WO2014141789A1 - Sputtering target for forming magnetic recording film, and carbon raw material used for production of said target - Google Patents
Sputtering target for forming magnetic recording film, and carbon raw material used for production of said target Download PDFInfo
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- WO2014141789A1 WO2014141789A1 PCT/JP2014/053005 JP2014053005W WO2014141789A1 WO 2014141789 A1 WO2014141789 A1 WO 2014141789A1 JP 2014053005 W JP2014053005 W JP 2014053005W WO 2014141789 A1 WO2014141789 A1 WO 2014141789A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
- G11B5/851—Coating a support with a magnetic layer by sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/18—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by cathode sputtering
- H01F41/183—Sputtering targets therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
Definitions
- the present invention relates to a sputtering target used for forming a granular magnetic thin film on a magnetic recording medium, and a carbon raw material used for manufacturing the target.
- a material based on a ferromagnetic metal such as Co, Fe, or Ni is used as a material for a magnetic thin film in a magnetic recording medium.
- a Co—Cr-based or Co—Cr—Pt-based ferromagnetic alloy containing Co as a main component has been used for a magnetic thin film of a hard disk employing an in-plane magnetic recording method.
- hard magnetic thin films employing perpendicular magnetic recording that have been put into practical use in recent years often use a composite material composed of Co—Cr—Pt-based ferromagnetic alloy mainly composed of Co and non-magnetic inorganic particles. It has been.
- the magnetic thin film is often produced by sputtering a sputtering target containing the above material as a component with a DC magnetron sputtering apparatus because of its high productivity.
- an FePt phase having an L1 0 structure has attracted attention as a material for an ultrahigh density recording medium.
- the FePt phase having the L1 0 structure is expected to be a material suitable for application as a magnetic recording medium since it has high crystal magnetic anisotropy and excellent corrosion resistance and oxidation resistance.
- the FePt phase is used as a material for an ultra-high density recording medium, there has been a development of a technique for aligning and dispersing the ordered FePt magnetic particles in as high a density as possible in a magnetically isolated state. It has been demanded.
- a granular structure magnetic thin film of FePt magnetic particles are isolated by a non-magnetic material such oxides or carbon having an L1 0 structure, as for a magnetic recording medium of the next generation hard disk employing a thermally assisted magnetic recording method Proposed.
- This granular structure magnetic thin film has a structure in which magnetic particles are magnetically insulated by interposition of a nonmagnetic substance.
- Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5 can be cited as magnetic recording media having a magnetic thin film having a granular structure and related documents.
- a magnetic thin film having an FePt phase having the L1 0 structure As the granular magnetic thin film having an FePt phase having the L1 0 structure, a magnetic thin film containing 10 to 50% by volume of C as a non-magnetic substance has been attracting attention because of its high magnetic properties. It is known that such a granular structure magnetic thin film is produced by simultaneously sputtering an Fe target, a Pt target, and a C target, or by simultaneously sputtering an Fe—Pt alloy target and a C target. However, in order to simultaneously sputter these sputtering targets, an expensive simultaneous sputtering apparatus is required.
- the present inventor previously used a technique for producing a high-density sputtering target by uniformly dispersing C particles, which are nonmagnetic materials, in a base metal in a Fe—Pt-based sputtering target in which C particles are dispersed. (Patent Document 6). According to this technique, aggregation of C particles can be suppressed, but it is difficult to improve the sinterability of C particles because C particles are hardly sintered materials.
- Patent Documents 7 to 8 disclose a technique in which, in a sputtering target for forming a magnetic recording medium film, by dispersing the C phase in the FePt alloy phase, abnormal discharge during sputtering and differences due to the location of the sputtering rate can be suppressed.
- improvement of sinterability of C (carbon) there is no mention about improvement of sinterability of C (carbon).
- An object of the present invention is to provide an Fe—Pt-based sputtering target in which C particles are dispersed, which makes it possible to produce a granular structure magnetic thin film without using an expensive co-sputtering apparatus. It is an object to provide a sputtering target in which the amount of generated particles is reduced.
- the present inventor has conducted intensive research, and as a result, it is possible to improve the difficulty of sintering carbon by adjusting the fluorine content in the carbon raw material that is a non-magnetic material. I found. In addition, it has been found that the sputtering target produced in this manner can prevent the carbon from falling off and can suggest the generation amount of particles, so that the yield during film formation can be improved.
- the present invention 1) Carbon powder used for producing a sputtering target for forming a magnetic recording film, wherein the fluorine content is 50 wtppm or more, 2) The carbon powder according to 1) above, wherein the median diameter is 0.1 to 20 ⁇ m, 3) A sputtering target for forming a magnetic recording film, wherein the carbon powder described in 1) or 2) above is used as a raw material for the target, and is produced by a powder sintering method, 4) The sputtering target for forming a magnetic recording film according to 3) above, wherein the fluorine content is less than 0.05 wtppm, 5) After mixing the raw material powder containing the carbon powder described in 1) or 2) above, the mixed powder is molded and sintered, and the obtained sintered body is further subjected to isotropic hot pressing, And a method of manufacturing a sputtering target for forming a magnetic recording film, characterized by processing into a target shape.
- the Fe—Pt sputtering target in which C particles are dispersed according to the present invention enables the formation of a granular structure magnetic thin film without using an expensive simultaneous sputtering apparatus, and further reduces the amount of particles generated during sputtering. It has an excellent effect of providing a target.
- the present invention is characterized in that the fluorine (F) content in the carbon powder used for producing the sputtering target for forming a magnetic recording film is 50 wtppm or more.
- Carbon powder contains fluorine (F) as an impurity, and usually, a raw material with few such impurities is used.
- fluorine in the carbon raw material exists in a form bonded to carbon, but when this is exposed to a high temperature, a reaction (defluorination reaction) that breaks the bond occurs. At this time, a reaction occurs in which the carbons are bonded to each other by an extra bond.
- the present invention by using a carbon raw material powder containing a relatively large amount of fluorine in advance, the carbon-carbon bonding reaction is promoted during the defluorination reaction, and the difficulty of carbon sinterability can be improved.
- the present invention also includes the case where the median diameter of the carbon raw material powder used for manufacturing the sputtering target for forming a magnetic recording film is 0.1 to 20 ⁇ m.
- the surfaces of the carbon powders having a carbon-fluorine bond are preferably in contact as much as possible. If the median diameter of the carbon raw material powder is less than 0.1 ⁇ m, the amount of fluorine relative to the number of carbon particles may be insufficient. On the other hand, if the median diameter of the carbon raw material powder exceeds 20 ⁇ m, the carbon raw material itself may cause abnormal discharge, which is not preferable. Therefore, the median diameter of the carbon raw material powder is preferably 0.1 to 20 ⁇ m.
- the present invention also provides a magnetic recording film by sintering a carbon raw material powder having a fluorine (F) content of 50 wtppm or more and, if necessary, a median diameter of 0.1 to 20 ⁇ m.
- F fluorine
- a sputtering target is manufactured.
- the carbon raw material powder having such characteristics it is possible to promote the sintering of carbons, and therefore it is possible to suppress the generation of particles by dropping carbon from the target during sputtering.
- the present invention is characterized by the fluorine content and the like contained in the carbon raw material powder, and that known means can be used as the means for sintering.
- the present invention also includes the case where the fluorine content in the sputtering target for forming a magnetic recording film is less than 0.05 wtppm.
- the fluorine contained in the carbon raw material powder is reduced by being exposed to a high temperature during sintering to cause a defluorination reaction. This means, on the other hand, that the bonding (sintering) between carbons is promoted. Therefore, by adjusting the fluorine content in the carbon raw material powder and the fluorine content in the target, it is possible to quantitatively control the carbon-carbon bond amount. If the fluorine content in the target is 0.05 wtppm or more, fluorine may cause abnormal discharge and cause generation of particles, which is not preferable.
- a sputtering target for forming a magnetic recording film can be one having a known composition.
- a Pt content of 20 to 50 atomic ratio and a C content of 20 to 50 atomic ratio can be used.
- one or more metal elements selected from Ag, Cu, Au, B, Ru, and Mn can be added as an additive, and Si, Ti, Cr, Co, Fe, and B can be added.
- An oxide or nitride of one or more elements selected from Ta, Ga, Mn, Zn, Nb, Al, Mg, Zr, Y, and Ca can be added. Thereby, the produced magnetic thin film can obtain good magnetic properties.
- the sputtering target of the present invention is produced by a powder sintering method.
- each raw material powder Fe powder, Pt powder, C powder, etc.
- the C powder it is important to use a C powder containing a predetermined amount of fluorine, a C powder preliminarily fluorinated, or a mixed powder of a fluorinated C powder and other carbon raw materials.
- C powder having a particle size of 0.1 ⁇ m or more and 20 ⁇ m or less is desirably used. If the particle size of the raw material C powder is too small, there is a problem that the amount of fluorine is insufficient.
- the particle size of the raw material powder is large, it is difficult to finely disperse the C particles in the alloy, causing abnormal discharge. There is a risk of becoming. It is desirable to use other raw material powders of 0.1 ⁇ m or more and 20 ⁇ m or less. Further, an alloy powder (such as Fe—Pt powder) may be used as the raw material powder. In particular, an alloy powder containing Pt is effective for reducing the amount of oxygen in the raw material powder, although it depends on its composition. Also when using alloy powder, it is desirable to use a powder having a particle size of 0.1 to 20 ⁇ m.
- the above powder is weighed so as to have a desired composition and mixed using a known method such as a mortar.
- the mixed powder thus obtained is molded and sintered with a hot press.
- a plasma discharge sintering method or a hot isostatic pressing method can also be used.
- the holding temperature at the time of sintering depends on the composition of the sputtering target, but in most cases, it is in the temperature range of 900 to 1400 ° C.
- isotropic hot pressing is performed on the sintered body taken out from the hot press.
- Isotropic hot pressing is effective for improving the density of the sintered body.
- the holding temperature during the isotropic hot pressing is in the temperature range of 900 to 1400 ° C. depending on the composition of the sintered body.
- the pressure is set to 100 Mpa or more.
- the sputtering target of the present invention can be produced by processing the sintered body thus obtained into a desired shape using a lathe or the like.
- a sputtering target for forming a magnetic recording film with improved sinterability of carbon can be produced.
- the sputtering target of the present invention thus produced is less likely to generate particles during sputtering and is useful as a sputtering target used for forming a granular structure magnetic thin film.
- Example 1 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- C powder natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-30Pt-40C The fluorine content was analyzed by GDMS (glow discharge mass spectrometry). The same applies to the following examples and comparative examples.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). At this time, the number of particles was 130.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 94.8%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 4530.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 94.3%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1121.
- Example 2 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- the C powder a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle diameter of 5 ⁇ m to a raw material of Comparative Example 3 described later until the fluorine content becomes 60 wtppm and mixing in a mortar.
- the median diameter (D50) of C powder was 19.8 ⁇ m.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 327.
- both the weighed powders were put into a mortar with a capacity of 10 liters and rotated for 4 hours to mix.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 94.8%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 2,534.
- Example 3 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- the C powder a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle size of 10 ⁇ m to a raw material of Comparative Example 4 described later until the fluorine content becomes 200 wtppm and mixing in a mortar. Further, the median diameter (D50) of C powder was 13.4 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-30Pt-40C
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 86 pieces.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot pressing conditions were a vacuum atmosphere, a temperature rising rate of 300 ° C./hour, a holding temperature of 1200 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of temperature rising to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by Archimedes method, and the relative density was calculated to be 94.6%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1062.
- Example 4 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- the C powder natural graphite containing 40 wtppm of fluorine was used.
- the median diameter (D50) of C powder was 0.11 micrometer.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 432 pieces.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 94.2%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 3237.
- Example 5 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- the C powder a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle diameter of 5 ⁇ m to a raw material of Comparative Example 6 described later until the fluorine content becomes 15000 wtppm and mixing in a mortar was used.
- the median diameter (D50) of C powder was 5.6 ⁇ m.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by Archimedes method, and the relative density was calculated to be 96.0%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 78.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by Archimedes method, and the relative density was calculated to be 94.7%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1680.
- Example 6 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, Ag powder having an average particle diameter of 5 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- C powder natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-25Pt-5Ag-40C
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by Archimedes method, and the relative density was calculated to be 97.2%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 45.
- Comparative Example 7 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, Ag powder having an average particle diameter of 5 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- As the C powder a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-25Pt-5Ag-40C
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 289.
- Example 7 Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, C powder having an average particle diameter of 1 ⁇ m, and SiO 2 powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- C powder natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-36Pt-15C-8SiO 2
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1090 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method and the relative density was calculated to be 98.8%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 22.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1090 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method and the relative density was calculated to be 97.6%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 108.
- Fe powder having an average particle diameter of 3 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, Cu powder having an average particle diameter of 3.5 ⁇ m, and C powder having an average particle diameter of 1 ⁇ m were prepared as raw material powders.
- C powder natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-25Pt-5Cu-40C
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot pressing conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1060 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by Archimedes method, and the relative density was calculated to be 97.1%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 28.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot pressing conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1060 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.5%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 265.
- Example 9 Fe powder having an average particle size of 3 ⁇ m, Pt powder having an average particle size of 3 ⁇ m, Ag powder having an average particle size of 5 ⁇ m, BN powder having an average particle size of 10 ⁇ m, and C powder having an average particle size of 1 ⁇ m were prepared as raw material powders.
- C powder natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 ⁇ m. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g. Atomic ratio: Fe-25Pt-5Ag-20BN-20C
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method and the relative density was calculated to be 97.3%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 34.
- the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours.
- the mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
- the hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
- hot isostatic pressing was performed on the sintered body taken out from the hot press mold.
- the conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
- the sintered body thus produced had a fluorine content of less than 0.05 wtppm.
- the density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
- the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles having a diameter of 0.2 to 3.0 ⁇ m adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 326.
- Table 1 summarizes the above results. As shown in Table 1, in any case, the examples of the sputtering target of the present invention maintain the high density of the sputtering target, and the number of particles generated during sputtering is 500 or less, which is always less than that of the comparative example. Results were obtained.
- the present invention makes it possible to form a granular magnetic thin film without using an expensive co-sputtering apparatus, and further, a high-density Fe-Pt system in which C particles are dispersed in which the amount of particles generated during sputtering is reduced. It has the outstanding effect which can provide a sputtering target. Therefore, it is useful as a sputtering target for forming a magnetic thin film having a granular structure.
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Abstract
A carbon powder which can be used for the production of a sputtering target for forming a magnetic recording film, said carbon powder being characterized by having a fluorine content of 50 ppm by weight or more; and a sputtering target for forming a magnetic recording film, said sputtering target being characterized by being produced by a sintering method using the carbon powder. The present invention addresses the problem of enabling the production of a magnetic thin film having a granular structure without requiring the use of an expensive cosputtering device, and also addresses the problem of providing a highly dense sputtering target in which the amount of particles generated during sputtering is reduced.
Description
本発明は、磁気記録媒体におけるグラニュラー型の磁性薄膜の成膜に使用されるスパッタリングターゲット及び該ターゲットの製造に用いる炭素原料に関する。
The present invention relates to a sputtering target used for forming a granular magnetic thin film on a magnetic recording medium, and a carbon raw material used for manufacturing the target.
ハードディスクドライブに代表される磁気記録の分野では、磁気記録媒体中の磁性薄膜の材料として、強磁性金属であるCo、Fe、あるいは、Niをベースとした材料が用いられている。例えば、面内磁気記録方式を採用するハードディスクの磁性薄膜にはCoを主成分とするCo-Cr系やCo-Cr-Pt系の強磁性合金が用いられてきた。また、近年実用化された垂直磁気記録方式を採用するハードディスクの磁性薄膜には、Coを主成分とするCo-Cr-Pt系の強磁性合金と非磁性の無機物粒子からなる複合材料が多く用いられている。そして上記の磁性薄膜は、生産性の高さから、上記材料を成分とするスパッタリングターゲットをDCマグネトロンスパッタ装置でスパッタして作製されることが多い。
In the field of magnetic recording typified by a hard disk drive, a material based on a ferromagnetic metal such as Co, Fe, or Ni is used as a material for a magnetic thin film in a magnetic recording medium. For example, a Co—Cr-based or Co—Cr—Pt-based ferromagnetic alloy containing Co as a main component has been used for a magnetic thin film of a hard disk employing an in-plane magnetic recording method. In addition, hard magnetic thin films employing perpendicular magnetic recording that have been put into practical use in recent years often use a composite material composed of Co—Cr—Pt-based ferromagnetic alloy mainly composed of Co and non-magnetic inorganic particles. It has been. The magnetic thin film is often produced by sputtering a sputtering target containing the above material as a component with a DC magnetron sputtering apparatus because of its high productivity.
ハードディスクの記録密度は年々急速に増大しており、現状の600Gbit/in2の面密度から将来は1 Tbit/in2に達すると考えられている。1Tbit/in2に記録密度が達すると記録bitのサイズが10nmを下回るようになり、その場合、熱揺らぎによる超常磁性化が問題となってくると予想され、現在、使用されている磁気記録媒体の材料、例えばCo-Cr基合金にPtを添加して結晶磁気異方性を高めた材料では十分ではないことが予想される。10nm以下のサイズで安定的に強磁性として振る舞う磁性粒子は、より高い結晶磁気異方性を持っている必要があるからである。
Recording density of a hard disk is rapidly increasing year by year, it is believed to the future from the surface density of 600Gbit / in 2 the current reaches 1 Tbit / in 2. When the recording density reaches 1 Tbit / in 2 , the size of the recording bit becomes less than 10 nm. In that case, superparamagnetization due to thermal fluctuation is expected to be a problem, and magnetic recording media currently used It is expected that a material obtained by adding Pt to a material such as a Co—Cr base alloy to increase the magnetocrystalline anisotropy is not sufficient. This is because magnetic particles that behave stably as ferromagnetism with a size of 10 nm or less need to have higher crystal magnetic anisotropy.
上記のような理由から、L10構造を持つFePt相が超高密度記録媒体用材料として注目されている。L10構造を持つFePt相は高い結晶磁気異方性とともに、耐食性、耐酸化性に優れているため、磁気記録媒体としての応用に適した材料と期待されているものである。そして、FePt相を超高密度記録媒体用材料として使用する場合には、規則化したFePt磁性粒子を磁気的に孤立させた状態で出来るだけ高密度に方位をそろえて分散させるという技術の開発が求められている。
For the above reasons, an FePt phase having an L1 0 structure has attracted attention as a material for an ultrahigh density recording medium. The FePt phase having the L1 0 structure is expected to be a material suitable for application as a magnetic recording medium since it has high crystal magnetic anisotropy and excellent corrosion resistance and oxidation resistance. In the case where the FePt phase is used as a material for an ultra-high density recording medium, there has been a development of a technique for aligning and dispersing the ordered FePt magnetic particles in as high a density as possible in a magnetically isolated state. It has been demanded.
このようなことから、L10構造を有するFePt磁性粒子を酸化物や炭素といった非磁性材料で孤立させたグラニュラー構造磁性薄膜が、熱アシスト磁気記録方式を採用した次世代ハードディスクの磁気記録媒体用として提案されている。このグラニュラー構造磁性薄膜は、磁性粒子同士が非磁性物質の介在により磁気的に絶縁される構造となっている。グラニュラー構造の磁性薄膜を有する磁気記録媒体及びこれに関連する公知文献としては、特許文献1、特許文献2、特許文献3、特許文献4、特許文献5を挙げることができる。
For this reason, a granular structure magnetic thin film of FePt magnetic particles are isolated by a non-magnetic material such oxides or carbon having an L1 0 structure, as for a magnetic recording medium of the next generation hard disk employing a thermally assisted magnetic recording method Proposed. This granular structure magnetic thin film has a structure in which magnetic particles are magnetically insulated by interposition of a nonmagnetic substance. Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5 can be cited as magnetic recording media having a magnetic thin film having a granular structure and related documents.
上記L10構造を持つFePt相を有するグラニュラー構造磁性薄膜としては、非磁性物質としてCを体積比率として10~50%含有する磁性薄膜が、特にその磁気特性の高さから注目されている。このようなグラニュラー構造磁性薄膜は、Feターゲット、Ptターゲット、Cターゲットを同時にスパッタリングするか、あるいは、Fe-Pt合金ターゲット、Cターゲットを同時にスパッタリングすることで作製されることが知られている。しかしながら、これらのスパッタリングターゲットを同時スパッタするためには、高価な同時スパッタ装置が必要となる。
As the granular magnetic thin film having an FePt phase having the L1 0 structure, a magnetic thin film containing 10 to 50% by volume of C as a non-magnetic substance has been attracting attention because of its high magnetic properties. It is known that such a granular structure magnetic thin film is produced by simultaneously sputtering an Fe target, a Pt target, and a C target, or by simultaneously sputtering an Fe—Pt alloy target and a C target. However, in order to simultaneously sputter these sputtering targets, an expensive simultaneous sputtering apparatus is required.
また、一般にスパッタ装置で合金に非磁性材料の含まれるスパッタリングターゲットをスパッタしようとすると、スパッタ時に非磁性材料の不用意な脱離やスパッタリングターゲットに内包される空孔を起点として異常放電が生じパーティクル(基板上に付着したゴミ)が発生するという問題がある。この問題を解決するには、非磁性材料と母材合金との密着性を高め、スパッタリングターゲットを高密度化させる必要がある。一般に、合金に非磁性材料が含まれるスパッタリングターゲットの素材は粉末焼結法により作製される。ところが、Fe-PtにCが大量に含まれる場合、Cが難焼結材料であるため高密度な焼結体を得ることが困難であった。
In general, when a sputtering target containing a nonmagnetic material in an alloy is sputtered by a sputtering apparatus, abnormal discharge occurs due to inadvertent detachment of the nonmagnetic material or vacancies contained in the sputtering target at the time of sputtering. There is a problem that (dust attached to the substrate) is generated. In order to solve this problem, it is necessary to increase the adhesion between the nonmagnetic material and the base alloy and to increase the density of the sputtering target. Generally, a sputtering target material in which a nonmagnetic material is contained in an alloy is produced by a powder sintering method. However, when Fe—Pt contains a large amount of C, it is difficult to obtain a high-density sintered body because C is a difficult-to-sinter material.
また、本発明者は以前、C粒子が分散したFe-Pt系スパッタリングターゲットにおいて、非磁性材料であるC粒子を微細に母材金属に均一に分散させることによって、高密度スパッタリングターゲットを作製する技術を提案した(特許文献6)。この技術によれば、C粒子の凝集を抑制することができるが、C粒子が難焼結材料である以上、それ自体の焼結性を向上させることが困難であった。また、特許文献7~8には、磁気記録媒体膜形成用スパッタリングターゲットにおいて、FePt合金相中にC相を分散させることで、スパッタリング時の異常放電やスパッタレートの場所による違いを抑制できるという技術が記載されているが、C(炭素)の焼結性改善については何ら触れられていない。
In addition, the present inventor previously used a technique for producing a high-density sputtering target by uniformly dispersing C particles, which are nonmagnetic materials, in a base metal in a Fe—Pt-based sputtering target in which C particles are dispersed. (Patent Document 6). According to this technique, aggregation of C particles can be suppressed, but it is difficult to improve the sinterability of C particles because C particles are hardly sintered materials. Patent Documents 7 to 8 disclose a technique in which, in a sputtering target for forming a magnetic recording medium film, by dispersing the C phase in the FePt alloy phase, abnormal discharge during sputtering and differences due to the location of the sputtering rate can be suppressed. However, there is no mention about improvement of sinterability of C (carbon).
本発明の課題は、高価な同時スパッタ装置を用いることなく、グラニュラー構造磁性薄膜の作製を可能にする、C粒子が分散したFe-Pt系スパッタリングターゲットを提供することであり、さらには、スパッタリング時に発生するパーティクルの量を低減したスパッタリングターゲットを提供することを課題とする。
An object of the present invention is to provide an Fe—Pt-based sputtering target in which C particles are dispersed, which makes it possible to produce a granular structure magnetic thin film without using an expensive co-sputtering apparatus. It is an object to provide a sputtering target in which the amount of generated particles is reduced.
上記の課題を解決するために、本発明者は鋭意研究を行った結果、非磁性材料である炭素原料中のフッ素含有量を調整することによって、炭素の難焼結性を改善することができることを見出した。また、このようにして作られたスパッタリングターゲットは、炭素の脱落を防止することができ、パーティクルの発生量を提言することが可能となるので、成膜時の歩留まりを向上できることを見出した。
In order to solve the above problems, the present inventor has conducted intensive research, and as a result, it is possible to improve the difficulty of sintering carbon by adjusting the fluorine content in the carbon raw material that is a non-magnetic material. I found. In addition, it has been found that the sputtering target produced in this manner can prevent the carbon from falling off and can suggest the generation amount of particles, so that the yield during film formation can be improved.
このような知見に基づき、本発明は、
1)磁気記録膜形成用スパッタリングターゲットの製造に用いる炭素粉末において、フッ素含有量が50wtppm以上であることを特徴とする炭素粉末、
2)メジアン径が0.1~20μmであることを特徴とする上記1)記載の炭素粉末、
3)上記1)又は2)記載の炭素粉末をターゲットの原料として用い、粉末焼結法により作製したことを特徴とする磁気記録膜形成用スパッタリングターゲット、
4)フッ素含有量が0.05wtppm未満であることを特徴とする上記3)記載の磁気記録膜形成用スパッタリングターゲット、
5)上記1)又は2)記載の炭素粉末を含む原料粉末を混合した後、この混合粉末を成形、焼結し、得られた焼結体にさらに等方熱間加圧加工を施し、その後、ターゲット形状に加工することを特徴とする磁気記録膜形成用スパッタリングターゲットの製造方法、を提供する。 Based on such knowledge, the present invention
1) Carbon powder used for producing a sputtering target for forming a magnetic recording film, wherein the fluorine content is 50 wtppm or more,
2) The carbon powder according to 1) above, wherein the median diameter is 0.1 to 20 μm,
3) A sputtering target for forming a magnetic recording film, wherein the carbon powder described in 1) or 2) above is used as a raw material for the target, and is produced by a powder sintering method,
4) The sputtering target for forming a magnetic recording film according to 3) above, wherein the fluorine content is less than 0.05 wtppm,
5) After mixing the raw material powder containing the carbon powder described in 1) or 2) above, the mixed powder is molded and sintered, and the obtained sintered body is further subjected to isotropic hot pressing, And a method of manufacturing a sputtering target for forming a magnetic recording film, characterized by processing into a target shape.
1)磁気記録膜形成用スパッタリングターゲットの製造に用いる炭素粉末において、フッ素含有量が50wtppm以上であることを特徴とする炭素粉末、
2)メジアン径が0.1~20μmであることを特徴とする上記1)記載の炭素粉末、
3)上記1)又は2)記載の炭素粉末をターゲットの原料として用い、粉末焼結法により作製したことを特徴とする磁気記録膜形成用スパッタリングターゲット、
4)フッ素含有量が0.05wtppm未満であることを特徴とする上記3)記載の磁気記録膜形成用スパッタリングターゲット、
5)上記1)又は2)記載の炭素粉末を含む原料粉末を混合した後、この混合粉末を成形、焼結し、得られた焼結体にさらに等方熱間加圧加工を施し、その後、ターゲット形状に加工することを特徴とする磁気記録膜形成用スパッタリングターゲットの製造方法、を提供する。 Based on such knowledge, the present invention
1) Carbon powder used for producing a sputtering target for forming a magnetic recording film, wherein the fluorine content is 50 wtppm or more,
2) The carbon powder according to 1) above, wherein the median diameter is 0.1 to 20 μm,
3) A sputtering target for forming a magnetic recording film, wherein the carbon powder described in 1) or 2) above is used as a raw material for the target, and is produced by a powder sintering method,
4) The sputtering target for forming a magnetic recording film according to 3) above, wherein the fluorine content is less than 0.05 wtppm,
5) After mixing the raw material powder containing the carbon powder described in 1) or 2) above, the mixed powder is molded and sintered, and the obtained sintered body is further subjected to isotropic hot pressing, And a method of manufacturing a sputtering target for forming a magnetic recording film, characterized by processing into a target shape.
本発明のC粒子が分散したFe-Pt系スパッタリングターゲットは、高価な同時スパッタ装置を用いることなく、グラニュラー構造磁性薄膜の成膜を可能にし、さらには、スパッタリング時に発生するパーティクル量を低減したスパッタリングターゲットを提供できる優れた効果を有する。
The Fe—Pt sputtering target in which C particles are dispersed according to the present invention enables the formation of a granular structure magnetic thin film without using an expensive simultaneous sputtering apparatus, and further reduces the amount of particles generated during sputtering. It has an excellent effect of providing a target.
本発明は、磁気記録膜形成用スパッタリングターゲットの製造に用いる炭素粉末中のフッ素(F)含有量を50wtppm以上とすることを特徴とするものである。炭素粉末には不純物としてフッ素(F)が含有されており、通常は、このような不純物が少ない原料が使用されている。
ここで、炭素原料中のフッ素は、炭素と結合する形で存在しているが、これを高温に曝すことでこの結合が切れる反応(脱フッ素反応)が生じる。このとき、炭素は余った結合手によって炭素同士が結合する反応が生じる。本発明によれば、あらかじめフッ素を比較的多く含む炭素原料粉末を用いることにより、脱フッ素反応の際炭素同士の結合反応が促進して、炭素の難焼結性を改善することができる。 The present invention is characterized in that the fluorine (F) content in the carbon powder used for producing the sputtering target for forming a magnetic recording film is 50 wtppm or more. Carbon powder contains fluorine (F) as an impurity, and usually, a raw material with few such impurities is used.
Here, fluorine in the carbon raw material exists in a form bonded to carbon, but when this is exposed to a high temperature, a reaction (defluorination reaction) that breaks the bond occurs. At this time, a reaction occurs in which the carbons are bonded to each other by an extra bond. According to the present invention, by using a carbon raw material powder containing a relatively large amount of fluorine in advance, the carbon-carbon bonding reaction is promoted during the defluorination reaction, and the difficulty of carbon sinterability can be improved.
ここで、炭素原料中のフッ素は、炭素と結合する形で存在しているが、これを高温に曝すことでこの結合が切れる反応(脱フッ素反応)が生じる。このとき、炭素は余った結合手によって炭素同士が結合する反応が生じる。本発明によれば、あらかじめフッ素を比較的多く含む炭素原料粉末を用いることにより、脱フッ素反応の際炭素同士の結合反応が促進して、炭素の難焼結性を改善することができる。 The present invention is characterized in that the fluorine (F) content in the carbon powder used for producing the sputtering target for forming a magnetic recording film is 50 wtppm or more. Carbon powder contains fluorine (F) as an impurity, and usually, a raw material with few such impurities is used.
Here, fluorine in the carbon raw material exists in a form bonded to carbon, but when this is exposed to a high temperature, a reaction (defluorination reaction) that breaks the bond occurs. At this time, a reaction occurs in which the carbons are bonded to each other by an extra bond. According to the present invention, by using a carbon raw material powder containing a relatively large amount of fluorine in advance, the carbon-carbon bonding reaction is promoted during the defluorination reaction, and the difficulty of carbon sinterability can be improved.
また、本発明は、磁気記録膜形成用スパッタリングターゲットの製造に用いる炭素原料粉末のメジアン径を0.1~20μmとする場合も包含する。上記の脱フッ素反応により炭素原料同士の結合を促進するためには、炭素-フッ素の結合を有する炭素粉末同士の表面ができるだけ接していることが好ましい。炭素原料粉末のメジアン径を0.1μm未満とすると、炭素粒子数に対するフッ素量が不足することがある。一方、炭素原料粉末のメジアン径を20μm超とすると、炭素原料そのものが異常放電の原因となることがあり好ましくない。したがって、炭素原料粉末のメジアン径を0.1~20μmとすることが好ましい。
The present invention also includes the case where the median diameter of the carbon raw material powder used for manufacturing the sputtering target for forming a magnetic recording film is 0.1 to 20 μm. In order to promote the bonding between the carbon raw materials by the above defluorination reaction, the surfaces of the carbon powders having a carbon-fluorine bond are preferably in contact as much as possible. If the median diameter of the carbon raw material powder is less than 0.1 μm, the amount of fluorine relative to the number of carbon particles may be insufficient. On the other hand, if the median diameter of the carbon raw material powder exceeds 20 μm, the carbon raw material itself may cause abnormal discharge, which is not preferable. Therefore, the median diameter of the carbon raw material powder is preferably 0.1 to 20 μm.
また、本発明は、フッ素(F)含有量が50wtppm以上、必要に応じて、メジアン径が0.1~20μmの炭素原料粉末を用いて、これを焼結することにより、磁気記録膜形成用スパッタリングターゲットを製造することを特徴とするものである。このような特徴を有する炭素原料粉末を用いることにより、炭素同士の焼結を促進することができるので、スパッタリングの際にターゲットから炭素が脱落して、パーティクルが発生することを抑制することができる。なお、本発明は、炭素原料粉末に含まれるフッ素含有量等に特徴を有するもので、焼結の手段については、公知の手段を用いることができることは当然理解されるべきである。
The present invention also provides a magnetic recording film by sintering a carbon raw material powder having a fluorine (F) content of 50 wtppm or more and, if necessary, a median diameter of 0.1 to 20 μm. A sputtering target is manufactured. By using the carbon raw material powder having such characteristics, it is possible to promote the sintering of carbons, and therefore it is possible to suppress the generation of particles by dropping carbon from the target during sputtering. . It should be understood that the present invention is characterized by the fluorine content and the like contained in the carbon raw material powder, and that known means can be used as the means for sintering.
また、本発明は、磁気記録膜形成用スパッタリングターゲット中のフッ素の含有量が0.05wtppm未満である場合も包含する。炭素原料粉末中に含まれるフッ素は、焼結時に高温に曝されることで脱フッ素反応が生じて低減する。このことは、一方で、炭素同士の結合(焼結)が促進していることを意味する。したがって、炭素原料粉末中のフッ素含有量とターゲット中のフッ素含有量を調整することで、定量的に炭素同士の結合量を制御することが可能となる。ターゲット中のフッ素含有量が0.05wtppm以上であると、フッ素が異常放電の原因となって、パーティクルの発生を引き起こすことがあるため、好ましくない。
The present invention also includes the case where the fluorine content in the sputtering target for forming a magnetic recording film is less than 0.05 wtppm. The fluorine contained in the carbon raw material powder is reduced by being exposed to a high temperature during sintering to cause a defluorination reaction. This means, on the other hand, that the bonding (sintering) between carbons is promoted. Therefore, by adjusting the fluorine content in the carbon raw material powder and the fluorine content in the target, it is possible to quantitatively control the carbon-carbon bond amount. If the fluorine content in the target is 0.05 wtppm or more, fluorine may cause abnormal discharge and cause generation of particles, which is not preferable.
また、本発明において、磁気記録膜形成用スパッタリングターゲットにはすでに公知の組成のものを使用することができる。例えば、C粒子が分散したFe-Pt合金系ターゲットにおいて、Pt含有量が20以上50原子数比以下、C含有量が20以上50原子数比以下のものを使用することができる。また、本発明は、添加材として、Ag、Cu、Au、B、Ru、Mnから選択した1種以上の金属元素を添加することができ、さらに、Si、Ti、Cr、Co、Fe、B、Ta、Ga、Mn、Zn、Nb、Al、Mg、Zr、Y、Caから選択した1種以上の元素の酸化物もしくは窒化物を添加することができる。これにより、作製された磁性薄膜は良好な磁気特性が得られる。
In the present invention, a sputtering target for forming a magnetic recording film can be one having a known composition. For example, in a Fe—Pt alloy-based target in which C particles are dispersed, a Pt content of 20 to 50 atomic ratio and a C content of 20 to 50 atomic ratio can be used. In the present invention, one or more metal elements selected from Ag, Cu, Au, B, Ru, and Mn can be added as an additive, and Si, Ti, Cr, Co, Fe, and B can be added. An oxide or nitride of one or more elements selected from Ta, Ga, Mn, Zn, Nb, Al, Mg, Zr, Y, and Ca can be added. Thereby, the produced magnetic thin film can obtain good magnetic properties.
本発明のスパッタリングターゲットは、粉末焼結法によって作製する。作製にあたり、各原料粉末(Fe粉末、Pt粉末、C粉末など)を用意する。ここで、C粉末として、フッ素が所定量含有するC粉末、予めフッ素化処理したC粉末、あるいはフッ素化処理したC粉末とその他の炭素原料の混合粉末を使用することが重要である。
C粉末は、粒径0.1μm以上20μm以下のものを用いることが望ましい。原料C粉末の粒径が小さ過ぎると、フッ素量が不足するなどの問題があり、一方、原料粉末の粒径が大きいと、C粒子が合金中に微細分散することが難しく、異常放電の原因となるおそれがある。その他の原料粉末についても0.1μm以上20μm以下のものを用いることが望ましい。
さらに原料粉末として、合金粉末(Fe-Pt粉など)を用いてもよい。特にPtを含む合金粉末はその組成にもよるが、原料粉末中の酸素量を少なくするために有効である。合金粉末を用いる場合も、粒径が0.1μm以上20μm以下のものを用いることが望ましい。 The sputtering target of the present invention is produced by a powder sintering method. In preparation, each raw material powder (Fe powder, Pt powder, C powder, etc.) is prepared. Here, as the C powder, it is important to use a C powder containing a predetermined amount of fluorine, a C powder preliminarily fluorinated, or a mixed powder of a fluorinated C powder and other carbon raw materials.
C powder having a particle size of 0.1 μm or more and 20 μm or less is desirably used. If the particle size of the raw material C powder is too small, there is a problem that the amount of fluorine is insufficient. On the other hand, if the particle size of the raw material powder is large, it is difficult to finely disperse the C particles in the alloy, causing abnormal discharge. There is a risk of becoming. It is desirable to use other raw material powders of 0.1 μm or more and 20 μm or less.
Further, an alloy powder (such as Fe—Pt powder) may be used as the raw material powder. In particular, an alloy powder containing Pt is effective for reducing the amount of oxygen in the raw material powder, although it depends on its composition. Also when using alloy powder, it is desirable to use a powder having a particle size of 0.1 to 20 μm.
C粉末は、粒径0.1μm以上20μm以下のものを用いることが望ましい。原料C粉末の粒径が小さ過ぎると、フッ素量が不足するなどの問題があり、一方、原料粉末の粒径が大きいと、C粒子が合金中に微細分散することが難しく、異常放電の原因となるおそれがある。その他の原料粉末についても0.1μm以上20μm以下のものを用いることが望ましい。
さらに原料粉末として、合金粉末(Fe-Pt粉など)を用いてもよい。特にPtを含む合金粉末はその組成にもよるが、原料粉末中の酸素量を少なくするために有効である。合金粉末を用いる場合も、粒径が0.1μm以上20μm以下のものを用いることが望ましい。 The sputtering target of the present invention is produced by a powder sintering method. In preparation, each raw material powder (Fe powder, Pt powder, C powder, etc.) is prepared. Here, as the C powder, it is important to use a C powder containing a predetermined amount of fluorine, a C powder preliminarily fluorinated, or a mixed powder of a fluorinated C powder and other carbon raw materials.
C powder having a particle size of 0.1 μm or more and 20 μm or less is desirably used. If the particle size of the raw material C powder is too small, there is a problem that the amount of fluorine is insufficient. On the other hand, if the particle size of the raw material powder is large, it is difficult to finely disperse the C particles in the alloy, causing abnormal discharge. There is a risk of becoming. It is desirable to use other raw material powders of 0.1 μm or more and 20 μm or less.
Further, an alloy powder (such as Fe—Pt powder) may be used as the raw material powder. In particular, an alloy powder containing Pt is effective for reducing the amount of oxygen in the raw material powder, although it depends on its composition. Also when using alloy powder, it is desirable to use a powder having a particle size of 0.1 to 20 μm.
そして、上記の粉末を所望の組成になるように秤量し、乳鉢等の公知の手法を用いて混合する。こうして得られた混合粉末をホットプレスで成型・焼結する。ホットプレス以外にも、プラズマ放電焼結法、熱間静水圧焼結法を使用することもできる。焼結時の保持温度は、スパッタリングターゲットの組成にもよるが、多くの場合、900~1400°Cの温度範囲とする。
Then, the above powder is weighed so as to have a desired composition and mixed using a known method such as a mortar. The mixed powder thus obtained is molded and sintered with a hot press. In addition to hot pressing, a plasma discharge sintering method or a hot isostatic pressing method can also be used. The holding temperature at the time of sintering depends on the composition of the sputtering target, but in most cases, it is in the temperature range of 900 to 1400 ° C.
次に、ホットプレスから取り出した焼結体に等方熱間加圧加工を施す。等方熱間加圧加工は、焼結体の密度向上に有効である。等方熱間加圧加工時の保持温度は焼結体の組成にもよるが、多くの場合、900~1400°Cの温度範囲である。また加圧力は100Mpa以上に設定する。
このようにして得られた焼結体を旋盤等で所望の形状に加工することにより、本発明のスパッタリングターゲットは作製できる。 Next, isotropic hot pressing is performed on the sintered body taken out from the hot press. Isotropic hot pressing is effective for improving the density of the sintered body. In most cases, the holding temperature during the isotropic hot pressing is in the temperature range of 900 to 1400 ° C. depending on the composition of the sintered body. Further, the pressure is set to 100 Mpa or more.
The sputtering target of the present invention can be produced by processing the sintered body thus obtained into a desired shape using a lathe or the like.
このようにして得られた焼結体を旋盤等で所望の形状に加工することにより、本発明のスパッタリングターゲットは作製できる。 Next, isotropic hot pressing is performed on the sintered body taken out from the hot press. Isotropic hot pressing is effective for improving the density of the sintered body. In most cases, the holding temperature during the isotropic hot pressing is in the temperature range of 900 to 1400 ° C. depending on the composition of the sintered body. Further, the pressure is set to 100 Mpa or more.
The sputtering target of the present invention can be produced by processing the sintered body thus obtained into a desired shape using a lathe or the like.
以上により、炭素の難焼結性が改善した磁気記録膜形成用スパッタリングターゲットを作製することができる。このようにして製造した本発明のスパッタリングターゲットは、スパッタリングの際にパーティクルの発生が少なく、グラニュラー構造磁性薄膜の成膜に使用するスパッタリングターゲットとして有用である。
As described above, a sputtering target for forming a magnetic recording film with improved sinterability of carbon can be produced. The sputtering target of the present invention thus produced is less likely to generate particles during sputtering and is useful as a sputtering target used for forming a granular structure magnetic thin film.
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。
Hereinafter, description will be made based on examples and comparative examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
(実施例1)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C
なお、フッ素含有量はGDMS(グロー放電質量分析)にて分析した。以下の実施例、比較例についても同様である。 (Example 1)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
The fluorine content was analyzed by GDMS (glow discharge mass spectrometry). The same applies to the following examples and comparative examples.
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C
なお、フッ素含有量はGDMS(グロー放電質量分析)にて分析した。以下の実施例、比較例についても同様である。 (Example 1)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
The fluorine content was analyzed by GDMS (glow discharge mass spectrometry). The same applies to the following examples and comparative examples.
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときのパーティクル個数は130個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). At this time, the number of particles was 130.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときのパーティクル個数は130個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). At this time, the number of particles was 130.
(比較例1)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量1wtppm、メジアン径(D50)0.05μmのカーボンブラックを用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 1)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, carbon black having a fluorine content of 1 wtppm and a median diameter (D50) of 0.05 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量1wtppm、メジアン径(D50)0.05μmのカーボンブラックを用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 1)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, carbon black having a fluorine content of 1 wtppm and a median diameter (D50) of 0.05 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次に、ホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.8%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.8%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次に、ホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.8%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.8%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は4530個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 4530.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は4530個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 4530.
(比較例2)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)6.3μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 2)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 6.3 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)6.3μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 2)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 6.3 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.3%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.3%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は1121個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1121.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は1121個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1121.
(実施例2)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、後述する比較例3の原料に、平均粒子径5μmのフッ化グラファイト(フッ素含有割合40%)をフッ素含有量60wtppmとなるまで添加して乳鉢で混合したものを用いた。また、C粉末のメジアン径(D50)は、19.8μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Example 2)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle diameter of 5 μm to a raw material of Comparative Example 3 described later until the fluorine content becomes 60 wtppm and mixing in a mortar. The median diameter (D50) of C powder was 19.8 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、後述する比較例3の原料に、平均粒子径5μmのフッ化グラファイト(フッ素含有割合40%)をフッ素含有量60wtppmとなるまで添加して乳鉢で混合したものを用いた。また、C粉末のメジアン径(D50)は、19.8μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Example 2)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle diameter of 5 μm to a raw material of Comparative Example 3 described later until the fluorine content becomes 60 wtppm and mixing in a mortar. The median diameter (D50) of C powder was 19.8 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また
密度をアルキメデス法で測定し、相対密度を計算したところ96.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また
密度をアルキメデス法で測定し、相対密度を計算したところ96.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は327個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 327.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は327個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 327.
(比較例3)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)20.2μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 3)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 20.2 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)20.2μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 3)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 20.2 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を共に容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.8%であった。 Next, both the weighed powders were put into a mortar with a capacity of 10 liters and rotated for 4 hours to mix. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.8%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.8%であった。 Next, both the weighed powders were put into a mortar with a capacity of 10 liters and rotated for 4 hours to mix. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.8%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は2534個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 2,534.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は2534個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 2,534.
(実施例3)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、後述する比較例4の原料に平均粒子径10μmのフッ化グラファイト(フッ素含有割合40%)をフッ素含有量200wtppmとなるまで添加して乳鉢で混合したものを用いた。また、C粉末のメジアン径(D50)は、13.4μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Example 3)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle size of 10 μm to a raw material of Comparative Example 4 described later until the fluorine content becomes 200 wtppm and mixing in a mortar. Further, the median diameter (D50) of C powder was 13.4 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、後述する比較例4の原料に平均粒子径10μmのフッ化グラファイト(フッ素含有割合40%)をフッ素含有量200wtppmとなるまで添加して乳鉢で混合したものを用いた。また、C粉末のメジアン径(D50)は、13.4μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Example 3)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle size of 10 μm to a raw material of Comparative Example 4 described later until the fluorine content becomes 200 wtppm and mixing in a mortar. Further, the median diameter (D50) of C powder was 13.4 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は86個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 86 pieces.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は86個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 86 pieces.
(比較例4)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)13.9μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 4)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 13.9 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)13.9μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 4)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 13.9 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1200°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.6%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot pressing conditions were a vacuum atmosphere, a temperature rising rate of 300 ° C./hour, a holding temperature of 1200 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of temperature rising to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 94.6%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1200°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.6%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot pressing conditions were a vacuum atmosphere, a temperature rising rate of 300 ° C./hour, a holding temperature of 1200 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of temperature rising to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 94.6%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は1062個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1062.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は1062個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1062.
(実施例4)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を40wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は0.11μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C Example 4
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, natural graphite containing 40 wtppm of fluorine was used. Moreover, the median diameter (D50) of C powder was 0.11 micrometer. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を40wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は0.11μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C Example 4
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, natural graphite containing 40 wtppm of fluorine was used. Moreover, the median diameter (D50) of C powder was 0.11 micrometer. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は432個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 432 pieces.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は432個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 432 pieces.
(比較例5)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例4の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)0.13μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 5)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 4 in the atmosphere at 600 ° C. and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 0.13 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例4の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)0.13μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 5)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 4 in the atmosphere at 600 ° C. and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 0.13 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.2%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.2%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.2%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 94.2%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は3237個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 3237.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は3237個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 3237.
(実施例5)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、後述する比較例6の原料に、平均粒子径5μmのフッ化グラファイト(フッ素含有割合40%)をフッ素含有量15000wtppmとなるまで添加して乳鉢で混合したものを用いた。また、C粉末のメジアン径(D50)は、5.6μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Example 5)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle diameter of 5 μm to a raw material of Comparative Example 6 described later until the fluorine content becomes 15000 wtppm and mixing in a mortar was used. The median diameter (D50) of C powder was 5.6 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、後述する比較例6の原料に、平均粒子径5μmのフッ化グラファイト(フッ素含有割合40%)をフッ素含有量15000wtppmとなるまで添加して乳鉢で混合したものを用いた。また、C粉末のメジアン径(D50)は、5.6μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Example 5)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by adding graphite fluoride (fluorine content ratio 40%) having an average particle diameter of 5 μm to a raw material of Comparative Example 6 described later until the fluorine content becomes 15000 wtppm and mixing in a mortar was used. The median diameter (D50) of C powder was 5.6 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.0%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 96.0%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.0%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 96.0%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は78個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 78.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は78個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 78.
(比較例6)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)5.9μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 6)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 5.9 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素含有量5wtppm、メジアン径(D50)5.9μmの黒鉛を用いた。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-30Pt-40C (Comparative Example 6)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, graphite having a fluorine content of 5 wtppm and a median diameter (D50) of 5.9 μm was used. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-30Pt-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.7%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 94.7%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1400°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ94.7%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1400 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 94.7%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は1680個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1680.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は1680個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 1680.
(実施例6)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-40C (Example 6)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Ag powder having an average particle diameter of 5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-40C (Example 6)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Ag powder having an average particle diameter of 5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.2%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 97.2%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.2%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 97.2%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は45個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 45.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は45個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 45.
(比較例7)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例6の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-40C (Comparative Example 7)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Ag powder having an average particle diameter of 5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例6の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-40C (Comparative Example 7)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Ag powder having an average particle diameter of 5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.1%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は289個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 289.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は289個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 289.
(実施例7)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末、平均粒径1μmのSiO2粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-36Pt-15C-8SiO2 (Example 7)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, C powder having an average particle diameter of 1 μm, and SiO 2 powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-36Pt-15C-8SiO 2
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末、平均粒径1μmのSiO2粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-36Pt-15C-8SiO2 (Example 7)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, C powder having an average particle diameter of 1 μm, and SiO 2 powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-36Pt-15C-8SiO 2
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1090°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ98.8%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1090 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method and the relative density was calculated to be 98.8%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1090°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ98.8%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1090 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method and the relative density was calculated to be 98.8%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は22個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 22.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は22個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 22.
(比較例8)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末、平均粒径1μmのSiO2粉末を用意した。C粉末には、実施例7の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末はフッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-36Pt-15C-8SiO2 (Comparative Example 8)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, C powder having an average particle diameter of 1 μm, and SiO 2 powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 7 at 600 ° C. in the air and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-36Pt-15C-8SiO 2
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径1μmのC粉末、平均粒径1μmのSiO2粉末を用意した。C粉末には、実施例7の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末はフッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-36Pt-15C-8SiO2 (Comparative Example 8)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, C powder having an average particle diameter of 1 μm, and SiO 2 powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 7 at 600 ° C. in the air and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-36Pt-15C-8SiO 2
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1090°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.6%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1090 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method and the relative density was calculated to be 97.6%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1090°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度1100°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、1100°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.6%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1090 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a temperature increase rate of 300 ° C./hour, a holding temperature of 1100 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of the temperature increase to 1100 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method and the relative density was calculated to be 97.6%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は108個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 108.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は108個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 108.
(実施例8)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径3.5μmのCu粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Cu-40C (Example 8)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Cu powder having an average particle diameter of 3.5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Cu-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径3.5μmのCu粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Cu-40C (Example 8)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Cu powder having an average particle diameter of 3.5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Cu-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1060°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot pressing conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1060 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 97.1%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1060°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.1%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot pressing conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1060 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by Archimedes method, and the relative density was calculated to be 97.1%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は28個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 28.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は28個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 28.
(比較例9)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径3.5μmのCu粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例6の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Cu-40C (Comparative Example 9)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Cu powder having an average particle diameter of 3.5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Cu-40C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径3.5μmのCu粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例6の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Cu-40C (Comparative Example 9)
Fe powder having an average particle diameter of 3 μm, Pt powder having an average particle diameter of 3 μm, Cu powder having an average particle diameter of 3.5 μm, and C powder having an average particle diameter of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Cu-40C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1060°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.5%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot pressing conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1060 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.5%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度1060°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.5%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot pressing conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 1060 ° C., and a holding time of 2 hours, and pressurization was performed at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.5%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は265個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 265.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は265個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 265.
(実施例9)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径10μmのBN粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-20BN-20C Example 9
Fe powder having an average particle size of 3 μm, Pt powder having an average particle size of 3 μm, Ag powder having an average particle size of 5 μm, BN powder having an average particle size of 10 μm, and C powder having an average particle size of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-20BN-20C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径10μmのBN粉末、平均粒径1μmのC粉末を用意した。C粉末には、フッ素を150wtppm含有する天然黒鉛を用いた。また、C粉末のメジアン径(D50)は6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-20BN-20C Example 9
Fe powder having an average particle size of 3 μm, Pt powder having an average particle size of 3 μm, Ag powder having an average particle size of 5 μm, BN powder having an average particle size of 10 μm, and C powder having an average particle size of 1 μm were prepared as raw material powders. For the C powder, natural graphite containing 150 wtppm of fluorine was used. Further, the median diameter (D50) of the C powder was 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-20BN-20C
次に、秤量した粉末を容量10リットルの乳鉢に投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method and the relative density was calculated to be 97.3%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ97.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method and the relative density was calculated to be 97.3%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)にスパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は34個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 34.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は34個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then sputtering was performed on a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva).
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 34.
(比較例10)
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径10μmのBN粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例6の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-20BN-20C (Comparative Example 10)
Fe powder having an average particle size of 3 μm, Pt powder having an average particle size of 3 μm, Ag powder having an average particle size of 5 μm, BN powder having an average particle size of 10 μm, and C powder having an average particle size of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-20BN-20C
原料粉末として平均粒径3μmのFe粉末、平均粒径3μmのPt粉末、平均粒径5μmのAg粉末、平均粒径10μmのBN粉末、平均粒径1μmのC粉末を用意した。C粉末には、実施例6の原料を大気中、600°Cで焼成し、脱フッ素化処理を施したものを用いた。このC粉末は、フッ素含有量0.05wtppm未満、メジアン径(D50)6.1μmであった。これらの粉末を以下の原子数比で、合計重量が2600gとなるように秤量した。
原子数比:Fe-25Pt-5Ag-20BN-20C (Comparative Example 10)
Fe powder having an average particle size of 3 μm, Pt powder having an average particle size of 3 μm, Ag powder having an average particle size of 5 μm, BN powder having an average particle size of 10 μm, and C powder having an average particle size of 1 μm were prepared as raw material powders. As the C powder, a material obtained by firing the raw material of Example 6 at 600 ° C. in the atmosphere and subjecting it to defluorination treatment was used. This C powder had a fluorine content of less than 0.05 wtppm and a median diameter (D50) of 6.1 μm. These powders were weighed in the following atomic ratio so that the total weight would be 2600 g.
Atomic ratio: Fe-25Pt-5Ag-20BN-20C
次に、秤量した粉末を容量10リットルの乳鉢に封入投入し、4時間回転させて混合した。そして乳鉢から取り出した混合粉末をカーボン製の型に充填しホットプレスした。
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
ホットプレスの条件は、真空雰囲気、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時から保持終了まで30MPaで加圧した。保持終了後はチャンバー内でそのまま自然冷却させた。
次にホットプレスの型から取り出した焼結体に熱間等方加圧加工を施した。熱間等方加圧加工の条件は、昇温速度300°C/時間、保持温度950°C、保持時間2時間とし、昇温開始時からArガスのガス圧を徐々に高めて、950°C保持中は150MPaで加圧した。保持終了後は炉内でそのまま自然冷却させた。
こうして作製された焼結体のフッ素含有量は0.05wtppm未満であった。また密度をアルキメデス法で測定し、相対密度を計算したところ96.3%であった。 Next, the weighed powder was put into a mortar with a capacity of 10 liters and mixed by rotating for 4 hours. The mixed powder taken out from the mortar was filled into a carbon mold and hot pressed.
The hot press conditions were a vacuum atmosphere, a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., and a holding time of 2 hours, and pressure was applied at 30 MPa from the start of heating to the end of holding. After completion of the holding, it was naturally cooled in the chamber.
Next, hot isostatic pressing was performed on the sintered body taken out from the hot press mold. The conditions for hot isostatic pressing were a heating rate of 300 ° C./hour, a holding temperature of 950 ° C., a holding time of 2 hours, and gradually increasing the Ar gas pressure from the start of heating to 950 ° During C holding, the pressure was increased to 150 MPa. After completion of the holding, it was naturally cooled in the furnace.
The sintered body thus produced had a fluorine content of less than 0.05 wtppm. The density was measured by the Archimedes method, and the relative density was calculated to be 96.3%.
次に焼結体を直径180.0mm、厚さ5.0mmの形状へ旋盤で切削加工した後、マグネトロンスパッタ装置(キヤノンアネルバ製C-3010スパッタリングシステム)に取り付け、スパッタリングを行った。
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は326個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 326.
スパッタリングの条件は、投入電力1kW、Arガス圧1.7Paとし、2kWhrのプレスパッタリングを実施した後、4インチ径のシリコン基板上に20秒間成膜した。そして基板上へ付着した直径0.2~3.0μmのパーティクルの個数を表面異物検査装置(Surfscan6420、KLA-Tencor社製)で測定した。このときの個数は326個であった。 Next, the sintered body was cut into a shape having a diameter of 180.0 mm and a thickness of 5.0 mm with a lathe, and then attached to a magnetron sputtering apparatus (C-3010 sputtering system manufactured by Canon Anelva) and subjected to sputtering.
The sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa. After performing 2 kWhr of pre-sputtering, a film was formed on a 4-inch diameter silicon substrate for 20 seconds. The number of particles having a diameter of 0.2 to 3.0 μm adhering to the substrate was measured with a surface foreign matter inspection apparatus (Surfscan 6420, manufactured by KLA-Tencor). The number at this time was 326.
以上の結果をまとめたものが表1である。表1に示すように、本発明のスパッタリングターゲットの実施例はいずれの場合においても、スパッタリングターゲットの高密度が維持され、スパッタリング時に発生するパーティクルは500個以下であり、比較例に比べ常に少ないという結果が得られた。
Table 1 summarizes the above results. As shown in Table 1, in any case, the examples of the sputtering target of the present invention maintain the high density of the sputtering target, and the number of particles generated during sputtering is 500 or less, which is always less than that of the comparative example. Results were obtained.
本発明は、高価な同時スパッタ装置を用いることなく、グラニュラー構造磁性薄膜の成膜を可能にし、さらには、スパッタリング時に発生するパーティクル量を低減した高密度な、C粒子が分散したFe-Pt系スパッタリングターゲットを提供できる優れた効果を有する。したがってグラニュラー構造の磁性薄膜の成膜用スパッタリングターゲットとして有用である。
The present invention makes it possible to form a granular magnetic thin film without using an expensive co-sputtering apparatus, and further, a high-density Fe-Pt system in which C particles are dispersed in which the amount of particles generated during sputtering is reduced. It has the outstanding effect which can provide a sputtering target. Therefore, it is useful as a sputtering target for forming a magnetic thin film having a granular structure.
The present invention makes it possible to form a granular magnetic thin film without using an expensive co-sputtering apparatus, and further, a high-density Fe-Pt system in which C particles are dispersed in which the amount of particles generated during sputtering is reduced. It has the outstanding effect which can provide a sputtering target. Therefore, it is useful as a sputtering target for forming a magnetic thin film having a granular structure.
Claims (5)
- 磁気記録膜形成用スパッタリングターゲットの製造に用いる炭素粉末において、フッ素含有量が50wtppm以上であることを特徴とする炭素粉末。 Carbon powder used for manufacturing a sputtering target for forming a magnetic recording film, wherein the fluorine content is 50 wtppm or more.
- メジアン径が0.1~20μmであることを特徴とする請求項1記載の炭素粉末。 2. The carbon powder according to claim 1, wherein the median diameter is 0.1 to 20 μm.
- 請求項1又は2記載の炭素粉末をターゲットの原料として用い、粉末焼結法により作製したことを特徴とする磁気記録膜形成用スパッタリングターゲット。 A sputtering target for forming a magnetic recording film, wherein the carbon powder according to claim 1 or 2 is used as a target raw material and is produced by a powder sintering method.
- フッ素含有量が0.05wtppm未満であることを特徴とする請求項3記載の磁気記録膜形成用スパッタリングターゲット。 The sputtering target for forming a magnetic recording film according to claim 3, wherein the fluorine content is less than 0.05 wtppm.
- 請求項1又は2記載の炭素粉末を含む原料粉末を混合した後、この混合粉末を成形、焼結し、得られた焼結体にさらに等方熱間加圧加工を施し、その後、ターゲット形状に加工することを特徴とする磁気記録膜形成用スパッタリングターゲットの製造方法。 After mixing the raw material powder containing the carbon powder according to claim 1 or 2, the mixed powder is molded and sintered, and the obtained sintered body is further subjected to isotropic hot pressing, and then the target shape. A method for producing a sputtering target for forming a magnetic recording film, characterized by:
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JP2005247679A (en) * | 2003-12-12 | 2005-09-15 | Greatbatch Technologies Advanced Research Lab Inc | Medium rate and high rate battery |
WO2005095274A1 (en) * | 2004-03-31 | 2005-10-13 | Stella Chemifa Corporation | Carbon nanotubes aggregate, method for forming same, and biocompatible material |
JP2009527441A (en) * | 2006-02-21 | 2009-07-30 | カリフォルニア インスティテュート オブ テクノロジー | Electrochemistry of partially fluorinated carbon |
WO2012086335A1 (en) * | 2010-12-20 | 2012-06-28 | Jx日鉱日石金属株式会社 | Fe-pt-based sputtering target with dispersed c particles |
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JPS5918108A (en) * | 1983-05-20 | 1984-01-30 | Central Glass Co Ltd | Preparation of modified graphite fluoride |
JP2005247679A (en) * | 2003-12-12 | 2005-09-15 | Greatbatch Technologies Advanced Research Lab Inc | Medium rate and high rate battery |
WO2005095274A1 (en) * | 2004-03-31 | 2005-10-13 | Stella Chemifa Corporation | Carbon nanotubes aggregate, method for forming same, and biocompatible material |
JP2009527441A (en) * | 2006-02-21 | 2009-07-30 | カリフォルニア インスティテュート オブ テクノロジー | Electrochemistry of partially fluorinated carbon |
WO2012086335A1 (en) * | 2010-12-20 | 2012-06-28 | Jx日鉱日石金属株式会社 | Fe-pt-based sputtering target with dispersed c particles |
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