cristobalite at high temperatures the crystal structure of SiO 2 of silica in the same manner as in Example 1.
上記ＭｏＳｉ２粉９５ｗｔ％とＳｉＯ２粉末５ｗｔ％とをバインダーと混合し、この混合物を型から押出して棒状の成形体とした。この棒状の成形体（グリーン）を脱脂、一次焼結及び通電加熱焼結することによって、ＭｏＳｉ２製棒状発熱体を得た。
この発熱体について熱サイクル特性試験を実施した。この実施条件は、例えば１サイクル４８０°Ｃで１０時間保持する条件で行った。この結果、５００サイクル後でも粉状化（ペスト）せず、抗折試験でも３００ＭＰａ以上であった。
The above-mentioned MoSi 2 powder 95 wt% and SiO 2 powder 5 wt% were mixed with a binder, and the mixture was extruded from a mold to form a rod-shaped molded body. This rod-shaped molded body (green) was degreased, primary sintered and energized and heated to obtain a MoSi 2 rod-shaped heating element.
A heat cycle characteristic test was conducted on this heating element. This implementation condition was performed, for example, under the condition of holding one cycle at 480 ° C. for 10 hours. As a result, it was not pulverized (pested) even after 500 cycles, and was 300 MPa or more in the bending test.
（実施例３）
発熱体原料として純度３ＮレベルのＭｏＳｉ２粉末を用いた。この発熱体原料を希硝酸で洗浄した。酸による洗浄後の粉末の比表面積（ｍ２／ｇ）、酸素含有量（ｐｐｍ）、酸化膜の有無を実施例１と同様に、表１に示す。酸化膜の形成により、酸素は９００ｐｐｍから２１００ｐｐｍの上昇した。また、ＭｏＳｉ２粉末の比表面積が０．１３ｍ２／ｇから２．１ｍ２／ｇとなった。
(Example 3)
MoSi 2 powder having a purity level of 3N was used as a heating element material. This heating element material was washed with dilute nitric acid. Table 1 shows the specific surface area (m 2 / g), oxygen content (ppm), and presence / absence of an oxide film after washing with acid in the same manner as in Example 1. Oxygen increased from 900 ppm to 2100 ppm due to the formation of the oxide film. The specific surface area of the MoSi 2 powder became 2.1 m 2 / g from 0.13 m 2 / g.
一方、ＳｉＯ２粉末には市販品を用い実施例１と同様に処理した。そして、上記ＭｏＳｉ２粉９５ｗｔ％とＳｉＯ２粉末５ｗｔ％とをバインダーと混合し、この混合物を型から押出して棒状の成形体とした。この棒状の成形体（グリーン）を脱脂、一次焼結及び通電加熱焼結することによって、ＭｏＳｉ２製棒状発熱体を得た。
この発熱体について、実施例１と同様に熱サイクル特性試験を実施した。この実施条件は、１サイクル４８０°Ｃで１０時間保持する条件で行った。この結果、５００サイクル後でも粉状化（ペスト）せず、抗折試験でも３００ＭＰａ以上であった。
On the other hand, it was treated in the same manner as in Example 1 using commercially available products the SiO 2 powder. Then, the above-described MoSi 2 powder 95 wt% and SiO 2 powder 5 wt% is mixed with a binder, the mixture was from the mold extruded and molded body of the rod-shaped. This rod-shaped molded body (green) was degreased, primary sintered and energized and heated to obtain a MoSi 2 rod-shaped heating element.
With respect to this heating element, a thermal cycle characteristic test was conducted in the same manner as in Example 1. This execution condition was carried out under the condition of holding for 10 hours at one cycle of 480 ° C. As a result, it was not pulverized (pested) even after 500 cycles, and was 300 MPa or more in the bending test.
（比較例１）
一般に高純度と言われている市販品のＭｏＳｉ２粉末９５ｗｔ％（Ｏ：９００ｗｔｐｐｍ）と、同様に市販品であるＳｉＯ２粉末５ｗｔ％とを微粉砕後、バインダーと混合し、この混合物を型から押出して棒状の成形体とした。
この棒状の成形体（グリーン）を脱脂、一次焼結及び通電加熱焼結することによって、ＭｏＳｉ２製棒状発熱体を得た。
(Comparative Example 1)
A commercially available MoSi 2 powder of 95 wt% (O: 900 wt ppm), which is generally said to be of high purity, and a commercially available SiO 2 powder of 5 wt% are finely pulverized and mixed with a binder, and this mixture is removed from the mold. Extruded into a rod-shaped molded body.
This rod-shaped molded body (green) was degreased, primary sintered and energized and heated to obtain a MoSi 2 rod-shaped heating element.
この発熱体について熱サイクル特性試験を実施した。この実施条件は、例えば１サイクル４８０°Ｃで１０時間保持する条件で行った。この結果、５０サイクル後でも粉状化（ペスト）がいたるところで起き、抗折試験では２００ＭＰａ以下となり、脆弱な発熱体となった。
以上から、半導体製造装置用熱処理炉と使用する場合、発熱体のペストが生じ、発熱体材としては好ましくない結果が得られた。
A heat cycle characteristic test was conducted on this heating element. This implementation condition was performed, for example, under the condition of holding one cycle at 480 ° C. for 10 hours. As a result, powdering (pest) occurred everywhere even after 50 cycles. In the bending test, the pressure became 200 MPa or less, and a brittle heating element was obtained.
From the above, when used with a heat treatment furnace for a semiconductor manufacturing apparatus, the heating element was plague, and an undesirable result was obtained as a heating element material.
本発明は原料であるＭｏＳｉ２粉末を酸化性の酸で洗浄し、同粉末を酸化膜で覆うことにより、ＭｏＳｉ２を主成分とする発熱体のペスト（粉化現象）を効果的に防止できるという優れた効果、すなわち、酸洗浄という比較的簡単な操作により、低コストで発熱体のペスト（粉化現象）を抑制し、発熱体の寿命を大幅に向上させることができるという著しい効果を有する。また、同時にＭｏＳｉ２粉末内、すなわち同粉末を用いた発熱体内の不純物を低減することが可能であり、特に半導体ウエハの不純物による汚染を防止できるという効果を有するので、特に、半導体製造装置用熱処理炉（酸化・拡散炉を含む）の発熱体として有用である。 In the present invention, the MoSi 2 powder as a raw material is washed with an oxidizing acid, and the powder is covered with an oxide film, thereby effectively preventing the pest (powdering phenomenon) of the heating element mainly composed of MoSi 2. It has a remarkable effect that it can suppress the pest (powdering phenomenon) of the heating element at a low cost and can greatly improve the life of the heating element by a relatively simple operation such as acid cleaning. . At the same time, it is possible to reduce impurities in the MoSi 2 powder, that is, the heat generating body using the powder, and in particular, it has an effect of preventing contamination by impurities of the semiconductor wafer. It is useful as a heating element for furnaces (including oxidation and diffusion furnaces).
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