WO2012115136A1 - コージェライト質焼結体およびこのコージェライト質焼結体からなる半導体製造装置用部材 - Google Patents
コージェライト質焼結体およびこのコージェライト質焼結体からなる半導体製造装置用部材 Download PDFInfo
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- WO2012115136A1 WO2012115136A1 PCT/JP2012/054243 JP2012054243W WO2012115136A1 WO 2012115136 A1 WO2012115136 A1 WO 2012115136A1 JP 2012054243 W JP2012054243 W JP 2012054243W WO 2012115136 A1 WO2012115136 A1 WO 2012115136A1
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- sintered body
- cordierite
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- crystal phase
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Definitions
- the present invention relates to a cordierite sintered body and a member for a semiconductor manufacturing apparatus such as an electrostatic chuck, a stage, and a jig in a semiconductor manufacturing process made of the cordierite sintered body.
- Cordierite-based sintered bodies are conventionally known as low thermal expansion ceramics and are used for filters, honeycombs, refractories and the like. In recent years, a cordierite sintered body has been used as a member for a semiconductor manufacturing apparatus by utilizing this low thermal expansion property.
- a stage that is a support on which a silicon wafer is placed corresponds to the above-described member for a semiconductor manufacturing apparatus.
- the dimensional change due to heat during the exposure process is small and the shape stability is excellent, and the silicon wafer is less likely to vibrate after being mounted and moved. Therefore, in addition to low thermal expansibility, members constituting the stage are required to have high rigidity (Young's modulus) that is unlikely to generate vibration.
- a rare earth element oxide is compounded at a predetermined ratio, and the rare earth element oxide is present as a specific crystal phase at the grain boundary of the cordierite crystal.
- a cordierite sintered body having improved sinterability and improved Young's modulus without hindering low thermal expansion characteristics has been proposed (see Patent Document 1).
- the line width has been refined to a submicron order level due to the rapid progress of circuit miniaturization. There is a need for further improvement in accuracy.
- excellent mechanical strength that can cope with an increase in size of a semiconductor manufacturing apparatus is required.
- the material constituting the member for a semiconductor manufacturing apparatus is required to have a low specific gravity so that the weight can be reduced.
- the cordierite-based sintered body of the present invention has a main crystal phase of cordierite, an alumina, mullite and sapphirine as sub-crystal phases, and an amorphous phase containing Ca at grain boundaries.
- the crystal phase ratio of the main crystal phase is 95% by mass or more and 97.5% by mass or less
- the crystal phase ratio of the sub crystal phase is 2.5% by mass or more and 5% by mass or less
- the member for a semiconductor manufacturing apparatus of the present invention is characterized by comprising the cordierite sintered body of the present invention having the above-described configuration.
- the cordierite-based sintered body of this embodiment has cordierite, that is, a composite oxide represented by the general formula Mg 2 Al 4 Si 5 O 18 as a main crystal phase, and alumina (Al 2 O 3) as a sub-crystal phase. ), Mullite (Al 6 Si 2 O 13 ) and sapphirine ((Mg 4 Al 4 ) (Al 4 Si 2 ) O 20 ).
- cordierite that is, a composite oxide represented by the general formula Mg 2 Al 4 Si 5 O 18 as a main crystal phase, and alumina (Al 2 O 3) as a sub-crystal phase.
- Mullite Al 6 Si 2 O 13
- sapphirine (Mg 4 Al 4 ) (Al 4 Si 2 ) O 20 ).
- it is not limited to the thing of the stoichiometric composition shown by the general formula mentioned above, What shifted
- the crystal phase ratio determined by analysis is such that the main crystal phase is 95% by mass or more and 97.5% by mass or less, and the sub crystal phase is 2.5% by mass or more and 5% by mass or less.
- content of Ca is 0.4 mass% or more and 0.6 mass% or less in CaO conversion content with respect to 100 mass% (henceforth whole quantity) of the cordierite sintered compact.
- the thermal expansion coefficient is an absolute value of 0.1 ppm / ° C. or less
- the specific rigidity is 56.0 GPa ⁇ cm 3 / g or more
- the four-point bending strength is 240 MPa or more.
- the thermal conductivity is 4.0 W / m ⁇ K or more.
- the coefficient of thermal expansion can be reduced by cordierite (about ⁇ 0.19 ppm / ° C.), which is a main crystal phase having a negative coefficient of thermal expansion, and a sub-crystal phase having a positive coefficient of thermal expansion.
- cordierite about ⁇ 0.19 ppm / ° C.
- the alumina about 5.2 ppm / ° C.
- mullite about 5.0 ppm / ° C.
- sapphirine about 6.0 ppm / ° C.
- specific rigidity and mechanical strength can be increased because, in addition to the structure of the main crystal phase and the sub crystal phase described above, an amorphous phase containing Ca is present at the grain boundary, and the Ca content relative to the total amount is increased. This is because the content is 0.4% by mass or more and 0.6% by mass or less in terms of CaO.
- the Ca content in the total amount is 0.4% by mass or more and 0.6% by mass or less in terms of CaO, the grain growth of the cordierite crystal as the main crystal phase is promoted and the sinterability is increased.
- the specific rigidity and mechanical strength can be increased by suppressing the cordierite crystal from becoming too large due to the presence of the sub-crystal phase having the above-described crystal phase ratio while improving.
- Ca has a smaller atomic weight and lower specific gravity than the rare earth element (RE) used in Patent Document 1, and thus contributes to an increase in specific rigidity.
- the content of Ca is calculated
- ICP Inductively * Coupled * Plasma
- EPMA wavelength dispersion type
- the thermal expansion coefficient can be measured by a laser interference method in accordance with JIS R 3251-1995, the specific gravity can be measured by the Archimedes method, and the Young's modulus at room temperature can be measured by an ultrasonic pulse method in accordance with JIS R 1602-1995. Good.
- the four-point bending strength may be measured according to JIS R1601-2008.
- the thermal conductivity may be measured by a laser flash method.
- the presence of Ca can be confirmed by observing the grain boundary with a transmission electron microscope (TEM).
- the occupancy ratio of the sub-crystal phase in the crystal phase ratio is 35% to 45% for alumina, 25% to 35% for mullite, and 25% to 40% for sapphirine.
- the coefficient of thermal expansion can be further reduced, and the specific rigidity and mechanical strength can be further increased.
- the absolute value of the thermal expansion coefficient is 0.03 ppm / ° C. or less
- the specific rigidity is 57.0 GPa ⁇ cm 3 / g or more
- the four-point bending strength is 250 MPa or more.
- the content of zirconia is 3.0% by mass or less with respect to the total amount including zirconia (ZrO 2 ).
- zirconia has a positive thermal expansion coefficient of about 9.2 ppm / ° C., it can be used as a thermal expansion coefficient adjusting agent.
- the thermal expansion coefficient is small, the specific rigidity is high, and the chemical resistance against chemicals such as acid and alkali can be enhanced while improving the mechanical strength.
- the content in terms of ZrO 2 with respect to the total amount is obtained by a fluorescent X-ray analyzer, an ICP emission spectroscopic analyzer, or a wavelength dispersive X-ray microanalyzer, and this content is converted to ZrO 2 You can ask for it.
- the color tone of the cordierite-based sintered body when it contains a transition metal element such as Cr, Mn, Fe, Co, Ni, Cu, etc., the color tone having excellent visibility and antifouling property can be obtained. it can. Furthermore, in order to suppress light scattering that affects exposure accuracy while providing visibility and antifouling properties, the color tone of the cordierite-based sintered body has a lightness index L * in the CIE 1976 L * a * b * color space. 70 to 82, and chromaticness indices a * and b * are preferably ⁇ 5 to 1 and preferably 0 to 2.
- the lightness index L *, chromaticness index a *, and b * in the CIE 1976 L * a * b * color space are measurements in a wavelength range of 360 to 740 nm using a spectrocolorimeter.
- a cordierite sintered body having the above-described color tone for example, Mn and Cr are used as colorants, and the content in terms of MnCr 2 O 4 with respect to the total amount is 0.3 mass% or more and 0 If it is 0.7 mass% or less, the cordierite sintered body having the above-described color tone can be obtained.
- the dimensional change due to heat during the exposure process is small, and the shape stability is excellent.
- the exposure accuracy can be improved.
- it can be set as the stage which has high reliability with the outstanding mechanical strength.
- the occupancy ratio of the sub-crystal phase ratio is 35% or more and 45% or less for alumina, 25% or more and 35% or less for mullite, and 25% or more for saphirin.
- the absolute value of the thermal expansion coefficient is 0.03 ppm / ° C. or less
- the specific rigidity is 57.0 GPa ⁇ cm 3 / g or more
- the four-point bending strength is 250 MPa or more. Therefore, the processing speed and exposure accuracy can be further improved, and the mechanical strength can be further improved, so that higher demands on the semiconductor manufacturing apparatus member can be met.
- a method for manufacturing the cordierite sintered body of this embodiment will be described.
- a synthetic cordierite powder obtained by calcining and pulverizing a mixed powder prepared in advance so as to have a predetermined ratio of magnesium carbonate powder, aluminum oxide powder, and silicon oxide powder, aluminum oxide powder, and calcium carbonate powder are used.
- the slurry which added the predetermined amount binder is obtained.
- the cordierite-based sintered body of the present embodiment is obtained by performing cutting as necessary, and then firing this in a firing furnace at a maximum temperature of 1400 ° C. or higher and exceeding 1400 ° C. Can do.
- the reason why the firing temperature exceeds 1400 ° C. is to generate mullite and sapphirine, which are subcrystalline phases, in the cordierite sintered body. Further, by adding alumina powder to the primary raw material, alumina, mullite, and sapphirine can be included as sub-crystal phases.
- zirconium oxide is adjusted so that the content of zirconia in the total amount is 3.0% by mass or less. What is necessary is just to add a powder to a primary raw material.
- a powder containing Cr, Mn, Fe, Co, Ni, Cu or the like may be added to the primary raw material as the raw material powder.
- MnCr 2 O 4 powder may be added to the primary material.
- a cordierite sintered body having an absolute value of a thermal expansion coefficient of 0.03 ppm / ° C. or less, a specific rigidity of 57.0 GPa ⁇ cm 3 / g or more, and a four-point bending strength of 250 MPa or more.
- the synthetic cordierite powder is 95% by mass or more
- the aluminum oxide powder is 3% by mass or more
- the content in terms of CaO with respect to the total amount is 0.4% by mass or more and 0.6% by mass or less. What is necessary is just to comprise a primary raw material with a calcium carbonate powder and to produce with the manufacturing method mentioned above.
- a densified cordierite sintered body can be obtained by hot isostatic pressing at 1000 to 1350 ° C. while applying a pressure of 100 to 200 MPa after firing.
- Synthetic cordierite powder having an average particle size of 3 ⁇ m, aluminum oxide powder having an average particle size of 1 ⁇ m, calcium carbonate powder, and powder containing a transition metal element are prepared.
- the calcium carbonate powder was weighed at the ratio shown, so that the calcium carbonate powder has the ratio shown in Table 1 in terms of CaO, and the powder containing the transition metal element in terms of oxide of the transition metal element shown in Table 1. It measured so that it might become a ratio shown in Table 1. And after adding pure water and mixing with a ball mill for 24 hours, it was set as the slurry which added the binder, and the slurry was sprayed by the spray granulation method, and the granulated body was obtained.
- the granulated body obtained is put in a mold and molded by applying a pressure of 1 t / cm 2 , fired at 1410 ° C. in an air atmosphere, and subsequently hot at 1300 ° C. while applying a pressure of 150 MPa.
- a pressure of 1 t / cm 2 fired at 1410 ° C. in an air atmosphere, and subsequently hot at 1300 ° C. while applying a pressure of 150 MPa.
- the thermal expansion coefficient is a laser interference method based on JISR 3251-1995
- the specific gravity is Archimedes method
- the Young's modulus at room temperature is JIS R1602- It was measured by an ultrasonic pulse method based on 1995.
- the 4-point bending strength was measured according to JIS R1601-2008.
- the thermal conductivity was determined by a laser flash method.
- the amount of Ca in the cordierite sintered body was obtained with a wavelength dispersive X-ray microanalyzer (EPMA), and it was confirmed that the content was as shown in Table 1 when converted to CaO.
- EPMA wavelength dispersive X-ray microanalyzer
- the amounts of Mn, Cr, and Fe in the cordierite sintered body were similarly determined by EPMA.
- 1 to 6 and 10 to 14 since it was confirmed that the existing regions of Mn and Cr overlapped, it is considered that MnCr 2 O 4 is present, and the obtained Cr amount was used for MnCr It was converted into 2 O 4.
- the Mn content is converted to MnO 2
- the Cr content is converted to Cr 2 O 3
- the Fe content is converted to Fe 2 O 3
- the content of the transition metal powder element shown in Table 1 is the content. It was confirmed. Further, for each sample, the grain boundary was observed with a transmission electron microscope (TEM). Except for 12, it was confirmed that Ca was present at the grain boundaries.
- Sample No. to which no aluminum oxide powder was added was obtained. Although the specific gravity of Nos. 10 and 11 was low, the Young's modulus was 139 GPa or less, so the specific rigidity was less than 56.0 GPa ⁇ cm 3 / g. Sample No. No. 12 was low in both the specific rigidity and the 4-point bending strength because the amount of Ca added was small and Ca did not exist at the grain boundaries. Sample No. In Nos. 13 and 14, since the ratio of the crystal phase of cordierite as the main crystal phase is less than 95% by mass, the thermal expansion coefficients increased to 0.19 ppm / ° C. and 0.2 ppm / ° C., respectively.
- the absolute value of the thermal expansion coefficient is 0.1 ppm / ° C. or less
- the specific rigidity is 56.0 GPa ⁇ cm 3 / g or more
- the four-point bending strength is 240 MPa or more.
- the occupancy ratio of the sub-crystal phase in the crystal phase ratio is 35% to 45% for alumina, 25% to 35% for mullite, and 25% to 40% for sapphirine.
- Nos. 1 to 5 have an absolute value of thermal expansion coefficient of 0.03 ppm / ° C. or less, a specific rigidity of 57 GPa ⁇ cm 3 / g or more, a four-point bending strength of 250 MPa or more, and an excellent cordierite quality It was found to be a sintered body.
- sample no. 1 to 9 sample No. 1 containing MnCr 2 O 4 as the crystal phase. Nos. 1 to 6 showed little color unevenness in visual confirmation.
- 1 to 3 and 5 have the above-mentioned excellent characteristics, have a gray color tone, have little color unevenness, have visibility and antifouling properties, and have light scattering that affects exposure accuracy. It was found to be a cordierite sintered body in order to suppress this.
- Example 1 3 Sample No. in Example 1 3 was used, and the amount of synthetic cordierite powder added was reduced by the amount of zirconium oxide powder added, thereby producing a cordierite sintered body.
- the addition amount of aluminum oxide powder and calcium carbonate and the production method were the same as in Example 1, and sample No. 15-22 were obtained.
- the cordierite sintered body of the present embodiment has the above-described excellent characteristics, it has been found that it is suitable for a member for a semiconductor manufacturing apparatus.
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Abstract
Description
Claims (6)
- 主結晶相がコージェライトであり、副結晶相として、アルミナ、ムライトおよびサフィリンを含み、粒界にCaを含む非晶質相が存在してなり、前記主結晶相の結晶相比率が95質量%以上97.5質量%以下であり、前記副結晶相の結晶相比率が2.5質量%以上5質量%以下であり、全量中に対するCaの含有量がCaO換算で0.4質量%以上0.6質量%以下であることを特徴とするコージェライト質焼結体。
- 前記副結晶相の結晶相比率における占有率が、前記アルミナが35%以上45%以下であり、前記ムライトが25%以上35%以下であり、前記サフィリンが25%以上40%以下であることを特徴とする請求項1に記載のコージェライト質焼結体。
- さらにジルコニアを含み、全量中に対するジルコニアの含有量が3.0質量%以下であることを特徴とする請求項1に記載のコージェライト質焼結体。
- CIE1976L*a*b*色空間における明度指数L*が70以上82以下であり、クロマティクネス指数a*、b*がそれぞれ-5以上1以下であり、0以上2以下であることを特徴とする請求項1に記載のコージェライト質焼結体。
- 結晶相としてMnCr2O4を含んでいることを特徴とする請求項1に記載のコージェライト質焼結体。
- 請求項1乃至請求項5のいずれかに記載のコージェライト質焼結体からなることを特徴とする半導体製造装置用部材。
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JP2013501087A JP5762522B2 (ja) | 2011-02-24 | 2012-02-22 | コージェライト質焼結体およびこのコージェライト質焼結体からなる半導体製造装置用部材 |
EP12749386.4A EP2679562B1 (en) | 2011-02-24 | 2012-02-22 | Cordierite sintered body and member for semiconductor device composed of cordierite sintered body |
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JP2018002586A (ja) * | 2016-06-24 | 2018-01-11 | 京セラ株式会社 | セラミックスの製造方法および低熱膨張セラミックス |
KR20200076774A (ko) * | 2018-12-19 | 2020-06-30 | 한국세라믹기술원 | 세라믹 히터용 코디어라이트계 세라믹 조성물 |
JPWO2020175317A1 (ja) * | 2019-02-28 | 2021-11-18 | 日本碍子株式会社 | ハニカム構造体、及びその製造方法 |
WO2022186072A1 (ja) * | 2021-03-05 | 2022-09-09 | Agc株式会社 | コーディエライト質焼結体およびその製造方法 |
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JP6340034B2 (ja) * | 2016-05-16 | 2018-06-06 | 黒崎播磨株式会社 | 非接触式形状測定機校正用のセラミックス基準器用部材 |
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JP5762522B2 (ja) | 2015-08-12 |
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