JP4071691B2 - Manufacturing method of heating element mainly composed of MoSi2 and having excellent thermal shock resistance, and heating element - Google Patents
Manufacturing method of heating element mainly composed of MoSi2 and having excellent thermal shock resistance, and heating element Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 title claims description 133
- 230000035939 shock Effects 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 229910020968 MoSi2 Inorganic materials 0.000 title 1
- 239000011521 glass Substances 0.000 claims description 85
- 229910016006 MoSi Inorganic materials 0.000 claims description 65
- 239000000463 material Substances 0.000 claims description 33
- 239000012535 impurity Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、耐熱衝撃性に著しく優れたＭｏＳｉ２を主成分とする発熱体の製造方法及び発熱体、特に半導体製造装置用熱処理炉（酸化・拡散炉を含む）に有用である耐熱衝撃性に優れたＭｏＳｉ２を主成分とする基材からなる発熱体の製造方法及び発熱体に関する。
なお、本明細書で使用するＭｏＳｉ２を主成分とする基材は、ＭｏＳｉ２基材に絶縁性酸化物であるガラス相（ＳｉＯ２系酸化物）を含有させて電気抵抗を増加させた耐熱衝撃性に優れたＭｏＳｉ２を主成分とする基材を意味する。
INDUSTRIAL APPLICABILITY The present invention has a heat shock resistance which is useful for a method of manufacturing a heating element mainly composed of MoSi 2 and having a remarkable thermal shock resistance and a heating element, particularly a heat treatment furnace (including an oxidation / diffusion furnace) for semiconductor manufacturing equipment. The present invention relates to a method for producing a heating element comprising a base material mainly composed of excellent MoSi 2 and a heating element.
Incidentally, the substrate of the MoSi 2 to be used herein as a main component, a glass phase is an insulating oxide MoSi 2 substrate contain a (SiO 2 based oxide) increases the electric resistance heat It means a base material mainly composed of MoSi 2 having excellent impact properties.
ＭｏＳｉ２を主成分とする発熱体は、６７３°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）と言う低温酸化が起こるが、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。本発明は、このような緻密なシリカ保護被膜を形成した発熱体を含み、ガラス質成分の添加は、このような緻密なシリカ保護被膜の形成に有効である。 A heating element mainly composed of MoSi 2 is called pest (powdering phenomenon) in which simultaneous oxidation of Mo and Si occurs in the range of 673 ° K to 873 ° K, and further evaporation of Mo oxide is accompanied. Although low-temperature oxidation occurs, in order to prevent this, oxidation treatment is performed at 1500 ° K. or higher to form a dense silica protective film. The present invention includes a heating element on which such a dense silica protective coating is formed, and the addition of a vitreous component is effective in forming such a dense silica protective coating.
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.
ＭｏＳｉ２を主成分とする発熱体は、そのための材料強度（耐熱性）や材料脆化現象を防止するため、あるいはペスト（粉化現象）と呼ばれている低温酸化を防止するために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行われている（例えば、特許文献１、特許文献２参照）。
これらのＭｏＳｉ２を主成分とする発熱体を半導体製造装置の熱処理炉に使用した場合、雰囲気温度で１００〜１５０°Ｃ／分の昇温速度を達成することが可能であり、金属発熱体より格段に優れた特性を出すことができた。この場合のＭｏＳｉ２製発熱体自体の表面温度は、およそ１８００〜３６００°Ｃ／分（３０〜６０°Ｃ／秒）の速度で変化する。
The heating element mainly composed of MoSi 2 is 1500 ° in order to prevent the material strength (heat resistance), the material embrittlement phenomenon, or the low-temperature oxidation called pest (powdering phenomenon). Development of materials for the heating element itself has been performed, such as forming a dense silica protective film by oxidation treatment at K or higher (see, for example, Patent Document 1 and Patent Document 2).
When these heating elements mainly composed of MoSi 2 are used in a heat treatment furnace of a semiconductor manufacturing apparatus, it is possible to achieve a temperature increase rate of 100 to 150 ° C./min at an ambient temperature. It was possible to obtain outstanding characteristics. In this case, the surface temperature of the MoSi 2 heating element itself changes at a rate of approximately 1800 to 3600 ° C./minute (30 to 60 ° C./second).
最近では、さらに１００〜３００°Ｃ／秒の超高速昇温のニーズが生じており、その急激な温度変化に耐え得る耐熱衝撃性に優れた発熱体が要求されるようになってきた。しかし、従来のＭｏＳｉ２を主成分とする発熱体では、このような耐熱衝撃性（強度）を持つに至っていないのが現状である。
一方、半導体製造装置においては、不純物の混入が大きな問題であるが、処理炉の加熱体から発生する不純物については、特に従来問題視されていなかった。また、そのようなことがあったとしても、止む得ないものとして、無視されてきたのが現状である。
On the other hand, in a semiconductor manufacturing apparatus, mixing of impurities is a big problem, but impurities generated from a heating body of a processing furnace have not been particularly regarded as a problem. Even if such a situation occurs, it has been ignored as an unavoidable situation.
本発明は、耐熱衝撃性に著しく優れた発熱体、特に半導体製造装置用熱処理炉（酸化・拡散炉を含む）に有用である耐熱衝撃性に優れ、かつ熱処理炉の汚染を防止できるＭｏＳｉ２を主成分とする基材からなる発熱体を提供する。 The present invention provides a heating element that is remarkably excellent in thermal shock resistance, in particular, MoSi 2 that is useful in a heat treatment furnace for semiconductor manufacturing equipment (including an oxidation / diffusion furnace) and that can prevent contamination of the heat treatment furnace. A heating element comprising a base material as a main component is provided.
上記の課題を解決するために、本発明者らは、発熱体中のガラス相（ＳｉＯ２系酸化物）、特にシリカ（ＳｉＯ２）相を低減することにより、耐熱衝撃性を向上させ、かつガラス相中の不純物を低減した、特に半導体製造装置用熱処理炉（酸化・拡散炉を含む）の急速加熱冷却が可能であるＭｏＳｉ２を主成分とする発熱体を低コストで提供できるとの知見を得た。
本発明はこの知見に基づき、
１）ＭｏＳｉ２粉末とＳｉＯ ２ に酸化物を固溶させて熱膨張率を０．５〜８．０×１０ −６ ／°Ｃの範囲に調整したガラス粉末とを発熱体原料とし、この発熱体原料を混合後、有機バインダーと混合し、この混合物を成形体とした後、焼結して発熱体を製造する方法であって、発熱体の基材内部に存在するガラス相が６〜１６ｖｏｌ％（表面酸化被膜を除く）で、発熱体に存在するガラス相の熱膨張率が０．５〜８．０×１０ −６ ／°Ｃ、最大粒径が３０μｍ以下、発熱体中に含まれる不純物のＦｅ、Ｎａ、Ｋがそれぞれ２００ｗｔｐｐｍ以下であることを特徴とする耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体の製造方法
２）ＳｉＯ ２ に固溶させる酸化物がＡｌ ２ Ｏ ３ 、ＭｇＯ、ＣａＯ、Ｂａ ２ Ｏ ３ 、ＺｎＯから選択したいずれか一種以上であることを特徴とする上記１記載の耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体の製造方法
３）混合物を７０〜２００°Ｃに加熱した型から押出して棒状の成形体とすることを特徴とする上記１又は２記載の耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体の製造方法
４）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を特徴とする請求項３記載の耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体の製造方法。
５）発熱体の基材内部における発熱体断面に存在するガラス相の平均面積率が６〜１６％（表面酸化被膜を除く）であることを特徴とする上記１〜４のいずれかに記載の耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体の製造方法、を提供する。
In order to solve the above problems, the inventors have improved the thermal shock resistance by reducing the glass phase (SiO 2 oxide), particularly the silica (SiO 2 ) phase in the heating element, and Knowledge that heating elements based on MoSi 2 that can reduce the impurities in the glass phase, especially heat treatment furnaces for semiconductor manufacturing equipment (including oxidation / diffusion furnaces) and that can be rapidly heated and cooled, can be provided at low cost. Got.
The present invention is based on this finding,
1) The heat generation material is made of MoSi 2 powder and glass powder in which an oxide is dissolved in SiO 2 and the coefficient of thermal expansion is adjusted to the range of 0.5 to 8.0 × 10 −6 / ° C. After mixing the body material, it is mixed with an organic binder, and this mixture is made into a molded body, and then sintered to produce a heating element, in which the glass phase present in the base material of the heating element is 6 to 16 vol. % (Excluding the surface oxide film), the thermal expansion coefficient of the glass phase present in the heating element is 0.5 to 8.0 × 10 −6 / ° C., the maximum particle size is 30 μm or less, and is contained in the heating element A method for producing a heating element mainly composed of MoSi 2 having excellent thermal shock resistance, characterized in that impurities Fe, Na, and K are each 200 wtppm or less 2) An oxide that is dissolved in SiO 2 is Al 2 O 3, MgO, CaO, was selected from Ba 2 O 3, ZnO Rod-like manufacturing process 3) a mixture of the heating element to the MoSi 2 having excellent thermal shock resistance of the 1, wherein a is shifted one or more as a main component from the mold heated to 70 to 200 ° C and extruded 4. A method for producing a heating element mainly composed of MoSi 2 having excellent thermal shock resistance as described in 1 or 2 above , characterized in that it is a molded body of 4) Degreasing, primary sintering, and rod-shaped molded body (green) method for producing a heating element that the MoSi 2 having excellent thermal shock resistance according to claim 3, wherein the energizing heat sintering mainly.
5) average area ratio of the glass phase existing in the heating element cross section in the base material inside the heating element according to any one of the above 1 to 4, characterized in that a 6-16% (excluding the surface oxide coating) Provided is a method for producing a heating element mainly composed of MoSi 2 having excellent thermal shock resistance.
本発明は、また、
６）ＭｏＳｉ２を主成分とし、残余ガラス相と不純物からなる発熱体において、該発熱体の基材内部に存在するガラス相はＳｉＯ ２ に酸化物を固溶させて熱膨張率を０．５〜８．０×１０ −６ ／°Ｃの範囲に調整したガラス相であり、ガラス相の割合が６〜１６ｖｏｌ％（表面酸化被膜を除く）で、最大粒径が３０μｍ以下であり、前記発熱体の不純物のＦｅ、Ｎａ、Ｋがそれぞれ２００ｗｔｐｐｍ以下であることを特徴とする耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体
７）ＭｏＳｉ２を主成分とし、残余ガラス相と不純物からなる発熱体において、該発熱体の基材内部における発熱体断面に存在するガラス相の平均面積率が６〜１６％（表面酸化被膜を除く）であることを特徴とする上記６記載の耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体
８）半導体製造装置用熱処理炉に使用することを特徴とする上記６又は７記載の耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体、を提供する。
The present invention also provides
6) In a heating element composed mainly of MoSi 2 and composed of a residual glass phase and impurities, the glass phase present inside the base material of the heating element has a thermal expansion coefficient of 0.5 by dissolving an oxide in SiO 2. A glass phase adjusted to a range of ˜8.0 × 10 −6 / ° C. , a glass phase ratio of 6 to 16 vol% (excluding a surface oxide film), a maximum particle size of 30 μm or less, and the heat generation Heating element mainly composed of MoSi 2 having excellent thermal shock resistance, characterized in that Fe, Na, and K of impurities in the body are each 200 wtppm or less 7) From MoSi 2 as a main component and from the remaining glass phase and impurities The heat-resistant shock as described in 6 above, wherein the average area ratio of the glass phase present in the cross-section of the heat generator inside the base material of the heat generator is 6 to 16% (excluding the surface oxide film). MoSi with excellent properties The heating element comprising 2 as a main component 8) The heating element having MoSi 2 as a main component having excellent thermal shock resistance as described in 6 or 7 above, which is used in a heat treatment furnace for a semiconductor manufacturing apparatus.
ＭｏＳｉ２を主成分とし、残余ガラス相と不純物からなる発熱体において、該発熱体の基材内部に存在するガラス相を６〜１６ｖｏｌ％とし、かつ不純物のＦｅ、Ｎａ、Ｋがそれぞれ２００ｗｔｐｐｍ以下とすることによって、耐熱衝撃性に著しく優れかつ加熱処理炉の汚染の少ない、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を主成分とする基材からなる発熱体を提供できるという優れた効果を有する。 In the heating element composed mainly of MoSi 2 and composed of the remaining glass phase and impurities, the glass phase present in the base material of the heating element is 6 to 16 vol%, and impurities Fe, Na, and K are each 200 wtppm or less. Heat generated from a base material mainly composed of MoSi 2 which is extremely excellent in thermal shock resistance and has little contamination of the heat treatment furnace, and is particularly useful for heat treatment furnaces for semiconductor manufacturing equipment (including oxidation and diffusion furnaces). It has an excellent effect of providing a body.
本発明のＭｏＳｉ２を主成分とし、残余ガラス相と不可避的不純物からなる発熱体（以下、特に記載しない限り、「ＭｏＳｉ２製発熱体」と称する。）は、該発熱体の基材内部のガラス相を６〜１６ｖｏｌ％とする。但し、該発熱体の表面に緻密に形成されたＳｉＯ２の酸化被膜を除く。
また、このガラス相の比率（量）は、発熱体の基材内部の任意断面におけるガラス相の平均断面積に近似するので、発熱体断面に存在するガラス相の平均面積率６〜１６％（表面酸化被膜を除く）により特定することができる。これによって、耐熱衝撃性に優れたＭｏＳｉ２を主成分とする発熱体を得ることができる。
表面の緻密な酸化膜層の厚みは、ガラス相の種類により、また添加量によって差異があり、およそ５μｍ〜１００μｍの範囲で形成される。
A heating element (hereinafter, referred to as “MoSi 2 heating element” unless otherwise specified) which is mainly composed of MoSi 2 of the present invention and includes a residual glass phase and unavoidable impurities is provided inside the base material of the heating element. The glass phase is 6-16 vol%. However, the oxide film of SiO 2 densely formed on the surface of the heating element is excluded.
Moreover, since the ratio (amount) of the glass phase approximates the average cross-sectional area of the glass phase in an arbitrary cross section inside the base material of the heating element, the average area ratio 6 to 16% of the glass phase existing in the cross section of the heating element ( (Excluding surface oxide film). As a result, a heating element mainly composed of MoSi 2 having excellent thermal shock resistance can be obtained.
The thickness of the dense oxide film layer on the surface varies depending on the type of glass phase and the amount added, and is formed in the range of about 5 μm to 100 μm.
この耐熱衝撃性を向上させるために上記の通りガラス相を含有させるのであるが、ここで重要なことは、ベントナイト等の通常のガラスを添加すると必然的に不純物が混入することである。このような不純物の混入は加熱処理炉の発熱体の中では、着目されておらず、何らの対策も講じられていなかった。しかし、発熱体からの不純物は、昨今の微小回路又は各種機能材を形成する半導体装置において問題となるものである。
本発明は、この点に着目し、特に原料として添加されるガラス粉末から混入する不純物のＦｅ、Ｎａ、Ｋをそれぞれ０．１ｗｔ％以下とするものである。
これによって、耐熱衝撃性に著しく優れると共に、加熱処理炉の汚染の少ない、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を主成分とする基材からなる発熱体を提供できるという優れた効果が得られるようになった。
In order to improve the thermal shock resistance, a glass phase is contained as described above, but what is important here is that impurities are inevitably mixed when ordinary glass such as bentonite is added. Such impurity contamination has not been noticed in the heating element of the heat treatment furnace, and no measures have been taken. However, the impurities from the heating element become a problem in a semiconductor device that forms a recent microcircuit or various functional materials.
The present invention pays attention to this point, and in particular, impurities Fe, Na, and K mixed from glass powder added as a raw material are each 0.1 wt% or less.
As a result, the heat generated from the base material mainly composed of MoSi 2 which is remarkably excellent in thermal shock resistance and has little contamination of the heat treatment furnace, and is particularly useful for heat treatment furnaces for semiconductor manufacturing equipment (including oxidation and diffusion furnaces). The excellent effect of being able to provide a body has come to be obtained.
現在、市販されているＭｏＳｉ２製発熱体は、ＳｉＯ２を主としたシリカ系酸化物相のガラス相からなる。しかし、ＭｏＳｉ２とＳｉＯ２との熱膨張係数は、それぞれ８．０×１０−６／°Ｃ、０．５×１０−６／°Ｃで両者の差が非常に大きい。
また、熱伝導率においてもＭｏＳｉ２は３０Ｗ／ｍ・Ｋ及びＳｉＯ２は１．５Ｗ／ｍ・Ｋであり、両者の差が大きい。
以上の物性から、超高速昇温におけるＭｏＳｉ２発熱体内部の挙動を考察すると、ガラス相は熱伝導率が低く、ＭｏＳｉ２に比べ昇温されにくい。また、ガラス相はＭｏＳｉ２相より熱膨張係数が小さいので、さらに膨張差が広がり、これによって発生する歪から基材が破損し、あるいは劣化して寿命が短くなる問題がある。
Currently, a commercially available heating element made of MoSi 2 consists of a glass phase of a silica-based oxide phase mainly composed of SiO 2 . However, the thermal expansion coefficients of the MoSi 2 and SiO 2, the difference between them is very large, respectively 8.0 × 10 -6 /°C,0.5×10 -6 / ° C.
Further, in terms of thermal conductivity, MoSi 2 is 30 W / m · K and SiO 2 is 1.5 W / m · K, and the difference between the two is large.
Considering the behavior inside the MoSi 2 heating element at an ultra-high temperature rise from the above physical properties, the glass phase has a low thermal conductivity and is harder to be heated than MoSi 2 . Further, since the glass phase has a smaller thermal expansion coefficient than the MoSi 2 phase, there is a problem that the expansion difference is further widened, and the base material is damaged or deteriorated due to the strain generated thereby, resulting in a short life.
本発明は、上記の通りガラス相を極力少なくすることによって耐熱衝撃性を改善することができる。さらに、発熱体の製造工程において熱膨張率がＭｏＳｉ２に近似する２〜１３×１０−６／°Ｃのガラス質材料を選択し、発熱体の内部の熱膨張差による歪を小さくすることが可能であり、これを併用することにより一層耐熱衝撃性を改良することができる。熱膨張率は、Ａｌ２Ｏ３やＭｇＯ等を含むガラス相にすることにより、効果的に大きくすることができる。
しかし、本発明においては、熱膨張率がＭｏＳｉ２に近似する２〜１３×１０−６／°Ｃのガラス質材料を選択することが望ましいが、この範囲をややはずれる範囲であっても、本発明に含まれるものである。上記熱膨張率は、本発明の発熱体を製造する上において、より望ましい範囲を示すものである。
The present invention can improve the thermal shock resistance by reducing the glass phase as much as possible as described above. Further, in the manufacturing process of the heating element, a glassy material having a thermal expansion coefficient of 2 to 13 × 10 −6 / ° C. that approximates to MoSi 2 is selected, and distortion due to the thermal expansion difference inside the heating element can be reduced. The thermal shock resistance can be further improved by using this together. The thermal expansion coefficient can be effectively increased by using a glass phase containing Al 2 O 3 or MgO.
However, in the present invention, it is desirable to select a vitreous material having a thermal expansion coefficient of 2 to 13 × 10 −6 / ° C. that is close to that of MoSi 2. It is included in the invention. The coefficient of thermal expansion indicates a more desirable range in producing the heating element of the present invention.
また、本発明は基材内部に含まれるガラス相の最大粒径を３０μｍ以下とし均一に分散させ、歪が局所的に発生させないようにすることが望ましい。しかし、この範囲をややはずれる範囲であっても、本発明に含まれるものである。上記最大粒径は、本発明の発熱体を製造する上において、あくまでより好ましい範囲を示すものである。
ガラス相が１６ｖｏｌ％を超えると耐熱衝撃性が不十分であり、６ｖｏｌ％未満では基材の緻密化が困難となり、高温での柔軟性が低下し、Ｕ字形曲げ等の加工が困難となる。
上記のＭｏＳｉ２を主成分とする発熱体は、急速加熱・冷却を行う半導体製造装置用熱処理炉に有用である。
Further, in the present invention, it is desirable that the maximum particle size of the glass phase contained in the base material is 30 μm or less to be uniformly dispersed so that no strain is locally generated. However, even a range slightly deviating from this range is included in the present invention. The maximum particle size is a more preferable range in producing the heating element of the present invention.
If the glass phase exceeds 16 vol%, the thermal shock resistance is insufficient, and if it is less than 6 vol%, it becomes difficult to densify the base material, the flexibility at high temperature decreases, and processing such as U-shaped bending becomes difficult.
The heating element mainly composed of MoSi 2 is useful for a heat treatment furnace for a semiconductor manufacturing apparatus that performs rapid heating and cooling.
このＭｏＳｉ２製発熱体は、ＭｏＳｉ２原料粉とガラス粉末とを混合粉砕した後、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、密度の高い耐熱衝撃性に優れたＭｏＳｉ２製発熱体を製造する。
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、半導体製造装置用熱処理炉に設置する。
This MoSi 2 heating element is obtained by mixing and pulverizing MoSi 2 raw material powder and glass powder, then mixing with a binder, and further forming into a rod shape or a flat plate shape by extrusion, for example. The molded body thus obtained is degreased, primary sintered, and energized and heated to produce a MoSi 2 heating element having a high density and excellent thermal shock resistance.
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. As described above, after the MoSi 2 heating element is formed into various shapes, it is installed in a heat treatment furnace for a semiconductor manufacturing apparatus.
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.
（参考例１、実施例２、参考例３、実施例４）
発熱体原料とするＭｏＳｉ２粉末（平均粒径４μｍ）とガラス粉末を混合後、さらに熱可塑性の有機バインダーと混合し、この混合物を７０〜２００°Ｃに加熱した型から押出して棒状の成形体とした。また、ガラス粉末の不純物を制限し、発熱体中のＦｅ、Ｎａ、Ｋの不純物の量を２００ｗｔｐｐｍ以下とした。
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φ３の棒状発熱体を得た。
( Reference Example 1, Example 2, Reference Example 3, Example 4 )
After mixing MoSi 2 powder (average particle size 4 μm) as a heating element raw material and glass powder, it is further mixed with a thermoplastic organic binder, and this mixture is extruded from a mold heated to 70 to 200 ° C. to form a rod-shaped molded body. It was. Moreover, the impurity of glass powder was restrict | limited and the quantity of the impurity of Fe, Na, and K in a heat generating body was 200 wtppm or less.
This rod-shaped molded body (green) was degreased, primary sintered and energized and heated to obtain a rod-shaped heating element of MoSi 2 φ3.
作製した発熱体は、発熱体断面のＳＥＭ像（二次電子像）をもとに、以下の方法でガラス相の最大粒径、平均面積率を算出した。
基材内部に含まれるガラス相の最大粒径の測定は、発熱体断面をＳＥＭ観察することにより行うことができる。ＳＥＭ像では、ガラス相は周辺（ＭｏＳｉ２相）より暗部になるため、散在している暗部の中で最大の粒径を測定することにより、本来は３次元的に存在するガラス相の最大粒径と近似させることができる。
The produced heating element was calculated based on the SEM image (secondary electron image) of the section of the heating element by the following method to calculate the maximum particle size and average area ratio of the glass phase.
The maximum particle size of the glass phase contained in the substrate can be measured by SEM observation of the cross section of the heating element. In the SEM image, since the glass phase becomes darker than the surrounding (MoSi 2 phase), the maximum particle size of the glass phase originally existing three-dimensionally is measured by measuring the maximum particle size in the scattered dark portion. It can be approximated with a diameter.
一方、ガラス相の平均面積率の測定は、発熱体断面のＳＥＭ像をＰＣで画像処理することにより行うことができる。ＳＥＭ像では、ガラス相は周辺（ＭｏＳｉ２相）より暗部になるため、この画像の濃淡の違いを利用し、画像処理ソフトでガラス相のみを識別することができる。
識別したガラス相は、その面積を累積する処理を行い、画像全体の面積に対する割合を計算することにより、ガラス相の平均面積率とすることができる。
上記によって得られる発熱体断面に存在するガラス相の平均面積率、ガラス相の最大粒径、添加ガラスの熱膨張係数（×１０−６／°Ｃ）、添加ガラスの不純物量を変化させた場合の、参考例１、実施例２、参考例３、実施例４を表１に示す。
On the other hand, the average area ratio of the glass phase can be measured by subjecting the SEM image of the cross section of the heating element to image processing with a PC. In the SEM image, since the glass phase is darker than the surrounding (MoSi 2 phase), only the glass phase can be identified by image processing software using the difference in light and shade of this image.
The identified glass phase is subjected to a process of accumulating its area, and the ratio to the total area of the image is calculated to obtain the average area ratio of the glass phase.
When the average area ratio of the glass phase present in the cross section of the heating element obtained as described above, the maximum particle size of the glass phase, the thermal expansion coefficient of the added glass (× 10 −6 / ° C.), and the amount of impurities in the added glass are changed. Table 1 shows Reference Example 1, Example 2, Reference Example 3, and Example 4 .
因みに、添加ガラス量はＭｏＳｉ２粉末と混合する時の秤量で調整した。また、添加ガラスの粒径はＭｏＳｉ２粉末と混合する以前のガラス粉末の粉砕工程を調整し、篩により篩別した。
添加ガラスの熱膨張係数は、純ＳｉＯ２（０．５×１０−６／°Ｃ）から、Ａｌ２Ｏ３、ＭｇＯ、ＣａＯ、Ｂａ２Ｏ３、ＺｎＯ等を任意に固溶させたガラスを作製することにより、０．５〜８．０×１０−６／°Ｃの範囲で調整した。
Incidentally, the amount of added glass was adjusted by weighing when mixed with MoSi 2 powder. Moreover, the particle size of the added glass was adjusted by a pulverization step of the glass powder before mixing with the MoSi 2 powder, and sieved with a sieve.
The thermal expansion coefficient of the additive glass is a glass in which Al 2 O 3 , MgO, CaO, Ba 2 O 3 , ZnO or the like is arbitrarily dissolved in pure SiO 2 (0.5 × 10 −6 / ° C.). By preparing, it adjusted in the range of 0.5-8.0 * 10 < -6 > / (degreeC).
耐熱衝撃性の評価は、各発熱体基材を急速昇温および急速冷却処理した後、ＪＩＳ規格に基づく３点曲げ試験を室温中で行ない抗折強度の値から行った。
急速昇温処理は、通電加熱により発熱体基材を室温から１４００°Ｃまで５秒間で昇温(平均昇温速度：約２８０°Ｃ／秒)し、１４００°Ｃで２０秒保持する加熱パターンを１００回繰り返して行った。
また、急速冷却処理は通電加熱により６００°Ｃで保持中の発熱体基材を、通電停止後、直ちに十分な量のある水（約２０°Ｃ）の中に漬けて行った。
それぞれの発熱体基材の急速加熱処理後及び急速冷却後の抗折強度結果を、同様に表１に示す。
The thermal shock resistance was evaluated by subjecting each heating element base material to rapid heating and cooling, and then performing a three-point bending test based on JIS standards at room temperature from the value of bending strength.
The rapid heating process is a heating pattern in which the heating element base material is heated from room temperature to 1400 ° C for 5 seconds by heating (average heating rate: about 280 ° C / second) and held at 1400 ° C for 20 seconds. Was repeated 100 times.
The rapid cooling treatment was performed by immersing the heating element base material held at 600 ° C. by energization heating in a sufficient amount of water (about 20 ° C.) immediately after the energization was stopped.
Table 1 similarly shows the bending strength results after rapid heating treatment and rapid cooling of each heating element base material.
（比較例１−２）
実施例と同様の製造方法により、発熱体断面に存在するガラス相の平均面積率、ガラス相の最大粒径、添加ガラスの熱膨張係数（×１０−６／°Ｃ）、添加ガラスの不純物量を変化させた場合の比較例１−２を、同様に表１に示す。
(Comparative Example 1-2)
By the same production method as in the examples, the average area ratio of the glass phase present in the cross section of the heating element, the maximum particle size of the glass phase, the thermal expansion coefficient of the added glass (× 10 −6 / ° C.), and the impurity amount of the added glass Table 1 similarly shows Comparative Example 1-2 in the case where V is changed.
参考例１、実施例２、参考例３、実施例４はいずれも、発熱体の基材内部に存在するガラス相が１６ｖｏｌ％以下であり、急速加熱処理後及び急速冷却後の抗折強度は良好な特性値を示した。但し、表１に示す通り、実施例２と実施例４は、ガラス相の最大粒径が、それぞれ１０μｍ、１５μｍであったが、参考例１と参考例３は、ガラス相の最大粒径が、それぞれ３５μｍ、５０μｍとなった。
実施例４は発熱体の基材内部に存在するガラス相が１６ｖｏｌ％以下であり、添加ガラスの最大粒径が小さく、またガラスの熱膨張係数が大きくＭｏＳｉ２の熱膨張係数（８．０×１０−６／°Ｃ）に近似しているので、急速加熱処理後及び急速冷却後の抗折強度は最も良好な特性値を示した。
実施例２の発熱体組織の走査型電子顕微鏡（ＳＥＭ）写真を図１に示す。最大粒径は１０μｍ以下（平均の粒径は８〜１０μｍ）の微細なガラス相（黒い部分）が均一に分散した組織を示していた。
In all of Reference Example 1, Example 2, Reference Example 3, and Example 4 , the glass phase present in the base material of the heating element is 16 vol% or less, and the bending strength after rapid heating treatment and after rapid cooling is Good characteristic values were shown. However, as shown in Table 1, in Examples 2 and 4, the maximum particle size of the glass phase was 10 μm and 15 μm, respectively, but in Reference Example 1 and Reference Example 3, the maximum particle size of the glass phase was And 35 μm and 50 μm, respectively.
In Example 4, the glass phase present in the base material of the heating element is 16 vol% or less, the maximum particle size of the added glass is small, the thermal expansion coefficient of the glass is large, and the thermal expansion coefficient of MoSi 2 (8.0 × 10 −6 / ° C.), the bending strength after rapid heating treatment and after rapid cooling showed the best characteristic value.
A scanning electron microscope (SEM) photograph of the heating element structure of Example 2 is shown in FIG. It showed a structure in which a fine glass phase (black portion) having a maximum particle size of 10 μm or less (average particle size of 8 to 10 μm) was uniformly dispersed.
これらに対し、基材内部に存在するガラス相が１９ｖｏｌ％、添加ガラスの熱膨張係数が１．０×１０−６／°ＣとＭｏＳｉ２の熱膨張係数から大きく離れ、さらに添加ガラスの最大粒径が５０μｍである比較例１は急速加熱処理後及び急速冷却後の抗折強度が低い値を示した。
比較例１の発熱体組織の走査型電子顕微鏡（ＳＥＭ）を図２に示す。この組織のガラス相（黒い部分）は不均一に分散しており、５０μｍの巨大ガラス相がところどころに観察された。また、ガラス相が４０．０ｖｏｌ％である比較例２は水冷時に破損するという結果になった。
以上から、急速加熱処理後及び急速冷却後の抗折強度改善に、基材内部に存在するガラス相の存在量を低減させること及び添加ガラスの熱膨張係数をＭｏＳｉ２の熱膨張係数（８．０×１０−６／°Ｃ）に近似させることが、極めて有効であることが分かる。
These contrast, glass phase 19Vol% present inside the base material, the thermal expansion coefficient of the doped glass is far from the thermal expansion coefficient of 1.0 × 10 -6 / ° C and MoSi 2, further added the maximum particle of glass Comparative Example 1 having a diameter of 50 μm showed a low value of bending strength after the rapid heating treatment and after rapid cooling.
A scanning electron microscope (SEM) of the heating element structure of Comparative Example 1 is shown in FIG. The glass phase (black part) of this structure was disperse | distributed nonuniformly, and the 50-micrometer giant glass phase was observed in some places. Moreover, the comparative example 2 whose glass phase is 40.0 vol% resulted in being damaged at the time of water cooling.
From the above, in order to improve the bending strength after the rapid heat treatment and rapid cooling, the amount of glass phase present in the substrate is reduced, and the thermal expansion coefficient of the added glass is set to the thermal expansion coefficient of MoSi 2 (8. It can be seen that approximation to 0 × 10 −6 / ° C. is extremely effective.
発熱体中のガラス相（ＳｉＯ２系酸化物）、特にシリカ（ＳｉＯ２）相を低減することにより、耐熱衝撃性を向上させ、かつガラス相中の不純物を低減したものであり、特に急速加熱冷却する半導体製造装置用熱処理炉（酸化・拡散炉を含む）用ＭｏＳｉ２を主成分とする発熱体として有用である。 By reducing the glass phase (SiO 2 -based oxide) in the heating element, especially the silica (SiO 2 ) phase, the thermal shock resistance is improved and the impurities in the glass phase are reduced, especially rapid heating. It is useful as a heating element mainly composed of MoSi 2 for a heat treatment furnace (including an oxidation / diffusion furnace) for semiconductor manufacturing equipment to be cooled.
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