WO2020071178A1 - 半導電性セラミック部材 - Google Patents

半導電性セラミック部材

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Publication number
WO2020071178A1
WO2020071178A1 PCT/JP2019/037299 JP2019037299W WO2020071178A1 WO 2020071178 A1 WO2020071178 A1 WO 2020071178A1 JP 2019037299 W JP2019037299 W JP 2019037299W WO 2020071178 A1 WO2020071178 A1 WO 2020071178A1
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WIPO (PCT)
Prior art keywords
oxide
mass
content
terms
region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/037299
Other languages
English (en)
French (fr)
Inventor
立山　泰治
義宜 平野
尚也 藤田
千里 辻岳
高坂　祥二
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Corp
Original Assignee
Kyocera Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyocera Corp filed Critical Kyocera Corp
Priority to US17/279,203 priority Critical patent/US12027405B2/en
Priority to JP2020550314A priority patent/JP7036938B2/ja
Publication of WO2020071178A1 publication Critical patent/WO2020071178A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C04B2235/85—Intergranular or grain boundary phases
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/76—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches
    • H10P72/7604—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches the wafers being placed on a susceptor, stage or support
    • H10P72/7616—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches the wafers being placed on a susceptor, stage or support characterised by a coating, a hardness or a material

Definitions

  • the present invention relates to a semiconductive ceramic member.
  • Semiconductive ceramic members are used for holding and transporting wafers in exposure apparatuses and the like.
  • the semiconductive ceramic member has a low electric resistance capable of releasing static electricity in order to prevent dust and suspended particles from adhering to the wafer in addition to high mechanical strength.
  • an aluminum oxide ceramic containing aluminum oxide (Al 2 O 3 ) as a main component and titanium oxide (TiO 2 ) is known. Then, such aluminum oxide ceramics are given conductivity by firing in a reducing atmosphere (for example, see Patent Document 1).
  • the semiconductive ceramic member of the present disclosure contains a plurality of aluminum oxide crystal particles and a plurality of titanium oxide crystal particles. Further, out of 100% by mass of all components, the sum of aluminum oxide and titanium oxide is 99% by mass or more. In addition, of the total of 100% by mass of the aluminum oxide and the titanium oxide, the aluminum oxide is from 86% by mass to 96% by mass, and the titanium oxide is from 4% by mass to 14% by mass. In the measurement by X-ray photoelectron spectroscopy, a peak of TiO x (0 ⁇ x ⁇ 2) exists in a range of a binding energy of 456 eV to 462 eV.
  • the first region surrounded by two aluminum oxide crystal particles and one titanium oxide crystal particle contains silicon, and the content of the silicon in terms of oxide in the first region is the aluminum oxide crystal. More than the content of silicon in the grain boundary of the particles and the titanium oxide crystal particles in terms of oxide.
  • 1 is an example of an enlarged view of a cross section of a semiconductive ceramic member of the present disclosure.
  • 1 is an example of an X-ray photoelectron spectroscopy (XPS) chart of a semiconductive ceramic member of the present disclosure.
  • XPS X-ray photoelectron spectroscopy
  • 9 is another example of the XPS chart of the semiconductive ceramic member of the present disclosure.
  • 9 is another example of the XPS chart of the semiconductive ceramic member of the present disclosure.
  • the semiconductive ceramic member 10 of the present disclosure contains a plurality of aluminum oxide crystal particles 1 and a plurality of titanium oxide crystal particles 2.
  • FIG. 1 is an example of an enlarged view of a cross section of the semiconductive ceramic member 10, in which two aluminum oxide crystal particles 1, one titanium oxide crystal particle 2, a first region 3 formed by these, and A grain boundary 4 between each crystal grain is shown.
  • the total of aluminum oxide and titanium oxide is 99% by mass or more of 100% by mass of all components constituting the semiconductive ceramic member 10.
  • the semiconductive ceramic member 10 of the present disclosure has high mechanical strength.
  • aluminum oxide is 86% by mass or more and 96% by mass or less
  • titanium oxide is 4% by mass or more and 14% by mass or less.
  • the semiconductive ceramic member 10 has a TiO x (0 ⁇ x) in the range of 456 eV or more and 462 eV or less in the measurement by X-ray photoelectron spectroscopy (XPS). The peak of ⁇ 2) exists.
  • TiO x (0 ⁇ x ⁇ 2) is a state in which TiO 2 is oxygen-deficient. Note that there is a case where TiO 2 that is not oxygen-deficient is partially present and TiO x (0 ⁇ x ⁇ 2) and TiO 2 coexist. In this case, the peak of TiO 2 exists in the range of the binding energy of 456 eV or more and 462 eV or less, and the peak of TiO x (0 ⁇ x ⁇ 2) is located on the higher energy side than the peak of TiO 2 . Specifically, in FIGS.
  • the horizontal axis represents the binding energy (eV) and the vertical axis represents the intensity of the number of photoelectrons (c / s; count / second), and the peak of TiO 2 is about 458. 0.6 eV, and the peak of TiO x (0 ⁇ x ⁇ 2) appears at about 459.8 eV.
  • the semiconductive ceramic member 10 of the present disclosure has a low electric resistance.
  • the low electric resistance means that the volume resistivity is from 10 3 ⁇ ⁇ cm to 10 10 ⁇ ⁇ cm.
  • the volume resistivity may be measured by cutting out the semiconductive ceramic member 10 into a shape conforming to JIS C # 2141 (1992) by a three-terminal method.
  • a super insulation resistance meter 8340A manufactured by ADC Corporation can be used.
  • the sum of aluminum oxide and titanium oxide is 99% by mass or more, and of the total 100% by mass of aluminum oxide and titanium oxide, aluminum oxide is If it is less than 86% by mass, the volume resistivity may be less than 10 3 ⁇ ⁇ cm.
  • the sum of aluminum oxide and titanium oxide is 99% by mass or more, and of the total 100% by mass of aluminum oxide and titanium oxide, aluminum oxide is If it exceeds 96% by mass, the volume resistivity may exceed 10 10 ⁇ ⁇ cm.
  • the volume resistivity may exceed 10 10 ⁇ ⁇ cm.
  • the sum of aluminum oxide and titanium oxide is 99% by mass or more, and of the total 100% by mass of aluminum oxide and titanium oxide, titanium oxide is If it exceeds 14% by mass, the volume resistivity may be less than 10 3 ⁇ ⁇ cm.
  • the peak of TiO x (0 ⁇ x ⁇ 2) does not exist in the range of the binding energy of 456 eV or more and 462 eV or less, the electric resistance increases, and the electric resistance may exceed 10 10 ⁇ ⁇ cm.
  • the presence of the peak of TiO x (0 ⁇ x ⁇ 2) means that the peak of TiO x (0 ⁇ x ⁇ 2) appears only when the peak of TiO x (0 ⁇ x ⁇ 2) clearly appears as shown in FIGS.
  • FIG. 4 a case where the peak swells on the high energy side of the TiO 2 peak is included.
  • the content of each component constituting the semiconductive ceramic member 10 of the present disclosure is measured by using a fluorescent X-ray analyzer (XRF) or a high-frequency inductively coupled plasma emission analyzer (ICP-AES). Then, the content of each element can be determined, and the content of each element can be converted into the content of each oxide from the determined content of the element.
  • XRF fluorescent X-ray analyzer
  • ICP-AES high-frequency inductively coupled plasma emission analyzer
  • the content of each element can be determined, and the content of each element can be converted into the content of each oxide from the determined content of the element.
  • the content of Al may be obtained by measurement with XRF or ICP-AES, and converted into Al 2 O 3 .
  • the content of Ti may be obtained by measurement with XRF or ICP-AES, and converted into TiO 2 .
  • Whether or not a peak of TiO x (0 ⁇ x ⁇ 2) exists in a range of a binding energy of 456 eV to 462 eV can be measured by the following method.
  • the measuring device for example, an X-ray photoelectron spectroscopy (XPS) device (PHIMQuantera SXM) manufactured by ULVAC-PHI, Inc. is used, and the semiconductive ceramic member 10 of the present disclosure may be measured under the following measuring conditions.
  • XPS X-ray photoelectron spectroscopy
  • PHIMQuantera SXM X-ray photoelectron spectroscopy
  • the semiconductive ceramic member 10 of the present disclosure may be measured under the following measuring conditions.
  • the X-rays for irradiation AlK ⁇ rays monochromatized by a monochromator are used. Further, the output of the X-ray is 25 W, the acceleration voltage is 15 kV, the measurement area is about 100 ⁇ m in diameter, the measurement interval of the binding energy is 0.100 eV, and the measurement range of the binding energy is 448 to 470 eV.
  • the semiconductive ceramic member 10 of the present disclosure further contains silicon (Si), and the first region 3 (surrounded by two aluminum oxide crystal particles 1 and one titanium oxide crystal particle 2).
  • silicon oxide (SiO 2 ) in the first region 3 in terms of oxide (SiO 2 ) is determined by the grain boundaries 4 of the aluminum oxide crystal particles 1 and the titanium oxide crystal particles 2 (hereinafter simply referred to as the grain boundaries 4).
  • the content is larger than the content in terms of oxide of silicon (SiO 2 ) in the following.
  • the semiconductive ceramic member 10 of the present disclosure a current flows from one titanium oxide crystal particle 2 to the other titanium oxide crystal particle 2 through the first region 3 and the grain boundary 4.
  • the shorter the flow path the smaller the variation in electrical resistance. Therefore, by satisfying such a structure, the electric resistance of the first region 3 becomes higher than the electric resistance of the grain boundary 4, and it becomes difficult for a current to flow through the first region 3 having a large volume.
  • the path through which the current flows becomes shorter. Therefore, the semiconductive ceramic member 10 of the present disclosure has a low electric resistance and a small variation in the electric resistance.
  • the variation of the electric resistance of the semiconductive ceramic member 10 of the present disclosure may be measured by the following method. First, the semiconductive ceramic member 10 is divided into three or more pieces. Then, the volume resistivity of each of the divided samples is measured by a three-terminal method according to JIS C # 2141 (1992). Then, the difference between the maximum value of the volume resistivity and the minimum value of the volume resistivity in each sample is calculated. Then, when this difference is divided by the average value of the volume resistivity of each sample, it is the value of the variation of the electric resistance.
  • the semiconductive ceramic member 10 of the present disclosure contains, for example, 0.02 parts by mass or more and 0.3 parts by mass or less of silicon in terms of oxides based on 100 parts by mass of aluminum oxide and titanium oxide in total. You may.
  • the content of silicon in the first region 3 in terms of oxide is 0.5% by mass or more than the content of silicon in the grain boundary 4 in terms of oxide. May be more. If such a configuration is satisfied, the difference between the electric resistance of the first region 3 and the electric resistance of the grain boundary 4 increases, and it becomes more difficult for a current to flow through the first region 3.
  • the conductive ceramic member 10 has a smaller variation in electric resistance.
  • the first region 3 may have a silicon oxide content of 1% by mass or more and 6% by mass or less, for example, of 100% by mass of all components constituting the first region 3.
  • the first region 3 has, for example, a content in terms of an aluminum oxide (Al 2 O 3 ) and a titanium oxide (TiO 2 ) of 100% by mass of all components constituting the first region 3. May be 70% by mass or more.
  • the grain boundary 4 may have, for example, a content in terms of oxide of silicon of 2% by mass or less based on 100% by mass of all components constituting the grain boundary 4. Further, the grain boundary 4 is, for example, the content in terms of aluminum oxide (Al 2 O 3 ) and titanium oxide (TiO 2 ) in 100% by mass of all components constituting the grain boundary 4. The total content may be 70% by mass or more.
  • the semiconductive ceramic member 10 of the present disclosure further contains calcium (Ca), and the content of the calcium oxide (CaO) in the first region 3 in terms of calcium oxide (CaO) is It may be higher than the content in terms of CaO).
  • the electric resistance of the first region 3 becomes higher than the electric resistance of the grain boundary 4, and the current hardly flows through the first region 3.
  • the ceramic member 10 has a smaller variation in electric resistance.
  • the semiconductive ceramic member 10 of the present disclosure contains, for example, 0.03 parts by mass or more and 0.2 parts by mass or less of calcium in terms of oxide based on 100 parts by mass of the total of aluminum oxide and titanium oxide. You may.
  • the content of calcium in the first region 3 in terms of oxide is 0.6% by mass or more than the content of calcium in the grain boundary 4 in terms of oxide. May be more.
  • the conductive ceramic member 10 has a smaller variation in electric resistance.
  • the first region 3 may have, for example, a content of calcium oxide equivalent of 0.2% by mass or more and 3% by mass or less of 100% by mass of all components constituting the first region 3. .
  • the grain boundary 4 may have, for example, a content of calcium of 0.6% by mass or less in terms of oxide of 100% by mass of all components constituting the grain boundary 4.
  • the content of each component constituting the first region 3 and the grain boundary 4 may be measured and calculated by the following method.
  • the semiconductive ceramic member 10 of the present disclosure is cut, and the cut surface is observed with a transmission electron microscope (TEM). Then, it is determined whether the crystal particles are aluminum oxide crystal particles 1 or titanium oxide crystal particles 2 by electron beam diffraction using a TEM.
  • TEM transmission electron microscope
  • the crystal particles can also be determined by using an energy dispersive X-ray spectrometer (EDS) attached to the TEM.
  • EDS energy dispersive X-ray spectrometer
  • the composition of crystal grains is quantitatively analyzed by EDS, if the total content of aluminum (Al) and oxygen (O) is 90% by mass or more, the crystal grains are aluminum oxide crystal grains 1.
  • the composition of the crystal particles is quantitatively analyzed by EDS, if the total content of titanium (Ti) and oxygen (O) is 90% by mass or more, the crystal particles are titanium oxide crystal particles 2.
  • the first region 3 surrounded by the two aluminum oxide crystal grains 1 and the one titanium oxide crystal grain 2 and the grain boundary 4 of the aluminum oxide crystal grains 1 and the titanium oxide crystal grains 2 are subjected to EDS. Quantitative analysis may be performed. The total amount of each component measured by the quantitative analysis by EDS may be 100% by mass of all components constituting the first region 3 and the grain boundary 4.
  • the first region 3 and the grain boundary 4 may have zirconium (Zr).
  • the content of zirconium in the first region 3 in terms of oxide may be smaller than the content of zirconium in the grain boundary 4 in terms of oxide.
  • Zirconium oxide generally has a property of easily forming oxygen vacancies. When there are many oxygen vacancies, the electric resistance tends to decrease. Therefore, when the zirconium content in the grain boundaries 4 is large, oxygen vacancies in the grain boundaries 4 increase, and the electrical resistance tends to decrease. Further, when the zirconium content in the first region is small, oxygen vacancies are reduced, so that the electric resistance in the first region 3 tends to increase. Therefore, the electric resistance of the first region 3 becomes higher than the electric resistance of the grain boundary 4, so that the current hardly flows through the first region 3 having a large volume, and the current easily flows through the grain boundary 4. As a result, the path through which the current flows becomes shorter. Therefore, variation in the electrical resistance of the semiconductive ceramic member 10 of the present disclosure is small.
  • the content of zirconium in the first region 3 in terms of oxide may be smaller than the content of zirconium in the grain boundary 4 in terms of oxide by 0.3% by mass or more.
  • Semiconductive ceramic member 10 described above may be created by using a large amount of ZrO2 in fine powder than ZrO 2 powder and coarse powder as a raw material. Even when the zirconium content is constant, when both the fine powder ZrO 2 powder and the coarse powder ZrO 2 powder are used as raw materials, the zirconium content of the grain boundary 4 is increased by increasing the proportion of the fine powder ZrO 2 . It tends to be larger than the zirconium content in the region 3. In other words, the zirconium content of the first region 3 tends to be smaller than the zirconium content of the grain boundary 4.
  • the fine powder ZrO 2 powder means a particle diameter of 0.1 ⁇ m or more and 0.3 ⁇ m or less when the particle diameter of the powder is measured by a laser diffraction method and the cumulative volume ratio from small particles is 50% by volume. It may be a powder.
  • the coarse powder ZrO 2 powder may be a powder having a size of 0.8 ⁇ m or more and 2 ⁇ m or less in the same measurement.
  • first region 3 and the grain boundary 4 may have sodium (Na).
  • the content of sodium in the first region 3 in terms of oxide may be larger than the content of sodium in the grain boundary 4 in terms of oxide.
  • the content of sodium in the first region in terms of oxide may be 0.2% by mass or more larger than the content of sodium in the grain boundary 4 in terms of oxide.
  • the above-mentioned semiconductive ceramic member 10 may be made by using a larger proportion of NaCl powder than Na 2 CO 3 powder as a raw material. Even when the content in terms of Na 2 O is constant, if the proportion of the NaCl powder is larger than that of the Na 2 CO 3 powder as the raw material, the proportion of the sodium in the first region 3 is greater than the proportion of the sodium in the grain boundaries 4. More likely to be.
  • the ratio between the Na 2 CO 3 powder and the NaCl powder may be a comparison between the mole% of Na 2 CO 3 and the mole% of NaCl.
  • ⁇ -alumina ( ⁇ -Al 2 O 3 ) powder, rutile-type titanium dioxide (TiO 2 ) powder, silicon oxide (SiO 2 ) powder, and a colloidal silica solution having an average particle diameter in the range of 10 nm to 100 nm are prepared.
  • the ⁇ -alumina powder is weighed to be 86% by mass or more and 96% by mass or less, and the titanium dioxide (TiO 2 ) powder is weighed by 4% by mass or more and 14% by mass or less. Further, the silicon oxide powder and the colloidal silica solution were mixed with each other so that silicon became 0.02 parts by mass or more and 0.3 parts by mass or less in terms of oxide with respect to 100 parts by mass of ⁇ -alumina powder and titanium dioxide powder in total. Weigh.
  • the compounding ratio of the silicon oxide powder and the colloidal silica solution is included in the colloidal silica solution in a total of 100% by mass of the silicon oxide powder and the content of silicon contained in the colloidal silica solution in terms of oxide.
  • the content of silicon in terms of oxide should be 2% by mass or more, and the remainder should be silicon oxide powder.
  • the content of silicon contained in the colloidal silica solution in terms of oxide was 3% by mass or more.
  • the content of silicon in the first region in terms of oxide becomes larger than the content of silicon in the grain boundary in terms of oxide by 0.5% by mass or more.
  • mixing raw materials the weighed ⁇ -alumina powder, titanium dioxide powder, silicon oxide powder, and colloidal silica solution (hereinafter, these may be referred to as mixing raw materials) are put into a ball mill, and further added to 100 parts by mass of the mixing raw materials.
  • 100 to 200 parts by mass of water as a solvent and 0.02 to 0.5 parts by mass of a dispersant are added and pulverized until a predetermined average particle size is reached.
  • a binder such as PEG (polyethylene glycol), PVA (polyvinyl alcohol), or an acrylic resin is added so that the solid content is 4 parts by mass or more and 10 parts by mass or less, and a slurry is obtained by mixing.
  • granules are obtained by spray-drying the obtained slurry using a spray drier.
  • the obtained granules are used as a raw material for molding, and a molded body having a desired shape is formed by a powder press molding method, an isostatic pressing method or the like, and a cutting process is performed as necessary.
  • the molded body is fired in an air atmosphere at a temperature of 1500 ° C. or more and 1600 ° C. or less for 2 hours or more and 12 hours or less to obtain a sintered body. If necessary, the obtained sintered body may be subjected to grinding.
  • the obtained sintered body is held at a temperature of 1300 ° C. or more and 1400 ° C. or less for 1 hour or more and 5 hours or less in a reducing gas having a hydrogen: nitrogen ratio of 1: 3.
  • a peak of TiO x (0 ⁇ x ⁇ 2) exists in a binding energy range of 456 eV to 462 eV in the measurement by XPS.
  • the semiconductive ceramic member of the present disclosure is obtained.
  • a first calcium carbonate (CaCO 3 ) powder having an average particle diameter of 1 ⁇ m to 3 ⁇ m and a second calcium carbonate powder having an average particle diameter of 0.5 ⁇ m or less are prepared.
  • the first calcium carbonate was prepared so that calcium was 0.03 parts by mass or more and 0.2 parts by mass or less in terms of oxide based on 100 parts by mass of the total of ⁇ -alumina powder and titanium dioxide powder in the raw material for preparation.
  • the powder and the second calcium carbonate powder are weighed and added.
  • the mixing ratio of the first calcium carbonate powder and the second calcium carbonate powder is such that the second calcium carbonate powder is 2% by mass or more of the total 100% by mass of the first calcium carbonate powder and the second calcium carbonate powder, and the balance is Is the first calcium carbonate powder.
  • the fine second calcium carbonate powder forms a solid solution in the first region more than the grain boundary, and the content of calcium in the first region in terms of oxides is reduced. It is larger than the content in terms of oxide.
  • the second calcium carbonate powder is blended so as to be 3% by mass or more of the total 100% by mass of the first calcium carbonate powder and the second calcium carbonate powder, calcium in the first region in terms of oxide of calcium can be obtained.
  • the content is 0.6% by mass or more than the content of calcium in the grain boundary in terms of oxide.
  • ⁇ -alumina powder having an average particle size of 3 ⁇ m determined by a laser diffraction / scattering method, rutile titanium dioxide powder having an average particle size of 3 ⁇ m, silicon oxide powder having an average particle size of 2 ⁇ m, and average particle size
  • a colloidal silica solution having a particle size of 20 nm was prepared.
  • ⁇ -alumina powder was weighed so as to be 91% by mass and titanium dioxide powder was weighed so as to be 9% by mass.
  • the silicon oxide powder and the colloidal silica solution were weighed so that silicon had the value shown in Table 1 in terms of oxide with respect to 100 parts by mass of the total of ⁇ -alumina powder and titanium dioxide powder.
  • the mixing ratio of the silicon oxide powder and the colloidal silica solution is included in the colloidal silica solution in a total of 100% by mass of the silicon oxide powder and the content of silicon contained in the colloidal silica solution in terms of oxide.
  • the content of silicon in terms of oxide was adjusted to the value shown in Table 1. Then, these were blended to obtain a blending raw material.
  • a compact having a shape of 130 mm ⁇ 130 mm ⁇ 12 mm was obtained by a powder press molding method.
  • the compact was fired in an air atmosphere at a temperature of 1550 ° C. for 5 hours to obtain a sintered body.
  • the obtained sintered body was subjected to cutting to obtain a processed body having a shape of 100 mm ⁇ 100 mm ⁇ 3 mm.
  • each sample is held in a reducing gas having a hydrogen: nitrogen ratio of 1: 3 at a temperature of 1380 ° C. for 3 hours and further at 1100 ° C. for 12 hours to perform a reduction treatment.
  • each sample was measured using an XPS apparatus manufactured by ULVAC-PHI, Inc.
  • AlK ⁇ rays monochromatized by a monochromator were used as the X-rays to be irradiated, the output of the X-rays was 25 W, the acceleration voltage was 15 kV, the measurement area was about 100 ⁇ m in diameter, and the binding energy was The measurement interval was 0.100 eV, and the measurement range of the binding energy was 448 to 470 eV.
  • a peak of TiO x (0 ⁇ x ⁇ 2) was present in a range where the binding energy was 456 eV or more and 462 eV or less.
  • a TEM was attached to a first region surrounded by two aluminum oxide crystal particles and one titanium oxide crystal particle, and a grain boundary of the aluminum oxide crystal particle and the titanium oxide crystal particle. was subjected to quantitative analysis by EDS.
  • each sample was divided into four measurement samples having a size of about 50 mm ⁇ 50 mm ⁇ 3 mm.
  • the volume resistivity of each of the divided measurement samples was measured by a three-terminal method using a super insulation resistance meter 8340A manufactured by ADC Corporation in accordance with JIS C 2141 (1992).
  • the average value R, the maximum value, and the minimum value of the volume resistivity of each measurement sample were determined.
  • the maximum value-minimum value (denoted by ⁇ R) was obtained.
  • the ⁇ R / R was calculated by dividing the ⁇ R by the average value R.
  • the average value R of the volume resistivity of each sample was from 10 3 ⁇ ⁇ cm to 10 10 ⁇ ⁇ cm.
  • Example 1 As a method for preparing each sample, a first calcium carbonate powder having an average particle size of 2 ⁇ m and a second calcium carbonate powder having an average particle size of 0.2 ⁇ m were prepared, and ⁇ -alumina powder was used as a raw material for preparation. And the first calcium carbonate powder and the second carbonate so that calcium has the value shown in Table 2 in terms of oxide and the second calcium carbonate powder has the value shown in Table 2 with respect to a total of 100 parts by mass of the titanium dioxide powder.
  • Example 1 was repeated except that calcium powder was weighed and added. It was manufactured by the same manufacturing method as in Example 3. Table 2 shows the sample No. of Example 1. Sample No. 3 9 is described.
  • the variation of the electric resistance of 12 to 17 was as small as 0.18 or less. From this fact, if the calcium oxide content in the first region is 0.6% by mass or more larger than the calcium oxide content in the grain boundary, the variation in electric resistance is smaller. I understood.

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Abstract

本開示の半導電性セラミック部材は、酸化アルミニウム結晶粒子および酸化チタン結晶粒子をそれぞれ複数含有する。また、全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上である。また、前記酸化アルミニウムおよび前記酸化チタンの合計１００質量％のうち、前記酸化アルミニウムが８６質量％以上９６質量％以下であり、前記酸化チタンが４質量％以上１４質量％以下である。また、Ｘ線光電子分光による測定において、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在する。さらに、珪素を含有しており、第１領域における前記珪素の酸化物換算での含有量が、粒界における前記珪素の酸化物換算での含有量よりも多い。

Description

半導電性セラミック部材
　本発明は、半導電性セラミック部材に関する。
　露光装置等におけるウエハの保持および搬送に、半導電性セラミック部材が用いられている。半導電性セラミック部材は、高い機械的強度に加えて、塵および浮遊粒子等がウエハに静電付着することを防止するため、静電気を逃がすことができる低い電気抵抗を有している。
　このような半導電性セラミック部材として、例えば、酸化アルミニウム（Ａｌ2Ｏ3）を主成分とし、酸化チタン（ＴｉＯ2）を含む酸化アルミニウム質セラミックスが知られている。そして、このような酸化アルミニウム質セラミックスは、還元雰囲気中で焼成することにより導電性が付与される（例えば、特許文献１を参照）。
特開２００７－９１４８８号公報
　本開示の半導電性セラミック部材は、酸化アルミニウム結晶粒子および酸化チタン結晶粒子をそれぞれ複数含有する。また、全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上である。また、前記酸化アルミニウムおよび前記酸化チタンの合計１００質量％のうち、前記酸化アルミニウムが８６質量％以上９６質量％以下であり、前記酸化チタンが４質量％以上１４質量％以下である。また、Ｘ線光電子分光による測定において、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在する。さらに、珪素を含有しており、２個の前記酸化アルミニウム結晶粒子および１個の前記酸化チタン結晶粒子に囲まれた第１領域における前記珪素の酸化物換算での含有量が、前記酸化アルミニウム結晶粒子および前記酸化チタン結晶粒子の粒界における前記珪素の酸化物換算での含有量よりも多い。
本開示の半導電性セラミック部材の断面の拡大図の一例である。 本開示の半導電性セラミック部材におけるＸ線光電子分光（ＸＰＳ）チャートの一例である。 本開示の半導電性セラミック部材におけるＸＰＳチャートの他の例である。 本開示の半導電性セラミック部材におけるＸＰＳチャートの他の例である。
　本開示の半導電性セラミック部材について、図面を参照しながら、以下に詳細に説明する。
　本開示の半導電性セラミック部材１０は、酸化アルミニウム結晶粒子１および酸化チタン結晶粒子２をそれぞれ複数含有している。なお、図１は、半導電性セラミック部材１０の断面の拡大図の一例であり、２個の酸化アルミニウム結晶粒子１と、１個の酸化チタン結晶粒子２と、これらによる第１領域３と、それぞれの結晶粒子間にあたる粒界４とを示している。
　そして、本開示の半導電性セラミック部材１０は、半導電性セラミック部材１０を構成する全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上である。このような構成を満足していることで、本開示の半導電性セラミック部材１０は、高い機械的強度を有する。
　また、酸化アルミニウムおよび酸化チタンの合計１００質量％のうち、酸化アルミニウムが８６質量％以上９６質量％以下であり、酸化チタンが４質量％以上１４質量％以下である。
　さらに、本開示の半導電性セラミック部材１０は、図２～図４に示すように、Ｘ線光電子分光（ＸＰＳ）による測定において、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在する。
　ここで、ＴｉＯx（０＜ｘ＜２）とは、ＴｉＯ2が酸素欠損した状態である。なお、酸素欠損していないＴｉＯ2が一部存在し、ＴｉＯx（０＜ｘ＜２）とＴｉＯ2とが共存している場合がある。この場合、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲には、ＴｉＯ2のピークが存在し、ＴｉＯx（０＜ｘ＜２）のピークはＴｉＯ2のピークよりも高エネルギー側に位置する。具体的には、図２～図４において、横軸は結合エネルギー（ｅＶ）、縦軸は光電子数の強度（ｃ／ｓ；カウント／秒）を示しているが、ＴｉＯ2のピークは約４５８．６ｅＶに現れ、ＴｉＯx（０＜ｘ＜２）のピークは約４５９．８ｅＶに現れている。
　よって、このような構成を満足していることで、本開示の半導電性セラミック部材１０は、低い電気抵抗を有する。ここで、低い電気抵抗とは、体積固有抵抗が１０3Ω・ｃｍ以上１０10Ω・ｃｍ以下であることである。
　ここで、体積固有抵抗は、ＪＩＳ　Ｃ　２１４１（１９９２年）に準拠した形状に半導電性セラミック部材１０を切り出し、３端子法により測定すればよい。なお、３端子法による測定には、例えば、エーデーシー株式会社製の超絶縁抵抗計８３４０Ａを用いることができる。
　また、半導電性セラミック部材１０を構成する全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上であり、酸化アルミニウムおよび酸化チタンの合計１００質量％のうち、酸化アルミニウムが８６質量％未満であれば、体積固有抵抗が１０3Ω・ｃｍ未満となるおそれがある。一方、半導電性セラミック部材１０を構成する全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上であり、酸化アルミニウムおよび酸化チタンの合計１００質量％のうち、酸化アルミニウムが９６質量％を超えると、体積固有抵抗が１０10Ω・ｃｍを超えるおそれがある。
　また、半導電性セラミック部材１０を構成する全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上であり、酸化アルミニウムおよび酸化チタンの合計１００質量％のうち、酸化チタンが４質量％未満であれば、体積固有抵抗が１０10Ω・ｃｍを超えるおそれがある。一方、半導電性セラミック部材１０を構成する全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上であり、酸化アルミニウムおよび酸化チタンの合計１００質量％のうち、酸化チタンが１４質量％を超えると、体積固有抵抗が１０3Ω・ｃｍ未満となるおそれがある。
　また、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在しない場合は、電気抵抗が高くなり、電気抵抗が１０10Ω・ｃｍを超えるおそれがある。なお、ＴｉＯx（０＜ｘ＜２）のピークが存在するというのは、図２および図３に示すように、ＴｉＯx（０＜ｘ＜２）のピークが明確に現れている場合のみならず、図４に示すように、ＴｉＯ2のピークの高エネルギー側において、ピークに膨らみがある場合を含む。
　ここで、本開示の半導電性セラミック部材１０を構成する各成分の含有量は、蛍光Ｘ線分析装置（ＸＲＦ）または高周波誘導結合プラズマ発光分析装置（ＩＣＰ－ＡＥＳ）を用いて測定を行なうことで、各元素の含有量を求め、求めた元素の含有量から各酸化物の含有量に換算することにより求めることができる。具体的には、ＸＲＦまたはＩＣＰ－ＡＥＳでの測定によりＡｌの含有量を求め、Ａｌ2Ｏ3に換算すればよい。また、ＸＲＦまたはＩＣＰ－ＡＥＳでの測定によりＴｉの含有量を求め、ＴｉＯ2に換算すればよい。
　そして、半導電性セラミック部材１０を構成する全成分１００質量％のうち９９質量％であるか否かは、ここで得られたＡｌ2Ｏ3への換算値と、ＴｉＯ2への換算値との合計で確認できる。また、酸化アルミニウムおよび酸化チタンの合計１００質量％のうちの含有量は、ここで得られたＡｌ2Ｏ3への換算値またはＴｉＯ2への換算値の一方を分子とし、Ａｌ2Ｏ3への換算値とＴｉＯ2への換算値との合計を分母として百分率で算出すれば一方の含有量を確認でき、１００から差し引くことで他方の含有量を確認することができる。
　また、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在するか否かについては、以下に示す方法で測定することができる。
　まず、測定装置として、例えばアルバック・ファイ株式会社製のＸ線光電子分光（ＸＰＳ）装置（PHI Quantera SXM）を使用し、以下の測定条件で本開示の半導電性セラミック部材１０を測定すればよい。照射するＸ線としては、モノクロメーターにより単色化されたＡｌＫα線を使用する。また、Ｘ線の出力は２５Ｗ、加速電圧は１５ｋＶ、１回の測定領域は直径約１００μｍの範囲、結合エネルギーの測定間隔は０．１００ｅＶ、結合エネルギーの測定範囲は４４８～４７０ｅＶとする。
　また、本開示の半導電性セラミック部材１０は、さらに珪素（Ｓｉ）を含有しており、２個の酸化アルミニウム結晶粒子１および１個の酸化チタン結晶粒子２に囲まれた第１領域３（以下、単に第１領域３と記載する）における珪素の酸化物（ＳｉＯ2）換算での含有量が、酸化アルミニウム結晶粒子１および酸化チタン結晶粒子２の粒界４（以下、単に粒界４と記載する）における珪素の酸化物（ＳｉＯ2）換算での含有量よりも多い。
　本開示の半導電性セラミック部材１０において、電流は、ある酸化チタン結晶粒子２から第１領域３および粒界４を通って、他の酸化チタン結晶粒子２に流れていくが、このとき電流が流れる経路が短い程、電気抵抗のばらつきが小さくなる。よって、このような構造を満足することで、第１領域３の電気抵抗が粒界４の電気抵抗よりも高くなり、体積の大きい第１領域３に電流が流れにくくなることから、結果として、電流が流れる経路が短くなる。よって、本開示の半導電性セラミック部材１０は、低い電気抵抗を有するとともに、電気抵抗のばらつきが小さい。
　ここで、本開示の半導電性セラミック部材１０の電気抵抗のばらつきは、以下の方法で測定すればよい。まず、半導電性セラミック部材１０を３個以上に分割する。そして、分割した各試料の体積固有抵抗を、ＪＩＳ　Ｃ　２１４１（１９９２年）に準拠して、３端子法により測定する。そして、各試料における、体積固有抵抗の最大値と体積固有抵抗の最小値との差を算出する。そして、この差を、各試料の体積固有抵抗の平均値で割れば、それが電気抵抗のばらつきの値である。
　なお、本開示の半導電性セラミック部材１０は、例えば、酸化アルミニウムおよび酸化チタンの合計１００質量部に対して、珪素を酸化物換算で０．０２質量部以上０．３質量部以下含有していてもよい。
　また、本開示の半導電性セラミック部材１０において、第１領域３における珪素の酸化物換算での含有量は、粒界４における珪素の酸化物換算での含有量よりも０．５質量％以上多くてもよい。このような構成を満足するならば、第１領域３の電気抵抗と粒界４の電気抵抗との差が大きくなり、第１領域３に電流がより流れにくくなることから、本開示の半導電性セラミック部材１０は、電気抵抗のばらつきがより小さくなる。
　なお、第１領域３は、例えば、第１領域３を構成する全成分１００質量％のうち、珪素の酸化物換算での含有量が１質量％以上６質量％以下であってもよい。また、第１領域３は、例えば、第１領域３を構成する全成分１００質量％のうち、アルミニウムの酸化物（Ａｌ2Ｏ3）換算での含有量およびチタンの酸化物（ＴｉＯ2）換算での含有量の合計が７０質量％以上であってもよい。
　また、粒界４は、例えば、粒界４を構成する全成分１００質量％のうち、珪素の酸化物換算での含有量が２質量％以下であってもよい。また、粒界４は、例えば、粒界４を構成する全成分１００質量％のうち、アルミニウムの酸化物（Ａｌ2Ｏ3）換算での含有量およびチタンの酸化物（ＴｉＯ2）換算での含有量の合計が７０質量％以上であってもよい。
　また、本開示の半導電性セラミック部材１０は、さらにカルシウム（Ｃａ）を含有し、第１領域３におけるカルシウムの酸化物（ＣａＯ）換算での含有量は、粒界４におけるカルシウムの酸化物（ＣａＯ）換算での含有量よりも多くてもよい。
　このような構成を満足するならば、第１領域３の電気抵抗が粒界４の電気抵抗よりもさらに高くなり、第１領域３に電流がより流れにくくなることから、本開示の半導電性セラミック部材１０は、電気抵抗のばらつきがより小さくなる。
　なお、本開示の半導電性セラミック部材１０は、例えば、酸化アルミニウムおよび酸化チタンの合計１００質量部に対して、カルシウムを酸化物換算で０．０３質量部以上０．２質量部以下含有していてもよい。
　また、本開示の半導電性セラミック部材１０において、第１領域３におけるカルシウムの酸化物換算での含有量は、粒界４におけるカルシウムの酸化物換算での含有量よりも０．６質量％以上多くてもよい。
　このような構成を満足するならば、第１領域３の電気抵抗と粒界４の電気抵抗との差が大きくなり、第１領域３に電流がより流れにくくなることから、本開示の半導電性セラミック部材１０は、電気抵抗のばらつきがより小さくなる。
　なお、第１領域３は、例えば、第１領域３を構成する全成分１００質量％のうち、カルシウムの酸化物換算での含有量が０．２質量％以上３質量％以下であってもよい。
　また、粒界４は、例えば、粒界４を構成する全成分１００質量％のうち、カルシウムの酸化物換算での含有量が０．６質量％以下であってもよい。
　ここで、第１領域３および粒界４を構成する各成分の含有量は、以下の方法で測定し算出すればよい。まず、本開示の半導電性セラミック部材１０を切断し、切断面を透過型電子顕微鏡（ＴＥＭ）で観察する。そして、ＴＥＭによる電子線回折により、結晶粒子が酸化アルミニウム結晶粒子１であるか、酸化チタン結晶粒子２であるか判別する。
　なお、結晶粒子の判別は、ＴＥＭに付設されているエネルギー分散形Ｘ線分光分析装置（ＥＤＳ）を用いても可能である。例えば、ＥＤＳで結晶粒子の組成を定量分析した場合に、アルミニウム（Ａｌ）および酸素（Ｏ）の合計含有量が９０質量％以上であれば、その結晶粒子は酸化アルミニウム結晶粒子１である。また、ＥＤＳで結晶粒子の組成を定量分析した場合に、チタン（Ｔｉ）および酸素（Ｏ）の合計含有量が９０質量％以上であれば、その結晶粒子は酸化チタン結晶粒子２である。
　そして、２個の酸化アルミニウム結晶粒子１および１個の酸化チタン結晶粒子２に囲まれた第１領域３、酸化アルミニウム結晶粒子１および酸化チタン結晶粒子２の粒界粒界４に対して、ＥＤＳによる定量分析を行なえばよい。なお、ＥＤＳによる定量分析により測定された各成分の合計量を、第１領域３や粒界４を構成する全成分１００質量％とすればよい。
　また、第１領域３および粒界４はジルコニウム（Ｚｒ）を有していてもよい。第１領域３におけるジルコニウムの酸化物換算での含有量は、粒界４におけるジルコニウムの酸化物換算での含有量よりも少なくてもよい。
　本開示の半導電性セラミック部材１０が上記の構成を有する場合、半導電性セラミック部材１０における電気抵抗のバラツキが小さい。
　酸化ジルコニウムは、一般的に、酸素欠陥を形成しやすい性質を有する。酸素欠陥が多いと、電気抵抗が小さくなる傾向がある。そのため、粒界４におけるジルコニウム含有量が多いと粒界４における酸素欠陥が増加し、電気抵抗が小さくなりやすい。また、第１領域のジルコニウム含有量が少ないと、酸素欠陥が少なくなるので、第１領域３における電気抵抗が大きくなりやすい。したがって、第１領域３の電気抵抗が粒界４の電気抵抗よりも高くなり、体積の大きい第１領域３に電流が流れにくくなり、粒界４に電流が流れやすくなる。結果として、電流が流れる経路が短くなる。よって、本開示の半導電性セラミック部材１０における電気抵抗のばらつきが小さい。
　また、第１領域３におけるジルコニウムの酸化物換算での含有量は、粒界４におけるジルコニウムの酸化物換算での含有量よりも０．３質量％以上少なくてもよい。
　上記の半導電性セラミック部材１０は、原料として粗粉のＺｒＯ2粉末よりも微粉のＺｒＯ２を多く用いることで作成してもよい。ジルコニウムの含有量が一定でも、原料として微粉のＺｒＯ2粉末と、粗粉のＺｒＯ2粉末の両方を用いた場合に、微粉のＺｒＯ２の割合を多くすると、粒界４のジルコニウム含有量が第１領域３のジルコニウム含有量よりも多くなりやすい。言い換えれば、第１領域３のジルコニウム含有量が粒界４のジルコニウム含有量よりも少なくなりやすい。一例として、微粉のＺｒＯ2粉末とは、粉末の粒子径をレーザ回折法により測定した場合、小さい粒子からの累積体積割合が５０体積％のときの粒径で０．１μｍ以上０．３μｍ以下である粉末であってもよい。粗粉のＺｒＯ2粉末とは、同様の測定で０．８μｍ以上２μｍ以下の粉末であってもよい。
　また、また、第１領域３および粒界４はナトリウム（Ｎａ）を有していてもよい。第１領域３におけるナトリウムの酸化物換算での含有量は、粒界４におけるナトリウムの酸化物換算での含有量よりも多くてもよい。
　本開示の半導電性セラミック部材１０が上記の構成を有する場合、半導電性セラミック部材１０における電気抵抗のバラツキが小さい。
　チタン存在下では、Ｎａ含有量が多いほどナトリウムによるイオン伝導が抑制されやすい。そのため、チタン存在下では、Ｎａ含有量が多いほど電気抵抗が高くなりやすい。したがって、第１領域３におけるＮａ含有量が粒界４におけるＮａ含有量よりも多いため、第１領域３における電気抵抗は粒界４における電気抵抗よりも高くなりやすい。そのため、体積の大きい第１領域３に電流が流れにくくなり、粒界４に電流が流れやすくなる。結果として、電流が流れる経路が短くなる。よって、本開示の半導電性セラミック部材１０における電気抵抗のばらつきが小さい。
　第１領域におけるナトリウムの酸化物換算での含有量は、粒界４におけるナトリウムの酸化物換算での含有量よりも０．２質量％以上多くてもよい。
　上記の半導電性セラミック部材１０は、原材料としてのＮａ2ＣＯ3粉末よりもＮａＣｌ粉末の割合を多く用いることで作成してもよい。Ｎａ2Ｏ換算での含有量が一定でも、原材料としてのＮａ2ＣＯ3粉末よりもＮａＣｌ粉末の割合を多く用いると、第１領域３のナトリウム量の割合が粒界４のナトリウムの割合よりも多くなりやすい。Ｎａ2ＣＯ3粉末とＮａＣｌ粉末の割合は、Ｎａ2ＣＯ3のモル％とＮａＣｌのモル％を比較してもよい。
　次に、本開示の半導電性セラミック部材の製造方法の一例を説明する。
　まず、α－アルミナ（α－Ａｌ2Ｏ3）粉末、ルチル型の二酸化チタン（ＴｉＯ2）粉末、酸化珪素（ＳｉＯ2）粉末、平均粒径が１０ｎｍ以上１００ｎｍ以下の範囲にあるコロイダルシリカ溶液を準備する。
　次に、α－アルミナ粉末が８６質量％以上９６質量％以下、二酸化チタン（ＴｉＯ2）粉末が４質量％以上１４質量％以下となるように秤量する。また、α－アルミナ粉末および二酸化チタン粉末の合計１００質量部に対して、珪素が酸化物換算で０．０２質量部以上０．３質量部以下となるように、酸化珪素粉末およびコロイダルシリカ溶液を秤量する。
　ここで、酸化珪素粉末とコロイダルシリカ溶液との配合割合は、酸化珪素粉末とコロイダルシリカ溶液に含まれる珪素の酸化物換算での含有量との合計１００質量％のうち、コロイダルシリカ溶液に含まれる珪素の酸化物換算での含有量が２質量％以上、残部が酸化珪素粉末となるようにする。このように配合することで、コロイダルシリカ溶液に含まれる微粒の珪素は、粒界よりも第１領域に固溶しやすく、第１領域における珪素の酸化物換算での含有量が、粒界における珪素の酸化物換算での含有量よりも多くなる。
　なお、酸化珪素粉末とコロイダルシリカ溶液に含まれる珪素の酸化物換算での含有量との合計１００質量％のうち、コロイダルシリカ溶液に含まれる珪素の酸化物換算での含有量が３質量％以上となるように配合すれば、第１領域における珪素の酸化物換算での含有量が、粒界における珪素の酸化物換算での含有量よりも０．５質量％以上多くなる。
　次に、秤量したα－アルミナ粉末、二酸化チタン粉末、酸化珪素粉末、コロイダルシリカ溶液（以下、これらを調合用原料と記載する場合がある）をボールミルへ入れ、さらに、調合用原料１００質量部に対して、１００質量部以上２００質量部以下の溶媒としての水と、０．０２質量部以上０．５質量部以下の分散剤とを添加し、所定の平均粒径となるまで粉砕する。
　その後、ＰＥＧ（ポリエチレングリコール）、ＰＶＡ（ポリビニルアルコール）、アクリル樹脂等のバインダーを固形分で４質量部以上１０質量部以下となるように添加し、混合することでスラリーを得る。次に、得られたスラリーを、スプレードライヤーを用いて噴霧乾燥することにより顆粒を得る。
　次に、得られた顆粒を成形原料とし、粉末プレス成形法または静水圧プレス法等により所望の形状の成形体とし、必要に応じて切削加工を施す。次に、成形体を、大気雰囲気において、１５００℃以上１６００℃以下の温度で２時間以上１２時間以下保持することで焼成し、焼結体を得る。なお、必要に応じて、得られた焼結体に研削加工を施してもよい。
　次に、得られた焼結体を、水素：窒素比＝１：３の還元用ガス中において、１３００℃以上１４００℃以下の温度で１時間以上５時間以下保持し、さらに、１０５０℃以上１１５０℃以下の温度で１時間以上３０時間以下保持して還元処理をすることにより、ＸＰＳによる測定において、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在するようになり、本開示の半導電性セラミック部材を得る。
　また、カルシウムを含有し、第１領域におけるカルシウムの酸化物換算での含有量を、粒界におけるカルシウムの酸化物換算での含有量よりも多くするには、次のようにすればよい。
　まず、平均粒径が１μｍ以上３μｍ以下の第１炭酸カルシウム（ＣａＣＯ3）粉末と、平均粒径が０．５μｍ以下の第２炭酸カルシウム粉末とを準備する。そして、調合用原料に、α－アルミナ粉末および二酸化チタン粉末の合計１００質量部に対して、カルシウムが酸化物換算で０．０３質量部以上０．２質量部以下となるように第１炭酸カルシウム粉末および第２炭酸カルシウム粉末を秤量し添加する。
　ここで、第１炭酸カルシウム粉末および第２炭酸カルシウム粉末の配合割合は、第１炭酸カルシウム粉末および第２炭酸カルシウム粉末の合計１００質量％のうち、第２炭酸カルシウム粉末が２質量％以上、残部が第１炭酸カルシウム粉末となるようにする。このように配合することで、微粒の第２炭酸カルシウム粉末が、粒界よりも第１領域に多く固溶し、第１領域におけるカルシウムの酸化物換算での含有量が、粒界におけるカルシウムの酸化物換算での含有量よりも多くなる。
　なお、第１炭酸カルシウム粉末および第２炭酸カルシウム粉末の合計１００質量％のうち、第２炭酸カルシウム粉末が３質量％以上となるように配合すれば、第１領域におけるカルシウムの酸化物換算での含有量が、粒界におけるカルシウムの酸化物換算での含有量よりも０．６質量％以上多くなる。
　以下、本開示の実施例を具体的に説明するが、本開示はこの実施例に限定されるものではない。
　第１領域と粒界とにおける、珪素の酸化物換算での含有量が異なる試料を作製し、電気抵抗のばらつきを評価した。
　まず、レーザ回折・散乱法により求めた平均粒径が３μｍであるα－アルミナ粉末、平均粒径が３μｍであるルチル型の二酸化チタン粉末、平均粒径が２μｍである酸化珪素粉末、平均粒径が２０ｎｍであるコロイダルシリカ溶液を準備した。
　次に、α－アルミナ粉末が９１質量％、二酸化チタン粉末が９質量％となるように秤量した。また、α－アルミナ粉末および二酸化チタン粉末の合計１００質量部に対して、珪素が酸化物換算で表１の値になるように、酸化珪素粉末およびコロイダルシリカ溶液を秤量した。このとき、酸化珪素粉末とコロイダルシリカ溶液との配合割合は、酸化珪素粉末とコロイダルシリカ溶液に含まれる珪素の酸化物換算での含有量との合計１００質量％のうち、コロイダルシリカ溶液に含まれる珪素の酸化物換算での含有量が表１の値となるようにした。そして、これらを調合して調合用原料を得た。
　次に、調合用原料１００質量部に対して、１５０質量部の水と、０．０５質量部の分散剤とを添加し、ボールミルにて所定の平均粒径となるまで粉砕した。その後、ＰＥＧ、ＰＶＡ、アクリル樹脂を固形分で合計６質量部となるように添加し、混合することによりスラリーを得た。次に、得られたスラリーを、スプレードライヤーを用いて噴霧乾燥することにより顆粒を得た。
　次に、得られた顆粒を成形原料とし、粉末プレス成形法により１３０ｍｍ×１３０ｍｍ×１２ｍｍの形状の成形体を得た。次に、大気雰囲気において、１５５０℃の温度で５時間保持して成形体を焼成し、焼結体を得た。そして、得られた焼結体に切削加工を施し、１００ｍｍ×１００ｍｍ×３ｍｍの形状の加工体を得た。
　次に、加工体を、水素：窒素比＝１：３の還元用ガス中において、１３８０℃の温度で３時間保持し、さらに、１１００℃で１２時間保持して還元処理をすることにより各試料を得た。
　次に、アルバック・ファイ株式会社製のＸＰＳ装置を使用し、各試料を測定した。測定条件としては、照射するＸ線としてモノクロメーターにより単色化されたＡｌＫα線を使用し、Ｘ線の出力を２５Ｗ、加速電圧を１５ｋＶ、１回の測定領域を直径約１００μｍの範囲、結合エネルギーの測定間隔を０．１００ｅＶ、結合エネルギーの測定範囲を４４８～４７０ｅＶとした。この結果、各試料には、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在していた。
　次に、各試料において、２個の酸化アルミニウム結晶粒子および１個の酸化チタン結晶粒子に囲まれた第１領域、酸化アルミニウム結晶粒子および酸化チタン結晶粒子の粒界粒界に対して、ＴＥＭ付設のＥＤＳによる定量分析を行なった。
　次に、各試料の電気抵抗および電気抵抗のばらつきを測定した。まず、各試料を約５０ｍｍ×５０ｍｍ×３ｍｍの大きさの測定用試料４個に分割した。次に、分割した各測定用試料の体積固有抵抗を、ＪＩＳ　Ｃ　２１４１（１９９２年）に準拠して、エーデーシー株式会社製の超絶縁抵抗計８３４０Ａを用いて、３端子法により測定した。そして、各測定用試料の体積固有抵抗の平均値Ｒ、最大値、最小値を求めた。次に、最大値－最小値（△Ｒと表記する。）を求めた。そして、この△Ｒを平均値Ｒで割ることで、電気抵抗のばらつきΔＲ／Ｒを算出した。なお、各試料の体積固有抵抗の平均値Ｒは、１０3Ω・ｃｍ以上１０10Ω・ｃｍ以下であった。
　結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、試料Ｎｏ．１に比べて、試料Ｎｏ．２～８の電気抵抗のばらつきは、０．２８以下と小さかった。このことから、第１領域における珪素の酸化物換算での含有量が、粒界における珪素の酸化物換算での含有量よりも多ければ、電気抵抗のばらつきが小さいことがわかった。
　また、試料Ｎｏ．２～８の中でも、試料Ｎｏ．３～８の電気抵抗のばらつきは、０．２６以下と小さかった。このことから、第１領域における珪素の酸化物換算での含有量が、粒界における珪素の酸化物換算での含有量よりも０．５質量％以上多ければ、電気抵抗のばらつきがより小さいことがわかった。
　第１領域と粒界とにおける、カルシウムの酸化物換算での含有量が異なる試料を作製し、電気抵抗のばらつきを評価した。
　なお、各試料の作製方法としては、平均粒径が２μｍの第１炭酸カルシウム粉末と、平均粒径が０．２μｍの第２炭酸カルシウム粉末とを準備し、調合用原料に、α－アルミナ粉末および二酸化チタン粉末の合計１００質量部に対して、カルシウムが酸化物換算で表２に示す値となり、第２炭酸カルシウム粉末が表２の値となるように、第１炭酸カルシウム粉末および第２炭酸カルシウム粉末を秤量して添加したこと以外は、実施例１のＮｏ．３と同じ作製方法で作製した。また、表２には、実施例１の試料Ｎｏ．３を、試料Ｎｏ．９として記載している。
　そして、各試料に対して、実施例１と同じ方法で、第１領域および粒界の成分の確認、電気抵抗ばらつきの測定を行なった。
　結果を表２に示す。
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、試料Ｎｏ．１１～１７の電気抵抗のばらつきは、０．２３以下と小さかった。このことから、第１領域におけるカルシウムの酸化物換算での含有量が、粒界におけるカルシウムの酸化物換算での含有量よりも多ければ、電気抵抗のばらつきがより小さくなることがわかった。
　また、試料Ｎｏ．１１～１７の中でも、試料Ｎｏ．１２～１７の電気抵抗のばらつきは、０．１８以下と小さかった。このことから、第１領域におけるカルシウムの酸化物換算での含有量が、粒界におけるカルシウムの酸化物換算での含有量よりも０．６質量％以上多ければ、電気抵抗のばらつきがより小さいことがわかった。
　１、１ａ、１ｂ：酸化アルミニウム結晶粒子
　２：酸化チタン結晶粒子
　３：第１領域
　４、４ａ、４ｂ：粒界
　１０：半導電性セラミック部材

Claims (6)

  1. 　酸化アルミニウム結晶粒子および酸化チタン結晶粒子をそれぞれ複数含有し、
    　全成分１００質量％のうち、酸化アルミニウムおよび酸化チタンの合計が９９質量％以上であり、
    　前記酸化アルミニウムおよび前記酸化チタンの合計１００質量％のうち、前記酸化アルミニウムが８６質量％以上９６質量％以下であり、前記酸化チタンが４質量％以上１４質量％以下であり、
    　Ｘ線光電子分光による測定において、結合エネルギーが４５６ｅＶ以上４６２ｅＶ以下の範囲にＴｉＯx（０＜ｘ＜２）のピークが存在し、
    　さらに珪素を含有しており、
    　２個の前記酸化アルミニウム結晶粒子および１個の前記酸化チタン結晶粒子に囲まれた第１領域における前記珪素の酸化物換算での含有量が、前記酸化アルミニウム結晶粒子および前記酸化チタン結晶粒子の粒界における前記珪素の酸化物換算での含有量よりも多い、半導電性セラミック部材。
  2. 　前記第１領域における前記珪素の酸化物換算での含有量は、前記粒界における前記珪素の酸化物換算での含有量よりも０．５質量％以上多い、請求項１に記載の半導電性セラミック部材。
  3. 　さらにカルシウムを含有し、
    　前記第１領域における前記カルシウムの酸化物換算での含有量が、前記粒界における前記カルシウムの酸化物換算での含有量よりも多い、請求項１または請求項２に記載の半導電性セラミック部材。
  4. 　前記第１領域における前記カルシウムの酸化物換算での含有量は、前記粒界における前記カルシウムの酸化物換算での含有量よりも０．６質量％以上多い、請求項３に記載の半導電性セラミック部材。
  5. 　前記第１領域におけるジルコニウムの酸化物換算での含有量は、前記粒界におけるジルコニウムの酸化物換算での含有量よりも少ない、請求項１乃至請求項４のいずれかに記載の半導電性セラミック部材。
  6. 　前記第１領域におけるナトリウムの酸化物換算での含有量が、前記粒界におけるナトリウムの酸化物換算での含有量よりも多い、請求項１乃至請求項５のいずれかに記載の半導電性セラミック部材。
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