Composite Sintered Body, Semiconductor Manufacturing Equipment Member, and Method for Manufacturing Composite Sintered Body

Abstract

To suppress uneven distribution of ZrO2 in an electrode.SOLUTION: A composite sintered body 20 includes a base material containing Al2O3 as a main material, and an electrode 23 arranged inside or on a surface of the base material. The electrode 23 includes Ru, ZrO2, and Al2O3. Thereby, uneven distribution of ZrO2 in the electrode 23 can be suppressed. As a result, cracks in the base material and peeling of the electrode 23 caused by a difference in a thermal expansion coefficient between the electrode 23 and the base material due to an influence of the uneven distribution can be suppressed.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a composite sintered body, a member for a semiconductor manufacturing apparatus, and a method for manufacturing a composite sintered body.

Background Art

[0002] Conventionally, in a semiconductor substrate manufacturing apparatus or the like, a susceptor such as an electrostatic chuck that adsorbs and holds a semiconductor substrate, a heater that heats the semiconductor substrate, and an electrostatic chuck heater that combines these has been used. The susceptor includes a base material mainly made of a ceramic sintered body and an electrode disposed inside the base material or the like. The electrode is usually formed mainly of a metal in order to reduce the resistivity.

[0003] The above-described susceptor is formed, for example, by integrally firing a base material and an electrode. In this firing, there is a risk of an adverse effect due to the difference in the thermal expansion coefficient between the base material and the electrode. For example, there is a risk that cracks may occur in the base material or the electrode may peel off from the base material. Further, when the base material is thin, there is also a risk that the base material may warp.

[0004] Therefore, in Patent Document 1, a technique has been proposed in which ruthenium is used as the main component of an electrode provided on a ceramic substrate that is a sintered body of aluminum oxide or a rare earth metal oxide, and zirconium oxide, titanium nitride, or aluminum oxide is added as a filler component to reduce the difference in the thermal expansion coefficient between the ceramic substrate and the electrode and suppress warping of the ceramic substrate.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] By the way, when printing and integrally firing a paste of an electrode material on the surface of a base material in the production of a susceptor, the paste may be sucked by the base material, and specific components in the electrode material may be biased toward the base material side. For example, when using an electrode in which zirconium oxide is added to ruthenium as in Patent Document 1, firing is performed with zirconium oxide in the paste being unevenly distributed on the base material side, so that the difference in the coefficient of thermal expansion between the electrode and the base material locally increases, and there is a risk of cracks in the base material or peeling of the electrode. The uneven distribution of the zirconium oxide is presumably due to the fact that ruthenium is rich in malleability and not easily pulverized, so the particle size of ruthenium in the paste is relatively large (for example, a dozen or so μm), while the particle size of zirconium oxide is small (for example, 0.1 μm).

[0007] The present invention has been made in view of the above problems, and an object thereof is to suppress the uneven distribution of specific components in an electrode.

Means for Solving the Problems

[0008] A composite sintered body according to a preferred embodiment of the present invention includes a base material mainly made of aluminum oxide, and an electrode disposed inside or on the surface of the base material. The electrode includes ruthenium, zirconium oxide, and aluminum oxide. The total content ratio of the ruthenium, the zirconium oxide, and the aluminum oxide in the solid matter in the electrode is 100% by volume. The content ratio of the aluminum oxide in the electrode is 0.2 times or more and 3.8 times or less the content ratio of the zirconium oxide. The content ratio of the ruthenium in the electrode is 36.8% by volume or more and 85.7% by volume or less.

[0009] Preferably, the absolute value of the difference in the coefficient of thermal expansion between the electrode and the base material is 0.3 ppm / °C or less in the range of 40°C or more and 1000°C or less.

[0010] Preferably, the resistivity of the electrode at room temperature is 3.0×10 -5 Ω·cm or less.

[0011] Preferably, the total content ratio of the zirconium oxide and the aluminum oxide in the electrode is 20% by volume or more.

[0015] Preferably, in the electrode, the intensity ratio of the main peaks of the ruthenium and the zirconium oxide obtained by X-ray diffraction is 0.80 or more and less than 1.0.

[0016] Preferably, when a cross-sectional SEM image of the electrode parallel to the thickness direction of the electrode is equally divided into three parts in the thickness direction, and is defined as a first region, a second region, and a third region in order from one side in the thickness direction, the area of the zirconium oxide in the central second region is 0.5 times or more and 2.0 times or less the area of the zirconium oxide in the first region between the second region and the base material.

[0017] Preferably, the adhesion strength of the electrode to the base material is 90 MPa or more.

[0018] The present invention is also directed to a semiconductor manufacturing apparatus member used in a semiconductor manufacturing apparatus. The semiconductor manufacturing apparatus member is produced using the above-described composite sintered body. The base material is disc-shaped. A semiconductor substrate is placed on the main surface of the base material.

[0019] The present invention is also directed to a method for manufacturing a composite sintered body. The method for manufacturing the composite sintered body includes: a) a step of preparing a first member and a second member, which are a molded body, a green compact, or a sintered body mainly made of aluminum oxide; b) a step of applying a paste-like electrode material containing ruthenium, zirconium oxide, and aluminum oxide on the first member and drying it; c) a step of laminating the second member on the first member to form a laminate; and d) a step of hot press sintering the laminate. The total content ratio of the ruthenium, the zirconium oxide, and the aluminum oxide in the solid matter in the electrode formed from the electrode material by the step d) is 100% by volume. The content ratio of the aluminum oxide in the electrode is 0.2 times or more and 3.8 times or less the content ratio of the zirconium oxide. The content ratio of the ruthenium in the electrode is 36.8% by volume or more and 85.7% by volume or less.

[0020] Preferably, the first member in the step a) is a green compact or a tape molded body.

[0021] Preferably, the absolute value of the difference in the coefficient of thermal expansion between the electrode and the first member after completion of the step d) is 0.3 ppm / °C or less in the range of 40°C or more and 1000°C or less.

[0022] Preferably, the firing temperature in the step d) is 1550°C or higher and 1650°C or lower.

Advantages of the Invention

[0023] In the present invention, the uneven distribution of zirconium oxide in the electrode can be suppressed.

Brief Description of the Drawings

[0024]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0025] FIG. 1 is a cross-sectional view of a susceptor 1 according to one embodiment of the present invention. The susceptor 1 is a semiconductor manufacturing apparatus member used in a semiconductor manufacturing apparatus. The susceptor 1 supports a substantially disc-shaped semiconductor substrate 9 (hereinafter simply referred to as "substrate 9") from the lower side in FIG. 1. In the following description, the upper side and the lower side in FIG. 1 are simply referred to as the "upper side" and the "lower side". Also, the vertical direction in FIG. 1 is simply referred to as the "vertical direction". The vertical direction in FIG. 1 does not necessarily coincide with the actual vertical direction when the susceptor 1 is installed in the semiconductor manufacturing apparatus.

[0026] The susceptor 1 includes a main body portion 21, a base portion 22, and an electrode 23. The main body portion 21 is a substantially plate-shaped (e.g., substantially disk-shaped) base material mainly made of ceramic. A substrate 9 is placed on the upper main surface (i.e., the upper surface) of the main body portion 21. The base portion 22 is a substantially plate-shaped (e.g., substantially disk-shaped) member that is larger than the main body portion 21 in plan view. The main body portion 21 is attached onto the base portion 22. In the example shown in FIG. 1, the electrode 23 is disposed (i.e., embedded) inside the main body portion 21. The electrode 23 is, for example, a substantially strip-shaped member that depicts a predetermined pattern in plan view. The electrode 23 is preferably formed of a material having a relatively high melting point. The main body portion 21 and the electrode 23 are composite sintered bodies formed of a plurality of materials. In the following description, the main body portion 21 and the electrode 23 are also collectively referred to as "composite sintered body 20". The materials of the main body portion 21 and the electrode 23 will be described later. Note that the shape of the electrode 23 may be variously changed. Also, the electrode 23 may be provided on the surface of the main body portion 21.

[0027] In the example shown in FIG. 1, the susceptor 1 is a heater that heats the substrate 9 by the heat generated when a DC voltage is applied to the electrode 23. That is, the electrode 23 is a resistive heating element that heats the substrate 9. In the susceptor 1, in addition to the electrode 23, a chuck electrode that electrostatically adsorbs the substrate 9 using the Coulomb force or the Johnson-Lambeck force may be provided inside the main body portion 21. Alternatively, the electrode 23 may be used as the chuck electrode.

[0028] The main body portion 21 is formed mainly of aluminum oxide (Al 2 O 3 ). In the main body portion 21, magnesium oxide (MgO) and / or an additive material such as magnesium aluminum spinel (MgAl 2 O 4 ) may be added to Al 2 O 3 . In the main body portion 21, the content of the main material Al 2 O 3 is 95% by mass to 100% by mass, and the content is adjusted according to the desired material characteristics of the main body portion 21.

[0029] The electrode 23 contains ruthenium (Ru), zirconium oxide (ZrO 2 ), and Al 2 O 3 . In this embodiment, the solid matter in the electrode 23 consists substantially of only Ru, ZrO 2 and Al 2 O 3 . In other words, the total content ratio of Ru, ZrO 2 and Al 2 O 3 in the solid matter in the electrode 23 (hereinafter, also simply referred to as "in the electrode 23") is 100% by volume.

[0030] The total content ratio of ZrO 2 and Al 2 O 3 in the electrode 23 is, for example, 10% to 65% by volume. Preferably, the total content ratio is 20% by volume or more. The content ratio of Al 2 O 3 in the electrode 23 is, for example, 0.2 times or more and 3.6 times or less the content ratio of ZrO 2 . In other words, the value obtained by dividing the content ratio of Al 2 O 3 in the electrode 23 by the content ratio of ZrO 2 (hereinafter, also referred to as the "Al 2 O 3 / ZrO 2 content ratio") is 0.2 or more and 3.6 or less. The content ratio of Al 2 O 3 in the electrode 23 may be, for example, more than 3.6 times and 3.8 times or less the content ratio of ZrO 2 . That is, the Al 2 O 3 / ZrO 2 content ratio is 0.2 or more and 3.8 or less. The Al 2 O 3 / ZrO 2 content ratio is preferably 0.3 or more and 1.3 or less.

[0031] In the electrode 23, the intensity ratio of the main peaks of Ru and ZrO obtained by X-ray diffraction (XRD) (hereinafter, also referred to as the "Ru-ZrO 2 peak ratio".) is, for example, 0.80 or more and less than 1.0, and is adjusted so that the difference in the coefficient of thermal expansion between the electrode 23 and the main body 21 substantially approaches 0. The Ru-ZrO 2 peak ratio is a value obtained by dividing the main peak intensity of Ru by the sum of the main peak intensity of Ru and the main peak intensity of ZrO 2 . 2

[0032] The coefficient of thermal expansion of Ru (also referred to as the coefficient of thermal expansion rate) is 7.6 ppm / °C (i.e., ppm / K) in the range of 40°C or more and 1000°C or less. The coefficient of thermal expansion in the following description is the coefficient of thermal expansion in the range of 40°C or more and 1000°C or less when there is no description of the temperature conditions. The coefficient of thermal expansion of ZrO 2 is 10.5 ppm / °C. The coefficient of thermal expansion of Al 2 O 3 is 8.1 ppm / °C. The coefficient of thermal expansion of the main body 21 varies depending on the type and ratio of the additive materials added to the main material Al 2 O 3 , but is, for example, 8.1 ppm / °C to 8.3 ppm / °C.

[0033] The coefficient of thermal expansion of Ru contained in the electrode 23 is lower than that of the main body 21. The coefficient of thermal expansion of ZrO 2 contained in the electrode 23 is higher than that of the main body 21. The coefficient of thermal expansion of Al 2 O 3 contained in the electrode 23 is approximately the same as that of the main body 21. The absolute value of the difference in the coefficient of thermal expansion between the electrode 23 and the main body 21 in the range of 40°C or more and 1000°C or less (hereinafter, also referred to as the "CTE difference") is, for example, 0.3 ppm / °C or less, preferably 0.2 ppm / °C or less. The lower limit of the CTE difference is not particularly limited, but is 0.0 ppm / °C or more.

[0034] The resistivity of the electrode 23 at room temperature is, for example, 3.0×10 -5is below Ω·cm, preferably below 2.5×10 -5 Ω·cm. The lower limit of the resistivity is not particularly limited, but for example, it is 1.0×10 -5 Ω·cm or more.

[0035] The adhesion strength of the main body portion 21 of the electrode 23 (hereinafter, also simply referred to as "adhesion strength") is preferably 50 MPa or more, more preferably 90 MPa or more. The upper limit of the adhesion strength of the electrode 23 is not particularly limited, but for example, it is 300 MPa or less. The adhesion strength of the electrode 23 is a value obtained by dividing the fracture shear force between the first member and the second member of the main body portion 21 by the electrode area. The fracture shear force between the first member and the second member is the fracture shear force when the first member and the second member are displaced parallel to the joint surface between the first member and the second member (that is, the shear force when the electrode 23 peels off from the first member and / or the second member).

[0036] Next, an example of a method for manufacturing the main body portion 21 and the electrode 23 (that is, the composite sintered body 20) of the susceptor 1 will be described with reference to FIG. 2. In this example, a substantially disc-shaped portion in the lower half of the main body portion 21 (hereinafter, referred to as "first member") and a substantially disc-shaped portion in the upper half (hereinafter, referred to as "second member") are created, and the material of the electrode 23 is sandwiched between the first member and the second member and fired to manufacture the main body portion 21 and the electrode 23.

[0037] In this manufacturing method, first, the first member and the second member of the main body portion 21 are prepared (step S11). The first member and the second member prepared in step S11 may be in any state of a green body, a pre-sintered body, and a sintered body. In step S11, first, the raw material powder of the main body portion 21 (that is, the first member and the second member) is weighed so as to have a predetermined composition, and after wet-mixing the raw material powder, it is formed into a green body having a predetermined shape by uniaxial pressing or the like.

[0038] In step S11, Al 2 O 3As raw materials, for example, commercially available high-purity fine powders are used. Also, when MgO is included in the main body 21, as the MgO raw material, for example, commercially available high-purity fine powders are used. When MgAl 2 O 4 is included, for example, a material obtained by heat-synthesizing the above-mentioned commercially available MgO powder and commercially available high-purity fine powder of Al 2 O 3 is used as the MgAl 2 O 4 raw material. Alternatively, commercially available high-purity fine powder of MgAl 2 O 4 may be used as the MgAl 2 O 4 raw material. The purity, average particle size, etc. of the Al 2 O 3 raw material, MgO raw material, and MgAl 2 O 4 raw material are determined as appropriate.

[0039] In step S11, the mixing conditions of the raw material powders (for example, mixing time, solvent type, etc.) are determined as appropriate. As the solvent, for example, an organic solvent or ion-exchanged water can be used. Note that in step S11, the raw material powders may be mixed by dry mixing.

[0040] In step S11, the molding conditions of the molded body (for example, the applied pressure, etc.) are determined as appropriate. When the shape of the molded body is plate-like, the molded body may be molded by filling the raw material powder into a hot press die or the like. The molding of the molded body may be performed by various other methods as long as the shape can be maintained. For example, after pouring the slurry after wet mixing into a mold while in a fluid state and then removing the solvent component, a molded body having a predetermined shape may be obtained. Alternatively, a predetermined Shape tape molded body may be formed by a tape molding method using a doctor blade or the like.

[0041] In step S11, when a green compact or a sintered body of the first member and / or the second member is prepared, the molded body formed by the above-described method is fired by a hot pressing method or the like to form a green compact (i.e., a semi-sintered body) or a sintered body. The firing conditions (e.g., pressing pressure, firing temperature, firing time, etc.) in the firing of the molded body are determined as appropriate. Further, the firing of the molded body may be performed by a method other than the hot pressing method.

[0042] Next, the raw material powder of the electrode 23 is weighed so as to have a predetermined composition, and after mixing the raw material powder, it is kneaded with a solvent, a binder, etc. to produce an electrode paste which is a precursor of the electrode 23 (step S12). In step S12, as the Ru raw material, ZrO 2 raw material and Al 2 O 3 raw material, for example, commercially available high-purity fine particles powder is used. The purity, average particle diameter, etc. of the Ru raw material, ZrO 2 raw material and Al 2 O 3 raw material are determined as appropriate. Since Ru is rich in ductility and not easy to grind, the average particle diameter of the Ru raw material is, for example, a dozen or so μm. Further, the average particle diameter of the ZrO 2 raw material and Al 2 O 3 raw material is, for example, less than 1 μm.

[0043] The mixing of the above-described raw material powder of the electrode 23 is performed, for example, by wet mixing. The mixing conditions of the raw material powder (e.g., mixing time, solvent type, etc.) are determined as appropriate. As the solvent, for example, an organic solvent or ion-exchanged water can be used. Note that in step S12, the raw material powder may be mixed by dry mixing. In step S12, the types of the above-described solvent (e.g., organic solvent) and binder kneaded with the raw material powder are determined as appropriate. Note that step S12 may be performed before step S11 or in parallel with step S11.

[0044] The electrode paste generated in step S12 is applied in a predetermined shape, such as by screen printing, onto the upper surface of the first member formed in step S11 (step S13). When the electrode paste is applied onto the first member which is a molded body in step S13, the first member is, for example, a tape molded body. In step S13, the application of the electrode paste may be performed by a method other than screen printing. Also, the first member which is a molded body or a green body may be regarded as a precursor of the first member. Therefore, when the electrode paste is applied onto the first member which is a molded body or a green body in step S13, it can also be regarded that the electrode paste is applied onto the upper surface of the precursor of the first member. Then, after the electrode paste is dried in the air or the like for a predetermined time (for example, 1 hour), the second member is laminated onto the first member and the electrode paste, and a laminate is formed (step S14).

[0045] Thereafter, the laminate formed in step S14 is fired by a hot press method or the like, whereby the first member and the second member are integrated, and the main body portion 21 and the electrode 23 (that is, the composite sintered body 20) are formed (step S15). The firing conditions (for example, press pressure, firing temperature, firing time, etc.) in step S15 are determined as appropriate. The firing temperature in step S15 (that is, the maximum temperature during firing) is, for example, 1550 °C or higher and 1650 °C or lower. The firing of the laminate in step S15 may be performed by a method other than the hot press method.

[0046] Next, with reference to Tables 1 to 3, Examples 1 to 26 of the composite sintered body 20 (that is, the main body portion 21 and the electrode 23) according to the present invention, and composite sintered bodies of Comparative Examples 1 to 4 for comparison with the composite sintered body 20 will be described. In Examples 1 to 26, the electrode 23 contains Ru, ZrO 2 and Al 2 O 3 whereas in Comparative Examples 1 to 4, the electrode 23 does not contain Al 2 O 3 .

[0047]

Table 1

[0048]

Table 2

[0049]

Table 3

[0050] In Examples 1 to 26 and Comparative Examples 1 to 4, the main body 21 and the electrode 23 were manufactured by the above-described steps S11 to S15. In Examples 1 to 26 and Comparative Examples 1 to 4, MgO was used as an additive to Al 2 O 3 When adding. As the raw material of Al 2 O 3 high-purity fine particle powder of commercially available Al 2 O 3 was used (purity: 99.99% or more, average particle diameter: 0.5 μm). Further, as the MgO raw material, high-purity fine particle powder of commercially available MgO (purity: 99% or more, average particle diameter: 1.2 μm) was used.

[0051] In Examples 1 to 26 and Comparative Examples 1 to 4, the wet mixing of the raw material powder in step S11 was performed by a ball mill using alumina balls and a poly pot. The mixing time was 20 hours, and the solvent used was an organic solvent. After drying the slurry produced by wet mixing and sieving it, the raw material powder of the main body 21 was obtained. Further, the forming of the formed body in step S11 was performed by filling the raw material powder into a mold for uniaxial pressure forming. The pressure during the uniaxial pressure forming was 100 kgf / cm 2 . In Examples 1 to 26 and Comparative Examples 1 to 4, a substantially disc-shaped formed body having a diameter of 50 mm and a thickness of 10 mm was formed. In Examples 1 to 26 and Comparative Examples 1 to 4, a test piece smaller than the actual composite sintered body 20 was produced and used.

[0052] In Examples 1 to 26 and Comparative Examples 1 to 4, in Steps S13 and S14, as the first member and the second member, any one of a molded body, a green compact, or a sintered body was used. When using a molded body as the first member or the second member, the one obtained in Step S11 described above was used.

[0053] When using a green compact as the first member or the second member, in Examples 1 to 26 and Comparative Examples 1 to 4, the molded body was produced and heat-treated by the same method as the above-described molded body. The firing temperature (i.e., the maximum temperature during heat treatment) was 800°C or higher and 1000°C or lower. Then, the obtained green compact was processed into a substantially disc shape with a diameter of 50 mm and a thickness of 5 mm. Note that the green compact may be produced by appropriately adopting existing methods such as heat-treating a molded body in which a molding aid such as an organic binder is added to raw material powder to maintain its shape, and the production conditions are not limited to the above.

[0054] When using a sintered body as the first member or the second member, the molded body was fired by the hot press method. Specifically, the above-described molded body was placed in a graphite mold for hot pressing, set in a hot press furnace, and fired. The press pressure during firing was 250 kgf / cm 2 2. The firing temperature (i.e., the maximum temperature during firing) was 1550°C or higher and 1650°C or lower. The firing time was 8 hours. The heating rate and the cooling rate were 300°C / h. The firing atmosphere was a nitrogen gas atmosphere. Then, the obtained sintered body was processed into a substantially disc shape with a diameter of 50 mm and a thickness of 5 mm.

[0055] In Examples 1 to 26 and Comparative Examples 1 to 4, in Step S12, as the Ru raw material, ZrO 2 raw material, and Al 2 O 3 raw material, commercially available high-purity fine Ru powder (purity 99.9% or higher, average particle size 15 μm), high-purity fine ZrO 2 powder (purity 99% or higher, average particle size 0.4 μm), and high-purity fine Al 2 O 3 powder (purity 99.99% or higher, average particle size 0.5 μm) were used.

[0056] In Examples 1 to 26 and Comparative Examples 1 to 4, the wet mixing of the raw material powder in Step S12 was performed by a ball mill using alumina balls and a poly pot. The mixing time was 20 hours, and the solvent used was an organic solvent. The slurry produced by wet mixing was dried and then sieved to obtain the raw material powder for the electrode 23. Further, butyl carbitol and polymethacrylic acid n-butyl were used as the solvent and binder kneaded with the raw material powder during the production of the electrode paste.

[0057] In Examples 1 to 26 and Comparative Examples 1 to 4, the application of the electrode paste in Step S13 was performed by screen printing. The application pattern of the electrode paste was a solid coating. In Examples 1 to 26 and Comparative Examples 1 to 4, the shape of the electrode paste applied on the first member was a substantially rectangular shape with a width of 5 mm and a length of 15 mm. The thickness of the electrode paste was 60 μm to 70 μm.

[0058] In Examples 1 to 26 and Comparative Examples 1 to 4, the firing after lamination in Step S15 was performed by the hot press method. Specifically, the above laminate was placed in a graphite mold for hot pressing, set in a hot press furnace, and fired. The press pressure during firing was 250 kgf / cm 2 . The firing temperature (i.e., the maximum temperature during firing) was 1550°C or higher and 1650°C or lower in Examples 1 to 26 and Comparative Examples 1 to 4. The firing time was 4 hours to 8 hours. The heating rate and the cooling rate were 300°C / h. The firing atmosphere was a nitrogen gas atmosphere.

[0059] In Tables 1 to 3, the thermal expansion coefficients of the base materials (i.e., the first member and the second member of the main body 21) were measured in the range of 40°C to 1000°C by a method according to JIS-R1618 using a sintered body sample cut out from the main body 21. The thermal expansion coefficient of the electrode 23 was the thermal expansion coefficient of each of Ru, ZrO 2 and Al 2 O 3 alone, and Ru, ZrO in the electrode 232 and Al 2 O 3 was determined based on the content rates thereof. Specifically, the sum of the product of the coefficient of thermal expansion of elemental Ru and the content rate (volume %) of Ru in the electrode 23, the product of the coefficient of thermal expansion of elemental ZrO 2 and the content rate (volume %) of ZrO 2 in the electrode 23, and the product of the coefficient of thermal expansion of elemental Al 2 O 3 and the content rate (volume %) of Al 2 O 3 in the electrode 23 was defined as the coefficient of thermal expansion of the electrode 23. The coefficient of thermal expansion of each of elemental Ru, ZrO 2 and Al 2 O 3 was measured in the range of 40°C to 1000°C by a method according to JIS-R1618, using bulk materials prepared by hot press firing commercially available Ru powder, ZrO 2 powder, and Al 2 O 3 powder under the same conditions as in step S11. The CTE difference is the absolute value of the difference between the coefficient of thermal expansion of the electrode 23 and that of the main body 21 described above.

[0060] The Ru-ZrO 2 peak ratio in the electrode 23 is the intensity ratio of the main peaks of Ru and ZrO 2 measured by the above-described XRD. The Ru-ZrO 2 peak ratio was calculated as I1 / (I1 + I2), where I1 is the intensity of the (101) plane, which is the main peak of Ru, and I2 is the intensity of the (111) plane, which is the main peak of ZrO 2 . Also, when performing the measurement by XRD, the second member was removed, and the electrode 23 located on the first member was exposed for measurement. As the X-ray diffractometer, an enclosed tube type X-ray diffractometer (D8-ADVANCE manufactured by Bruker AXS K.K.) was used. The measurement conditions were CuKα, 40 kV, 40 mA, 2θ = 10 to 70°, and the step width was 0.002°.

[0061] ZrO 2 occupancy area ratio is the ZrO 2It is a parameter indicating the degree of uneven distribution and was obtained as follows. First, a test piece having a cross section substantially parallel to the vertical direction (i.e., the thickness direction of the electrode 23) is cut out from the composite sintered body 20 formed in step S15. The test piece is cut out so that the electrode 23 is located at a substantially central portion in the vertical direction. Subsequently, the above cross section of the test piece is polished to a mirror finish, and an image of the cross section (i.e., a cross-sectional SEM image) is acquired using a scanning electron microscope (SEM).

[0062] Figure 3 is a cross-sectional SEM image of the composite sintered body 20 of Example 1. The whitish region at the central portion in the vertical direction in Figure 3 corresponds to the electrode 23. Also, the black band-shaped region below the electrode 23 corresponds to the first member of the main body portion 21, and the black band-shaped region above the electrode 23 corresponds to the second member of the main body portion 21. In the region corresponding to the electrode 23, the widest and palest region that forms the background is Ru, and the gray island-shaped regions darker in color than Ru are ZrO 2 2. The same applies to Figure 5 described later. Also, in the region corresponding to the electrode 23 in Figure 3, it is located substantially on ZrO 2 2 and is a black dot-shaped region darker in color than ZrO 2 2 is Al 2 2 3 O3

[0063] Next, the region corresponding to the electrode 23 in the cross-sectional SEM image (i.e., the cross-sectional SEM image of the electrode 23) is divided into three equal parts in the vertical direction, and three substantially rectangular regions arranged in the vertical direction are set. In the following description, these three regions are referred to as "first region 231", "second region 232", and "third region 233" in order from the lower side (i.e., the first member side), which is one side in the vertical direction. In Figure 3, the first region 231, the second region 232, and the third region 233 are each surrounded by a two-dot chain line and shown. Then, using image processing software (Hitachi High-Technologies Corporation "Image-Pro"), the area of ZrO2 in the first region 231 and the area of ZrO2 in the second region 232 are calculated. And the area of ZrO2 in the second region 232 is divided by the area of ZrO2 in the first region 231 Occupation area, and the area of ZrO2 in the second region 232 Occupation area Occupation area, and the area of ZrO2 in the first region 231 Occupation The ZrO2 occupied area ratio was calculated by dividing by the area.

[0064] ZrO 2 As the occupied area ratio approaches 1.0, the amount of ZrO 2 and the occupancy rate of ZrO in the second region 232 2 The difference between the occupancy rate of ZrO and that of 2 As the occupied area ratio approaches 1.0, the amount of ZrO 2 The ZrO 2 As the occupied area ratio becomes smaller within a range of 1.0 or less, the ZrO 2 The occupancy rate of ZrO in the second region 232 is 2 That is, the occupancy rate of ZrO 2 As the occupied area ratio becomes smaller within a range of 1.0 or less, the ZrO 2 The degree of uneven distribution of the

[0065] The resistivity of the electrode 23 was determined as follows. First, a roughly rectangular parallelepiped test piece with a width, length and thickness of 9 mm was cut out from the compound sintered body 20 formed in step S15. The test piece was cut out so that an electrode 23 with a width of 5 mm and a length of 9 mm was embedded in the center. The electrode 23 with a width of 5 mm was exposed on both end faces of the test piece. The cross-sectional area S (cm 2 ) was obtained by measuring the width and length of electrode 23 at the end face of the test piece using an optical microscope. In addition, the distance between both end faces of the test piece where electrode 23 was exposed was measured using a vernier caliper, and was defined as the length L (cm) of electrode 23. The circuit for measuring resistance was constructed by applying conductive paste to both end faces of electrode 23 and connecting lead wires. Then, in the atmosphere at room temperature, a minute current I (mA) in the range of 0 mA to 150 mA was applied to electrode 23, and the minute voltage value V (mV) generated at that time was measured, and the resistance R (Ω) of electrode 23 was obtained by R = V / I. Then, the resistivity ρ (Ω·cm) of electrode 23 was obtained by ρ = R × S / L.

[0066] The adhesion strength of the electrode 23 was determined as follows. First, a substantially cylindrical test piece extending in the vertical direction (i.e., the thickness direction of the composite sintered body 20) was cut out from the composite sintered body 20 formed in step S15. The composite sintered body 20 from which the test piece for measuring the adhesion strength was cut out differed in thickness and the coating shape of the electrode paste from those used for the other measurements. Specifically, the electrode paste was applied in a substantially circular shape with a diameter slightly smaller than that of the first member on a substantially disc-shaped first member having a diameter of 50 mm and a thickness of 10 mm. The thickness of the electrode paste was 50 μm to 60 μm. Then, a substantially disc-shaped second member having a diameter of 50 mm and a thickness of 10 mm was laminated on the first member and the electrode paste, thereby forming a substantially disc-shaped laminate having a diameter of 50 mm and a thickness of 20 mm. Thereafter, the laminate was fired at 1600°C to 1700°C to form the composite sintered body 20.

[0067] Five test pieces were cut out from the composite sintered body 20. The cutting positions of the test pieces in the composite sintered body 20 (i.e., the central positions of the respective test pieces in plan view) were the center of the composite sintered body 20 in plan view and four positions arranged at equal angular intervals in the circumferential direction on the same circumference around the center. The diameter of the cross section perpendicular to the longitudinal direction (i.e., the vertical direction) of the test piece was 9.9 mm. In the test piece, a substantially disc-shaped electrode 23 was present at a substantially central portion in the longitudinal direction, and the lower and upper portions of the electrode 23 were the first portion and the second portion of the main body portion 21, respectively. In the test piece, the electrode 23 was provided over substantially the entire upper end surface of the first portion and the lower end surface of the second portion.

[0068] Subsequently, as shown in FIG. 4, the test piece 200 arranged with its longitudinal direction horizontal was accommodated inside the jig 201. Inside the jig 201, an accommodation space having substantially the same shape as the test piece 200 is provided. The jig 201 includes two jig elements 202 and 203 adjacent in the left - right direction. The portion of the test piece 200 to the left of the electrode 23 is accommodated inside the jig element 202, and the portion of the test piece 200 to the right of the electrode 23 is accommodated inside the jig element 203. The boundary surface between the jig element 202 and the jig element 203 in surface contact in the left - right direction is located at the same position as the electrode 23 of the test piece 200 in the left - right direction. The lower surface of the jig element 202 protrudes downward more than the lower surface of the jig element 203, and the upper surface of the jig element 203 protrudes upward more than the upper surface of the jig element 202.

[0069] The jig 201 accommodating the test piece 200 is set to be sandwiched from above and below in the "Autograph AG - 10TD" manufactured by Shimadzu Corporation. Next, upward and downward loads are applied to the jig element 202 and the jig element 203, respectively. That is, a shear load is applied to the electrode 23. Then, the load is gradually increased, and the test is conducted until the left and right portions of the electrode 23 of the test piece 200 (that is, the first portion and the second portion of the main body portion 21) break. After that, the measured maximum load is divided by the area perpendicular to the longitudinal direction of the electrode 23 (that is, the cross - sectional area perpendicular to the longitudinal direction of the test piece 200) to obtain the adhesion strength of the electrode 23.

[0070] In Examples 1 - 26 and Comparative Examples 1 - 4, the main material of the main body portion 21 is Al 2 O 3 and the additive is MgO. Also, as described above, in Examples 1 - 26, the electrode 23 is formed of Ru, ZrO 2 and Al 2 O 3 . On the other hand, in Comparative Example 1, the electrode 23 is formed only of Ru and does not contain ZrO 2 and Al 2 O 3 . Also, in Comparative Examples 2 - 4, the electrode 23 is formed of Ru and ZrO 2 and does not contain Al 2 O3 does not include

[0071] In Example 1, the first member of the main body 21 to which the electrode paste is applied in step S13 is a green compact. Also, the second member laminated on the first member in step S14 is a molded body. The MgO content of the main body 21 is 0.025% by mass, and the thermal expansion coefficient of the main body 21 is 8.1 ppm / °C. Note that the remainder of the main body 21 other than MgO is Al 2 O 3 (the same applies to other examples and comparative examples). The total content of ZrO 2 and Al 2 O 3 in the electrode 23 is 23.8% by volume, and the Al 2 O 3 / ZrO 2 content ratio is 0.5. The thermal expansion coefficient of the electrode 23 is 8.1 ppm / °C. The firing temperature (i.e., the maximum temperature during firing) of the composite sintered body 20 is 1600°C.

[0072] In Example 1, the CTE difference (i.e., the absolute value of the difference in thermal expansion coefficients between the electrode 23 and the main body 21 in the range of 40°C or higher and 1000°C or lower) was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.96. The ZrO 2 occupied area ratio was 0.8. The resistivity of the electrode 23 was 1.8×10 -5 Ω·cm.

[0073] In Example 1, since the ZrO 2 occupied area ratio is close to 1.0, when the electrode paste applied on the first member is attracted to the first member, ZrO 2 in the electrode paste is suppressed from being biased toward the first member side (i.e., the lower side), and it can be seen that ZrO 2 is suppressed from being unevenly distributed on the first member side in the fired electrode 23. Also, the CTE difference is as small as 0.3 ppm / °C or less, and as described above, ZrO 2Since the uneven distribution of -5 was also suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Furthermore, the resistivity of the electrode 23 was as low as 3.0×10

[0074] In Example 2, the MgO content in the main body 21 was 1.0% by mass, and the coefficient of thermal expansion of the main body 21 was 8.2 ppm / °C. In the electrode 23, the total content of ZrO 2 and Al 2 O 3 was 27.0% by volume, and the Al 2 O 3 / ZrO 2 content ratio was 0.4. The coefficient of thermal expansion of the electrode 23 was 8.2 ppm / °C. Other conditions were the same as in Example 1.

[0075] In Example 2, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.91. The ZrO 2 occupied area ratio was 0.8. The resistivity of the electrode 23 was 1.9×10 -5 Ω·cm. In Example 2, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low.

[0076] In Example 3, the MgO content in the main body 21 was 5.0% by mass, and the coefficient of thermal expansion of the main body 21 was 8.3 ppm / °C. In the electrode 23, the total content of ZrO 2 and Al 2 O 3 was 30.2% by volume, and the Al 2 O 3 / ZrO 2 content ratio was 0.4. The coefficient of thermal expansion of the electrode 23 was 8.3 ppm / °C. Other conditions were the same as in Example 1.

[0077] In Example 3, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.86. The ZrO 2 occupancy area ratio was 1.2. The resistivity of the electrode 23 was 2.0×10 -5 Ω·cm. In Example 3, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0078] Focusing on Examples 1 to 3, even when the coefficient of thermal expansion of the main body 21 was changed within the above range (i.e., 8.1 ppm / °C to 8.3 ppm / °C), the CTE difference could be set to 0.0 ppm / °C, and the ZrO 2 occupancy area ratio could be set to 0.8 to 1.2, and cracks in the main body 21 and peeling of the electrode 23 could be prevented.

[0079] In Example 4, the total content rate of ZrO 2 and Al 2 O 3 in the electrode 23 was 19.7 vol%, and the Al 2 O 3 / ZrO 2 content rate ratio was 0.2. Other conditions were the same as in Example 1.

[0080] In Example 4, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.95. The ZrO 2 occupancy area ratio was 0.4. The resistivity of the electrode 23 was 1.6×10 -5 Ω·cm. In Example 4, since the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0081] In Example 5, the ZrO 2 and Al 2O 3 The total content ratio is 21.3% by volume, and Al 2 O 3 / ZrO 2 The content ratio is 0.3. Other conditions are the same as in Example 1.

[0082] In Example 5, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.97. The ZrO 2 occupancy area ratio was 0.5. The resistivity of electrode 23 was 1.7×10 -5 Ω·cm. In Example 5, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0083] In Example 6, the firing temperature of the composite sintered body 20 is 1550°C. Other conditions are the same as in Example 1.

[0084] In Example 6, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.95. The ZrO 2 occupancy area ratio was 0.7. The resistivity of electrode 23 was 1.8×10 -5 Ω·cm. In Example 6, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0085] In Example 7, the firing temperature of the composite sintered body 20 is 1650°C. Other conditions are the same as in Example 1.

[0086] In Example 7, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.96. The ZrO 2 occupancy area ratio was 2.0. The resistivity of electrode 23 was 1.5×10 -5It was Ω·cm. In Example 7, the CTE difference was small, and the uneven distribution of ZrO 2 was suppressed. Therefore, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0087] Focusing on Examples 1, 6, and 7, even when the firing temperature of the composite sintered body 20 was changed within the above range (i.e., 1550°C to 1650°C), the CTE difference could be set to 0.0 ppm / °C, and the ZrO 2 occupancy area ratio could be set to 0.7 to 2.0, and cracks in the main body 21 and peeling of the electrode 23 could be prevented.

[0088] In Example 8, the total content of ZrO 2 and Al 2 O 3 in the electrode 23 was 29.6% by volume, and the Al 2 O 3 / ZrO 2 content ratio was 1.0. Other conditions were the same as in Example 1.

[0089] In Example 8, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.95. The ZrO 2 occupancy area ratio was 1.2. The resistivity of the electrode 23 was 1.8×10 -5 Ω·cm. In Example 8, the CTE difference was small, and the uneven distribution of ZrO 2 was suppressed. Therefore, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0090] In Example 9, the total content of ZrO 2 and Al 2 O 3 in the electrode 23 was 63.8% by volume, and the Al 2 O 3 / ZrO 2 content ratio was 3.6. Other conditions were the same as in Example 1.

[0091] In Example 9, the CTE difference was 0.0 ppm / °C. Ru-ZrO 2 The peak ratio was 0.82. ZrO 2 The occupied area ratio was 1.4. The resistivity of the electrode 23 was 3.0×10 -5 Ω·cm. In Example 9, since the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0092] Example 1 ,4 , 5, 8, 9, when paying attention, even if the total content ratio of ZrO2 and Al2O3 in the electrode 23 is changed within the above range (i.e., 19.7 vol% to 63.8 vol%) and the Al2O3 / ZrO2 content ratio is changed within the above range (i.e., 0.2 to 3.6), the CTE difference can be set to 0.0 ppm / °C and the ZrO2 occupied area ratio can be 0.4~1.4 set to, and cracks in the main body 21 and peeling of the electrode 23 can be prevented.

[0093] In Examples 1, 5, 8, 9, the ZrO 2 and Al 2 O 3 total content ratio was 21.3 vol% to 63.8 vol% (i.e., 20 vol% or more), while in Example 4, the total content ratio was 19.7 vol% (i.e., less than 20 vol%). For this reason, the ZrO 2 occupied area ratio in Examples 1, 5, 8, 9 was 0.5 to 1.4 (i.e., 0.5 or more and 2.0 or less), while the ZrO 2 occupied area ratio in Example 4 was 0.4 (i.e., less than 0.5). In Examples 1, 5, 8, 9, compared with Example 4, the uneven distribution of ZrO 2 in the electrode 23 was more preferably suppressed.

[0094] In Example 10, the ZrO 2 and Al 2 O 3The total content ratio is 33.4% by volume, and Al 2 O 3 / ZrO 2 The content ratio is 0.3. Also, the thermal expansion coefficient of the electrode 23 is 8.4 ppm / °C. Other conditions are the same as in Example 1.

[0095] In Example 10, the CTE difference was 0.3 ppm / °C. The Ru-ZrO 2 peak ratio was 0.80. The ZrO 2 occupied area ratio was 1.3. The resistivity of the electrode 23 was 2.1×10 -5 Ω·cm. In Example 10, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0096] In Example 11, for ZrO 2 and Al 2 O 3 in the electrode 23, the total content ratio is 30.2% by volume, and Al 2 O 3 / ZrO 2 The content ratio is 0.4. Also, the thermal expansion coefficient of the electrode 23 is 8.3 ppm / °C. Other conditions are the same as in Example 1.

[0097] In Example 11, the CTE difference was 0.2 ppm / °C. The Ru-ZrO 2 peak ratio was 0.85. The ZrO 2 occupied area ratio was 1.2. The resistivity of the electrode 23 was 1.9×10 -5 Ω·cm. In Example 11, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0098] In Example 12, for ZrO 2 and Al 2O 3 The total content rate is 17.6% by volume, and Al 2 O 3 / ZrO 2 The content rate ratio is 0.8. Also, the thermal expansion coefficient of the electrode 23 is 7.9 ppm / °C. Other conditions are the same as in Example 1.

[0099] In Example 12, the CTE difference was 0.2 ppm / °C. The Ru-ZrO 2 peak ratio was 0.98. The ZrO 2 occupation area ratio was 0.6. The resistivity of the electrode 23 was 1.6×10 -5 Ω·cm. In Example 12, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0100] In Example 13, for ZrO 2 and Al 2 O 3 in the electrode 23, the total content rate is 14.3% by volume, and Al 2 O 3 / ZrO 2 The content rate ratio is 1.3. Also, the thermal expansion coefficient of the electrode 23 is 7.8 ppm / °C. Other conditions are the same as in Example 1.

[0101] In Example 13, the CTE difference was 0.3 ppm / °C. The Ru-ZrO 2 peak ratio was 0.99. The ZrO 2 occupation area ratio was 0.5. The resistivity of the electrode 23 was 1.5×10 -5 Ω·cm. In Example 13, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0102] Focusing on Examples 1, 10 to 13, for ZrO in the electrode 232 and Al 2 O 3 total content rate and Al 2 O 3 / ZrO 2 even when the content rate ratio is changed and the CTE difference is changed within the above range (i.e., 0.0 ppm / °C to 0.3 ppm / °C), the ZrO 2 occupation area ratio can be set to 0.5 to 1.3, and cracks in the main body portion 21 and peeling of the electrode 23 can be prevented.

[0103] In Example 14, the second member laminated on the first member in step S14 is a green compact. Other conditions are the same as in Example 1.

[0104] In Example 14, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.96. The ZrO 2 occupation area ratio was 0.8. The resistivity of the electrode 23 was 1.8×10 -5 Ω·cm. These numerical values in Example 14 are the same as those in Example 1. Therefore, in Example 14, cracks in the main body portion 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body portion 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low.

[0105] In Example 15, the second member laminated on the first member in step S14 is a sintered body. Other conditions are the same as in Example 1.

[0106] In Example 15, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.95. The ZrO 2 occupation area ratio was 0.7. The resistivity of the electrode 23 was 1.8×10 -5 Ω·cm. These numerical values in Example 15 are almost the same as those in Example 1. Therefore, in Example 15, cracks in the main body portion 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body portion 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low.

[0107] Focusing on Examples 1, 14, and 15, regardless of whether the second member laminated on the first member in step S14 is a green body, a calcined body, or a sintered body, the CTE difference is set to 0.0 ppm / °C, and ZrO 2 The occupied area ratio can be 0.7 to 0.8, and cracks in the main body portion 21 and peeling of the electrode 23 can be prevented.

[0108] In Example 16, the first member to which the electrode paste is applied in step S13 is a tape green body. Other conditions are the same as in Example 1.

[0109] In Example 16, the CTE difference was 0.0 ppm / °C. Ru-ZrO 2 The peak ratio was 0.95. ZrO 2 The occupied area ratio was 0.9. The resistivity of the electrode 23 was 1.9×10 -5 Ω·cm. In Example 16, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body portion 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body portion 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0110] In Example 17, the first member to which the electrode paste is applied in step S13 is a sintered body. Other conditions are the same as in Example 1.

[0111] In Example 17, the CTE difference was 0.0 ppm / °C. Ru-ZrO 2 The peak ratio was 0.97. ZrO 2 The occupied area ratio was 1.0. The resistivity of the electrode 23 was 1.7×10 -5 Ω·cm. In Example 17, since the CTE difference was small and the uneven distribution of ZrO 2 was suppressed, cracks in the main body portion 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body portion 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small.

[0112] Regarding Examples 1, 16, and 17, regardless of whether the first member to which the electrode paste is applied in step S13 is a green body, a molded body, or a sintered body, the CTE difference is set to 0.0 ppm / °C, and ZrO 2 The occupied area ratio can be 0.8 to 1.0, and cracks in the main body 21 and peeling of the electrode 23 could be prevented.

[0113] In Example 18, the second member laminated on the first member in step S14 is a green body. Other conditions are the same as in Example 17.

[0114] In Example 18, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.97. The ZrO 2 occupied area ratio was 1.1. The resistivity of the electrode 23 was 1.7×10 -5 Ω·cm. These numerical values in Example 18 are almost the same as those in Example 17. Therefore, in Example 18, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low.

[0115] In Example 19, the second member laminated on the first member in step S14 is a sintered body. Other conditions are the same as in Example 17.

[0116] In Example 19, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.96. The ZrO 2 occupied area ratio was 1.0. The resistivity of the electrode 23 was 1.8×10 -5 Ω·cm. These numerical values in Example 19 are almost the same as those in Example 17. Therefore, in Example 19, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients of the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low.

[0117] Focusing on Examples 17 to 19, regardless of whether the second member laminated on the first member in step S14 is a molded body, a calcined body, or a sintered body, the CTE difference is set to 0.0 ppm / °C, and ZrO 2 The occupied area ratio can be 1.0 to 1.1, and cracks in the main body portion 21 and peeling of the electrode 23 can be prevented.

[0118] In Example 20, in the electrode 23, ZrO 2 and Al 2 O 3 The total content rate is 30.1% by volume, and the Al 2 O 3 / ZrO 2 The content ratio is 1.1. Other conditions are the same as in Example 1.

[0119] In Example 20, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.98. The ZrO 2 occupied area ratio was 1.5. The resistivity of the electrode 23 was 2.0×10 -5 Ω·cm. In Example 20, since the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed, cracks in the main body portion 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body portion 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small. In Example 20, a test piece 200 (see FIG. 4) for measuring the adhesion strength of the electrode 23 was cut out, but it could not be measured because the first part and the second part separated during the cutting process.

[0120] In Example 21, in the electrode 23, ZrO 2 and Al 2 O 3 The total content rate is 36.7% by volume, and the Al 2 O 3 / ZrO 2 The content ratio is 1.8. Other conditions are the same as in Example 20.

[0121] In Example 21, the CTE difference was 0.0 ppm / °C. The Ru-ZrO2 The peak ratio was 0.96. ZrO 2 The occupied area ratio was 1.6. The resistivity of electrode 23 was 2.2×10 -5 Ω·cm. In Example 21, the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed. Therefore, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small. In Example 21, similar to Example 20, since the first part and the second part were separated during the cutting process, the adhesion strength of the electrode 23 could not be measured.

[0122] In Example 22, the total content of ZrO 2 and Al 2 O 3 in the electrode 23 was 43.2% by volume, and the content ratio of Al 2 O 3 / ZrO 2 was 2.7. Other conditions were the same as in Example 20.

[0123] In Example 22, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.83. The ZrO 2 occupied area ratio was 1.0. The resistivity of the electrode 23 was 2.7×10 -5 Ω·cm. In Example 22, the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed. Therefore, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small. Furthermore, the adhesion strength of the electrode 23 was 99 MPa. In Example 22, since the adhesion strength was 90 MPa or more and was relatively large, peeling of the electrode 23 from the main body 21 due to mechanical shock or the like could be preferably suppressed.

[0124] In Example 23, the total content of ZrO 2 and Al 2 O 3 in the electrode 23 was 46.6% by volume, and the content of Al 2O 3 / ZrO 2 The content ratio is 3.2. Other conditions are the same as in Example 20.

[0125] In Example 23, the CTE difference was 0.0 ppm / °C. Ru-ZrO 2 The peak ratio was 0.81. ZrO 2 The occupied area ratio was 0.9. The resistivity of Electrode 23 was 2.8×10 -5 Ω·cm. In Example 23, since the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small. Furthermore, the adhesion strength of the electrode 23 was 121 MPa. In Example 23, since the adhesion strength was 90 MPa or more and was relatively large, peeling of the electrode 23 from the main body 21 due to mechanical shock or the like could be preferably suppressed.

[0126] In Example 24, for ZrO 2 and Al 2 O 3 in the electrode 23, the total content ratio was 49.8 vol%, and the Al 2 O 3 / ZrO 2 content ratio was 3.8. Other conditions are the same as in Example 20.

[0127] In Example 24, the CTE difference was 0.0 ppm / °C. Ru-ZrO 2 The peak ratio was 0.83. ZrO 2 The occupied area ratio was 1.1. The resistivity of the electrode 23 was 2.9×10 -5 Ω·cm. In Example 24, since the CTE difference was small and 2Since the uneven distribution was relatively suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low. Furthermore, the adhesion strength of the electrode 23 was 146 MPa. In Example 24, since the adhesion strength was 90 MPa or more and was relatively large, peeling of the electrode 23 from the main body 21 due to mechanical shock or the like could be suitably suppressed.

[0128] Focusing on Examples 20 to 24, from the viewpoint of increasing the adhesion strength of the electrode 23, the total content of ZrO 2 and Al 2 O 3 in the electrode 23 is preferably 40% by volume or more. Also, the Al 2 O 3 / ZrO 2 content ratio is preferably 2.0 or more.

[0129] Focusing on Examples 20 to 23, even when the total content of ZrO 2 and Al 2 O 3 in the electrode 23 was changed within the above range (i.e., 30.1% by volume to 46.6% by volume) and the Al 2 O 3 / ZrO 2 content ratio was changed within the above range (i.e., 1.1 to 3.2), the CTE difference was set to 0.0 ppm / °C, and the ZrO 2 occupied area ratio could be set to 0.9 to 1.6, and cracks in the main body 21 and peeling of the electrode 23 could be prevented.

[0130] Also, in Example 24, even when the total content of ZrO 2 and Al 2 O 3 in the electrode 23 was 49.8% by volume and the Al 2 O 3 / ZrO 2 content ratio was 3.8, the CTE difference was set to 0.0 ppm / °C, and the ZrO 2 occupied area ratio could be set to 1.1, and cracks in the main body 21 and peeling of the electrode 23 could be prevented.

[0131] In Example 25, the MgO content in the main body 21 is 0.1% by mass. Also, in the electrode 23, the total content of ZrO 2 and Al 2 O 3 is 23.6% by volume, and the Al 2 O 3 / ZrO 2 content ratio is 0.5. Other conditions are the same as in Example 20.

[0132] In Example 25, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.92. The ZrO 2 occupied area ratio was 1.8. The resistivity of the electrode 23 was 1.9×10 -5 Ω·cm. In Example 25, since the CTE difference was small and the uneven distribution of ZrO 2 was relatively suppressed, cracks in the main body 21 and peeling of the electrode 23 due to the difference in the thermal expansion coefficients between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was small. Furthermore, the adhesion strength of the electrode 23 was 59 MPa. In Example 25, since the adhesion strength was 50 MPa or more, peeling of the electrode 23 from the main body 21 due to mechanical shock or the like could be suppressed.

[0133] In Example 26, the MgO content in the main body 21 is 0.1% by mass. Other conditions are the same as in Example 24.

[0134] In Example 26, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.82. The ZrO 2 occupied area ratio was 1.1. The resistivity of the electrode 23 was 2.9×10 -5 Ω·cm. In Example 26, since the CTE difference was small and 2Since the uneven distribution was relatively suppressed, cracks in the main body 21 or peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 did not occur. Also, the resistivity of the electrode 23 was low. Furthermore, the adhesion strength of the electrode 23 was 250 MPa. In Example 26, since the adhesion strength was 90 MPa or more and relatively large, peeling of the electrode 23 from the main body 21 due to mechanical shock or the like could be suitably suppressed.

[0135] Focusing on Examples 24 and 26, from the viewpoint of increasing the adhesion strength of the electrode 23, the content rate of MgO in the main body 21 is preferably 0.1 mass% or more.

[0136] In Comparative Example 1, as described above, the electrode 23 was formed only of Ru and did not contain ZrO 2 and Al 2 O 3 The coefficient of thermal expansion of the electrode 23 was 7.6 ppm / °C. Other conditions were the same as in Example 17. In Comparative Example 1, since the CTE difference was as large as 0.5 ppm / °C, cracks in the main body 21 or peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23 occurred.

[0137] In Comparative Example 2, as described above, the electrode 23 was formed of Ru and ZrO 2 and did not contain Al 2 O 3 The content rate of ZrO 2 in the electrode 23 was 10.0 volume%, and the coefficient of thermal expansion of the electrode 23 was 7.9 ppm / °C. Other conditions were the same as in Example 1.

[0138] In Comparative Example 2, the CTE difference was 0.2 ppm / °C. The Ru-ZrO 2 peak ratio was 0.99. The occupied area ratio of ZrO 2 was 0.2. The resistivity of the electrode 23 was 1.3×10 -5 Ω·cm. In Comparative Example 2, the occupied area ratio of ZrO 2 was much smaller than 1.0, and the occupied area ratio of ZrO 2is unevenly distributed on the first member side. For this reason, cracks in the main body 21 and peeling of the electrode 23 occurred due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23.

[0139] In Comparative Example 3, the content of ZrO in the electrode 23 2 was 17.2% by volume, and the coefficient of thermal expansion of the electrode 23 was 8.1 ppm / °C. Other conditions were the same as in Comparative Example 2.

[0140] In Comparative Example 3, the CTE difference was 0.0 ppm / °C. The Ru-ZrO 2 peak ratio was 0.95. The ZrO 2 occupied area ratio was 0.2. The resistivity of the electrode 23 was 1.5×10 -5 Ω·cm. In Comparative Example 3, the ZrO 2 occupied area ratio was much smaller than 1.0, and as shown in FIG. 5, the ZrO 2 was unevenly distributed on the first member side (i.e., the lower side in FIG. 5). For this reason, cracks in the main body 21 and peeling of the electrode 23 occurred due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23.

[0141] In Comparative Example 4, the content of ZrO in the electrode 23 2 was 27.6% by volume, and the coefficient of thermal expansion of the electrode 23 was 8.4 ppm / °C. Other conditions were the same as in Comparative Example 2.

[0142] In Comparative Example 4, the CTE difference was 0.3 ppm / °C. The Ru-ZrO 2 peak ratio was 0.81. The ZrO 2 occupied area ratio was 0.3. The resistivity of the electrode 23 was 1.8×10 -5 Ω·cm. In Comparative Example 4, the ZrO 2 occupied area ratio was much smaller than 1.0, and the ZrO 2 was unevenly distributed on the first member side. For this reason, cracks in the main body 21 and peeling of the electrode 23 occurred due to the difference in the coefficient of thermal expansion between the main body 21 and the electrode 23.

[0143] As described above, the composite sintered body 20 is Al 2 O3 A base material (the main body 21 in the above example) made of the above as the main material, and an electrode 23 disposed inside or on the surface of the base material. The electrode 23 contains Ru, ZrO 2 and Al 2 O 3 and. Thus, as shown in Examples 1 to 19, uneven distribution of ZrO 2 in the electrode 23 can be suppressed. As a result, cracks in the base material and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the electrode 23 and the base material caused by the uneven distribution can be suppressed. In addition, since an increase in the resistivity of the electrode 23 can also be suppressed, the calorific value generated by the electrode 23 can be accurately controlled.

[0144] As described above, the absolute value of the difference in the coefficient of thermal expansion between the electrode 23 and the base material is preferably 0.3 ppm / °C or less in the range of 40°C or more and 1000°C or less. Thereby, cracks in the base material and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the electrode 23 and the base material can be further suppressed.

[0145] As described above, the resistivity of the electrode 23 at room temperature is preferably 3.0×10 -5 Ω·cm or less. Thereby, the calorific value generated by the electrode 23 can be more accurately controlled.

[0146] As described above, the total content of ZrO 2 and Al 2 O 3 in the electrode 23 is preferably 20% by volume or more. Thereby, as shown by the comparison between Examples 1, 5, 8, 9 and Example 4, uneven distribution of ZrO 2 in the electrode 23 can be further suppressed.

[0147] As described above, the content of Al 2 O 3 in the electrode 23 is preferably 0.2 times or more and 3.6 times or less the content of ZrO 2 . Thereby, uneven distribution of ZrO 2 in the electrode 23 can be suitably suppressed.

[0148] Also, for Al in electrode 23 2 O 3 the content rate is preferably greater than 3.6 times and equal to or less than 3.8 times the content rate of ZrO 2 . Also in this case, uneven distribution of ZrO 2 in electrode 23 can be suitably suppressed.

[0149] As described above, for the solid matter in electrode 23, the total content rate of Ru, ZrO 2 and Al 2 O 3 is preferably 100% by volume. Thereby, an increase in manufacturing cost due to an increase in the types of materials for electrode 23 can be prevented.

[0150] As described above, in electrode 23, the intensity ratio of the main peaks of Ru and ZrO 2 obtained by X-ray diffraction method (that is, the Ru-ZrO 2 peak ratio) is preferably 0.80 or more and less than 1.0. In this way, by setting the composition ratio of Ru and ZrO 2 in electrode 23 within a suitable range, while suitably suppressing an increase in the resistivity of electrode 23, the difference in the thermal expansion coefficients between electrode 23 and the base material can be suitably reduced.

[0151] As described above, if a cross-sectional SEM image of electrode 23 parallel to the thickness direction of electrode 23 is equally divided into three in the thickness direction, and is made into a first region 231, a second region 232, and a third region 233 in order from one side in the thickness direction, then the area of ZrO 2 in the central second region 232 is preferably 0.5 times or more and 2.0 times or less the area of ZrO 2 in the first region 231 between the second region 232 and the base material. In this way, by suitably suppressing the uneven distribution of ZrO 2 in electrode 23, cracks in the base material and peeling of electrode 23 due to the difference in the thermal expansion coefficients between electrode 23 and the base material caused by the influence of such uneven distribution can be suitably suppressed.

[0152] As described above, the adhesion strength of the electrode 23 to the base material is preferably 90 MPa or more. Thereby, peeling of the electrode 23 from the base material due to mechanical impact or the like can be suitably suppressed.

[0153] As described above, in the composite sintered body 20, while suppressing an increase in the resistivity of the electrode 23, the uneven distribution of ZrO 2 in the electrode 23 can be suppressed, and cracks in the base material and peeling of the electrode 23 can be suppressed. For this reason, the composite sintered body 20 is suitable for a semiconductor manufacturing apparatus member used in a semiconductor manufacturing apparatus. The composite sintered body 20 is particularly suitable for a semiconductor manufacturing apparatus member used in a high-output semiconductor manufacturing apparatus such as a high-power etching apparatus. As a suitable example of a semiconductor manufacturing apparatus member formed using the composite sintered body 20, the above-described susceptor 1 is mentioned. In the susceptor 1, as described above, the main body portion 21 is disc-shaped, and the substrate 9 is placed on the main surface of the main body portion 21.

[0154] The manufacturing method of the above-described composite sintered body 20 includes a step (step S11) of preparing a first member and a second member that are a molded body, a green compact, or a sintered body mainly made of Al 2 O 3 , a step of applying and drying a paste-like electrode material containing Ru, ZrO 2 and Al 2 O 3 on the first member (step S13), a step of laminating the second member on the first member to form a laminate (step S14), and a step of hot press sintering the laminate (step S15). Thereby, similarly to the above, the uneven distribution of ZrO 2 in the electrode 23 can be suppressed. As a result, cracks in the base material and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the electrode 23 and the base material caused by the influence of the uneven distribution can be suppressed.

[0155] As described above, according to the manufacturing method, the uneven distribution of ZrO 2Since the uneven distribution can be suppressed, the manufacturing method is particularly suitable when the first member in step S11 is a fired body or a tape-formed body that can relatively easily attract the electrode paste.

[0156] As described above, the absolute value of the difference in the coefficient of thermal expansion between the electrode 23 and the first member after the completion of step S15 is preferably 0.3 ppm / °C or less in the range of 40°C or more and 1000°C or less. Thereby, cracking of the base material and peeling of the electrode 23 due to the difference in the coefficient of thermal expansion between the electrode 23 and the base material can be further suppressed.

[0157] As described above, the firing temperature in step S15 is preferably 1550°C or more and 1650°C or less. By firing in this temperature range, while sufficiently sintering the base material (in the above example, the main body portion 21), in the electrode 23, coarsening of the ZrO 2 domain associated with grain growth of Ru can be suppressed. As a result, the characteristics of the electrode 23 can be stabilized.

[0158] In the above-described composite sintered body 20, semiconductor manufacturing apparatus member, and method for manufacturing the composite sintered body 20, various modifications are possible.

[0159] For example, the CTE difference of the composite sintered body 20 may be larger than 0.3 ppm / °C.

[0160] The resistivity of the electrode 23 at room temperature may be higher than 3.0×10 -5 Ω·cm.

[0161] The total content ratio of ZrO 2 and Al 2 O 3 in the electrode 23 may be less than 20% by volume.

[0162] In the related art of the present invention, The content ratio of Al 2 O 3 / ZrO 2 in the electrode 23 may be less than 0.2 or may be greater than 3.8.

[0163] In the related art of the present invention, Ru, ZrO in the solid matter in electrode 23 2 and Al 2 O 3 The total content rate may be less than 100% by volume.

[0164] In electrode 23, the Ru-ZrO 2 peak ratio may be less than 0.80.

[0165] ZrO 2 The occupied area ratio may be less than 0.5 or may be greater than 2.0.

[0166] The adhesion strength of electrode 23 to the base material may be less than 90 MPa or may be less than 50 MPa.

[0167] In the method for manufacturing the composite sintered body 20, the firing temperature in step S15 described above may be less than 1550 °C or may be higher than 1650 °C.

[0168] The composite sintered body 20 may be manufactured by a method different from the above manufacturing method.

[0169] In addition to the susceptor 1, the composite sintered body 20 may be used for manufacturing other semiconductor manufacturing apparatus members (for example, rings, shower heads, etc.) provided in a semiconductor manufacturing apparatus. Further, members used in an apparatus other than the semiconductor manufacturing apparatus may be manufactured using the composite sintered body 20. For example, the composite sintered body 20 may be used for manufacturing a susceptor that supports a substrate other than a semiconductor substrate, or may be used for manufacturing a ceramic heater that heats an object.

[0170] The configurations in the above embodiments and each modification may be appropriately combined as long as they do not contradict each other.

Industrial Applicability

[0171] The present invention relates to the field of semiconductor manufacturing equipment, and can be used, for example, in the manufacture of a susceptor for holding and heating a semiconductor substrate.

Explanation of Signs

[0172] 1 susceptor 9 substrate 20 composite sintered body 21 main body part 23 electrode 231 first region 232 second region 233 third region S11~S15 steps

Claims

1. A composite sintered body comprising: a base material mainly made of aluminum oxide; an electrode disposed inside or on the surface of the base material; and the electrode comprises: ruthenium; zirconium oxide; aluminum oxide; and the total content ratio of ruthenium, zirconium oxide and aluminum oxide in the solid matter of the electrode is 100% by volume, the content ratio of aluminum oxide in the electrode is 0.2 times or more and 3.8 times or less the content ratio of zirconium oxide, and the content ratio of ruthenium in the electrode is 36.8% by volume or more and 85.7% by volume or less. A composite sintered body characterized by the above.

2. The composite sintered body according to claim 1, wherein the absolute value of the difference in the coefficient of thermal expansion between the electrode and the base material is 0.3 ppm / °C or less in the range of 40°C to 1000°C. A composite sintered body characterized by the above.

3. The composite sintered body according to claim 1 or 2, wherein The resistivity of the electrode at room temperature is 3.0×10 －５ Ω·cm or less, and the composite sintered body is characterized by this.

4. The composite sintered body according to any one of claims 1 to 3, wherein the total content ratio of zirconium oxide and aluminum oxide in the electrode is 20% by volume or more. A composite sintered body characterized by the above.

5. The composite sintered body according to any one of claims 1 to 4, wherein in the electrode, the intensity ratio of the main peaks of ruthenium and zirconium oxide obtained by X-ray diffraction is 0.80 or more and less than 1.

0. A composite sintered body characterized by the above.

6. The composite sintered body according to any one of claims 1 to 5, wherein when the cross-sectional SEM image of the electrode parallel to the thickness direction of the electrode is divided into three equal parts in the thickness direction, and is sequentially defined as a first region, a second region, and a third region from one side in the thickness direction, the area of zirconium oxide in the central second region is 0.5 times or more and 2.0 times or less the area of zirconium oxide in the first region between the second region and the base material. A composite sintered body characterized by the above.

7. The composite sintered body according to any one of claims 1 to 6, wherein the adhesion strength of the electrode to the base material is 90 MPa or more. A composite sintered body characterized by the above.

8. A semiconductor manufacturing apparatus member used in a semiconductor manufacturing apparatus, which is manufactured using the composite sintered body according to any one of claims 1 to 7. The base material is disc-shaped, and a semiconductor substrate is placed on the main surface of the base material. A semiconductor manufacturing apparatus member characterized by this.

9. A method for manufacturing a composite sintered body, a) A step of preparing a first member and a second member, which are a molded body, a green compact, or a sintered body mainly made of aluminum oxide, b) A step of applying a paste-like electrode material containing ruthenium, zirconium oxide, and aluminum oxide onto the first member and drying it, c) A step of laminating the second member on the first member to form a laminate, d) A step of hot press sintering the laminate, comprising, In the solid matter in the electrode formed from the electrode material in step d), the total content of the ruthenium, the zirconium oxide, and the aluminum oxide is 100% by volume, The content of the aluminum oxide in the electrode is 0.2 times or more and 3.8 times or less the content of the zirconium oxide, A method for manufacturing a composite sintered body, characterized in that the content of the ruthenium in the electrode is 36.8% by volume or more and 85.7% by volume or less.

10. A method for manufacturing a composite sintered body according to claim 9, A method for manufacturing a composite sintered body, characterized in that the first member in step a) is a green compact or a tape-formed body.

11. A method for manufacturing a composite sintered body according to claim 9 or 10, A method for manufacturing a composite sintered body, characterized in that the absolute value of the difference in the coefficient of thermal expansion between the electrode and the first member after the completion of step d) is 0.3 ppm / °C or less in the range of 40°C or more and 1000°C or less.

12. A method for manufacturing a composite sintered body according to any one of claims 9 to 11, A method for manufacturing a composite sintered body, characterized in that the sintering temperature in step d) is 1550°C or more and 1650°C or less.

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