WO2023037810A1 - Cible de pulvérisation contenant du nitrure dur - Google Patents

Cible de pulvérisation contenant du nitrure dur Download PDF

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WO2023037810A1
WO2023037810A1 PCT/JP2022/030289 JP2022030289W WO2023037810A1 WO 2023037810 A1 WO2023037810 A1 WO 2023037810A1 JP 2022030289 W JP2022030289 W JP 2022030289W WO 2023037810 A1 WO2023037810 A1 WO 2023037810A1
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less
sputtering target
nitride
alloy
hard nitride
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PCT/JP2022/030289
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Japanese (ja)
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孝充 山本
正紘 西浦
恭伸 渡邉
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田中貴金属工業株式会社
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Priority to CN202280059213.4A priority Critical patent/CN117980526A/zh
Publication of WO2023037810A1 publication Critical patent/WO2023037810A1/fr

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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
    • 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
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/64—Record carriers characterised by the selection of the material comprising only the magnetic material without bonding agent
    • 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
    • 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

Definitions

  • the present invention relates to hard nitride-containing sputtering targets and methods of making them , in particular alloy phases containing Fe or Co and AlN, BN, Cr2N , Si3N4 , HfN, NbN, TaN, TiN, VN and their and a non-magnetic phase containing a hard nitride selected from any combination of: and a hard nitride-containing sputtering target and a method for producing the same.
  • a sputtering target containing an oxide as a non-magnetic material it is possible to reduce the generation of particles during film formation by creating a non-magnetic material particle-dispersed structure in which the oxide is uniformly and finely dispersed between the alloy phases. Confirmed.
  • the oxides and the raw material powders forming the alloy phases are mixed by vigorously stirring using a medium stirring mill such as a zirconia ball mill. (Japanese Patent No. 4673448, Japanese Patent No. 6728094).
  • a sputtering target containing a nitride instead of an oxide has also been proposed, but a method of strongly stirring and mixing using a zirconia ball mill as with the oxide is adopted (Patent No. 5913620, Patent No. 6526837) publication).
  • Japanese Patent No. 4673448 discloses a phase (A) in which non-magnetic oxide particles are uniformly finely dispersed, and a spherical alloy phase (B) having a diameter of 50 to 200 ⁇ m in the phase (A), Disclosed is a non-magnetic material particle-dispersed ferromagnetic material sputtering target having a composition in which Cr is concentrated by 25 mol% or more near the center of the spherical alloy phase (B), and the Cr content is lower toward the outer periphery than in the center.
  • metal powder with a maximum particle size of 20 ⁇ m or less and non-magnetic material powder with a maximum particle size of 5 ⁇ m or less are sealed together with zirconia balls in a ball mill pot with a capacity of 10 liters, and rotated for 20 hours for pulverization. and mixing this mixed powder with Co--Cr spherical powder with a diameter of 50 to 200 ⁇ m in a planetary mixer, followed by sintering.
  • Japanese Patent No. 6728094 discloses an invention in which a Co—Pt phase, a Co phase, and a non-magnetic material are contained, the Co—Pt alloy phase is refined, and the Co phase is coarsened, in order to suppress the generation of particles during sputtering.
  • the average particle size of the Co—Pt alloy phase is 0.1 ⁇ m or more and 7 ⁇ m or less
  • the average particle size of the Co phase is 30 ⁇ m or more and 300 ⁇ m or less
  • the average particle size of the oxide non-magnetic material is 0.05 ⁇ m.
  • the powder should be 2 ⁇ m or less, and that a Co—Pt alloy powder with a median diameter of 0.1 ⁇ m or more and 7 ⁇ m or less and a non-magnetic material powder with a median diameter of 0.05 ⁇ m or more and 2 ⁇ m or less be used as raw materials. Further, as a method for mixing raw material powders, it is described that the raw material powders are enclosed together with zirconia balls in a ball mill having a capacity of 10 liters and mixed by rotating for 20 hours.
  • Japanese Patent No. 6526837 discloses an Fe—Pt-based sputtering target and a Co—Pt-based sputtering target using cubic BN, which is less prone to cracks in BN particles than hexagonal BN, and raw material powders are disclosed. It is put into a medium stirring mill with a capacity of 5 L together with zirconia balls, and mixed by rotating (rotation speed 300 rpm) for 2 hours, and the median diameter (D50) of the raw material mixed powder becomes 0.3 ⁇ m or more and 20 ⁇ m or less, preferably 5 ⁇ m or less. It is described to grind up to
  • the present invention solves the above-mentioned conventional problems, prevents the occurrence of arcing during sputtering due to the inclusion of relatively coarse zirconia particles, and a hard nitride-containing sputtering target that can suppress the generation of particles during film formation. It aims at providing the manufacturing method.
  • the present inventors have found that arcing during sputtering of hard nitride-containing sputtering targets is caused by the inclusion of relatively coarse zirconia particles, which are commonly used when mixing raw material powders in the manufacturing process of sputtering targets.
  • the present inventors have completed the present invention based on the idea that arcing during sputtering can be suppressed by preventing the contamination of zirconia impurity particles derived from the zirconia ball mill that is used.
  • an alloy phase containing Fe or Co a non-magnetic phase comprising hard nitrides selected from AlN, BN, Cr2N , Si3N4 , HfN, NbN, TaN, TiN, VN and any combination thereof; Zr impurity concentration when measured as metal Zr is regulated to 1000 ppm or less,
  • a hard nitride-containing sputtering target is provided, characterized by having a Vickers hardness Hv of 200 or more and 600 or less measured under a load condition of 3 kgf.
  • the Zr impurity concentration is preferably regulated to 500 ppm or less.
  • the non-magnetic phase is An average particle diameter of 4 ⁇ m or more and 20 ⁇ m or less obtained by image analysis of an observation field of view of 180 ⁇ m ⁇ 180 ⁇ m in EPMA surface analysis at a magnification of 500; An average grain size of 2 ⁇ m or more and 20 ⁇ m or less obtained by image analysis of an observation field of view of 90 ⁇ m ⁇ 90 ⁇ m in EPMA surface analysis at a magnification of 1000; A diameter of 1 ⁇ m or more and 20 ⁇ m or less; It is preferable to satisfy at least one of
  • the content of the non-magnetic phase in the sputtering target is preferably 5 mol % or more and 50 mol % or less.
  • the non-magnetic phase may further include one or more selected from C, B2O3 and SiO2 .
  • the alloy phase can contain 0 mol% or more and 60 mol% or less of Pt.
  • the alloy phase may further contain one or more elements selected from Ag, Au, Cr, Cu, Ge, Ir, Ni, Pd, Rh, Ru and B.
  • a method for manufacturing the hard nitride-containing sputtering target is also provided.
  • the raw material powders constituting the alloy phase and the non-magnetic phase are mixed in a zirconia ball mill at a rotation speed of 50 rpm or more and 150 rpm or less for 2 hours or more and 6 hours or less to prepare a mixed powder. and sintering the mixed powder.
  • the raw material powder constituting the alloy phase is preferably metal powder of each raw material or Fe-based or Co-based atomized alloy powder.
  • the raw material powder constituting the non-magnetic phase preferably contains hard nitride powder having an average particle size D50 of 1 ⁇ m or more and 40 ⁇ m or less.
  • the hard nitride-containing sputtering target of the present invention prevents the contamination of relatively coarse zirconia impurity particles with high electrical resistivity, and regulates the Zr impurity concentration when measured as metal Zr to 1000 ppm or less. It is possible to suppress the occurrence of arcing inside and reduce particles derived from zirconia particles during film formation.
  • 4 is a graph showing the relationship between the Zr concentration and the number of particles in the sputtering targets of Examples and Comparative Examples. 4 is a graph showing the relationship between the Vickers hardness and the number of particles in the sputtering targets of Examples and Comparative Examples. SEM observation photograph of the structure of the sputtering target of Example 1 (magnification: 1000). SEM observation photograph of the structure of the sputtering target of Example 2 (magnification: 1000). SEM observation photograph of the structure of the sputtering target of Comparative Example 2 (magnification: 1000).
  • the hard nitride-containing sputtering targets of the present invention are selected from alloy phases containing Fe or Co and AlN, BN, Cr2N , Si3N4 , HfN, NbN, TaN, TiN, VN and any combination thereof. and a non-magnetic phase containing hard nitrides, and the Zr impurity concentration when measured as metal Zr is regulated to 1000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less, and measured under a load condition of 3 kgf.
  • Vickers hardness Hv is 200 or more and 600 or less, preferably 250 or more and 600 or less.
  • the present invention relates to a hard nitride-containing sputtering target containing hard nitride as non-magnetic material particles.
  • Hard nitrides include AlN, BN , Cr2N , Si3N4 , HfN, NbN, TaN, TiN, VN and any combination thereof.
  • the hardness (GPa) of each nitride is 12.0 for AlN, 15.4 for Cr2N , 19.4 for Si3N4 , 15.7 for HfN, 14.3 for NbN, and 23.3 for TaN. 7, TiN is 20.1, VN is 12.8, cubic BN is 46.1, and hexagonal BN is 2.0 (Databook High Melting Point Compound Handbook, Ceramics Processing Handbook: From Basics to Application Examples, Ceramic Hardness).
  • Cubic BN and hexagonal BN are known as BN used in sputtering targets, but in the present invention, cubic BN, which is said to be the second hardest after diamond, is used. In addition, as long as cubic BN is contained, hexagonal BN may be mixed.
  • the non-magnetic phase contains hard nitrides with an average grain size of 1 ⁇ m or more, preferably 2 ⁇ m or more and 20 ⁇ m or less.
  • the average grain size of the non-magnetic phase can be measured by image analysis of the results of EPMA surface analysis. Image analysis by EPMA surface analysis is performed in the following procedure.
  • the sputtering surface of the sputtering target is polished, and an elemental mapping image is obtained at a magnification of 100 using an EPMA apparatus.
  • the obtained elemental mapping image is binarized by the "surface processing" function attached to the EPMA apparatus.
  • the elemental mapping image for which binarization processing has been completed is analyzed with image analysis software (ImageJ 1.53e) to measure the average grain size of the nitride. If there is one element (for example, element A) other than N (nitrogen) that constitutes the nitride, the locations where both element N and element A are detected are calculated from the elemental mapping image.
  • the magnification is increased by one step in the order of 500, 1000, 3000, and 10000 until the value is greater than the criterion. Repeat the procedure to calculate the average particle size at each magnification.
  • the hard nitride-containing sputtering target of the present invention preferably satisfies at least one of the following (A) to (C).
  • A An average particle diameter of 3.6 ⁇ m or more and 20 ⁇ m or less, preferably 4 ⁇ m or more and 15 ⁇ m or less, obtained by image analysis of an observation field of view of 180 ⁇ m ⁇ 180 ⁇ m in EPMA surface analysis at a magnification of 500;
  • B An average particle size of 1.8 ⁇ m or more and 20 ⁇ m or less, preferably 1.8 ⁇ m or more and 4 ⁇ m or less, more preferably 1.8 ⁇ m or more and 3 .6 ⁇ m or less;
  • C An average particle size of 1 ⁇ m or more and 20 ⁇ m or less, preferably 1 ⁇ m or more and 2 ⁇ m or less, more preferably 1 ⁇ m or more and 1.8 ⁇ m or less, as determined by image analysis of an observation field of 30 ⁇ m ⁇ 30 ⁇ m in EPMA surface analysis at a magnification of 3000.
  • the content of the non-magnetic phase in the sputtering target varies depending on the physical properties required for the deposited layer formed using the sputtering target, but is generally preferably 5 mol % or more and 50 mol % or less, more preferably 5 mol. % or more and 45 mol % or less. If the content of the non-magnetic phase is within the above range, the magnetic properties of the deposited layer can be maintained satisfactorily. It can exhibit the function as an isolating grain boundary material.
  • the non-magnetic phase may further include one or more non-magnetic materials selected from C, B2O3 and SiO2 commonly used in sputtering targets.
  • the content of the optionally added non-magnetic material in the sputtering target is preferably 0 mol % or more and 25 mol % or less, more preferably 0 mol % or more and 20 mol % or less. If the content of the optionally added non-magnetic material is within the above range, the magnetic properties of the deposited layer can be maintained satisfactorily, and the magnetic material in the deposited layer can be finely dispersed between adjacent magnetic materials. It can exert its function as a grain boundary material that separates materials from each other.
  • the alloy phase contains Fe or Co, which are ferromagnetic materials. It may be contained as Fe alone, Co alone, an alloy of Fe and Co, an alloy of Fe and other elements, an alloy of Co and other elements, or an alloy of Fe, Co and other elements. Fe or Co is included as a main component of the sputtering target.
  • the Fe content in the alloy phase containing Fe but not Co is preferably 35 mol % or more and 100 mol % or less, more preferably 40 mol % or more and 100 mol % or less.
  • the Co content in the alloy phase is preferably 50 mol % or more and 100 mol % or less, more preferably 55 mol % or more and 100 mol % or less.
  • the total content of Fe and Co in the alloy phase is preferably 35 mol % or more and 100 mol % or less, more preferably 40 mol % or more and 100 mol % or less.
  • the total amount of Fe and Co in the alloy phase is preferably 50 mol% or more and 100 mol% or less, more preferably 60 mol% or more and 100 mol% or less, and the Fe content in the alloy phase is 30 mol% or more.
  • the content of Co in the alloy phase is preferably 70 mol % or less, more preferably 35 mol % or more and 65 mol % or less, and the Co content in the alloy phase is preferably 20 mol % or more and 50 mol % or less, and more preferably 25 mol % or more and 45 mol % or less.
  • the alloy phase preferably contains 0 mol% or more and 60 mol% or less of Pt, more preferably more than 0 mol% and 55 mol% or less.
  • the alloy phase can further contain one or more elements selected from Ag, Au, Cr, Cu, Ge, Ir, Ni, Pd, Rh, Ru and B.
  • the content of the optionally added element in the alloy phase is preferably 0 mol % or more and 30 mol % or less, more preferably 0 mol % or more and 25 mol % or less. If the content of the optionally added element in the alloy phase is within the above range, the magnetic properties of the deposited layer can be maintained satisfactorily.
  • Specific design compositions include Fe-51Pt-7Si 3 N 4 , Fe-40Pt-20AlN, Fe-39Pt-25TaN, Fe-38Pt-15Cr 2 N, Fe-35Pt-25VN, Fe-40Pt-20NbN, Fe -40Pt-20HfN, Fe-28Pt-30BN, Fe-35Pt-25TiN, Fe-41Pt-5Cu-5BN-8Si 3 N 4 , Fe-46Pt-3B 2 O 3 -8Si 3 N 4 , Fe-41Pt-4SiO 2 -10AlN-3Si 3 N 4 , Fe-21Pt-21Co-10C-20AlN, Fe-30Pt-5C-30AlN, Fe-30Pt-5Ag-6C-11BN-20AlN, Fe-32Pt-6B-6Rh-20HfN, Fe- 34Pt-3Ge-5C-20TiN, Co-23Pt-7Si 3 N 4 , Co-20Pt-19AlN, Co-19Pt-25TaN,
  • the design composition of the sputtering target of the present invention may overlap with the composition of known sputtering targets, but the Zr concentration when measured as metal Zr is 1000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less. It differs from known sputtering targets in that the The Zr impurity in the sputtering target of the present invention is controlled in the production process so that the content is below the regulation value, unlike the unavoidable impurities in the composition of known sputtering targets. As shown in Examples and Comparative Examples to be described later, it was confirmed that even with sputtering targets having the same design composition, when the Zr concentration was restricted to 1000 ppm or less, the generation of particles was remarkably suppressed.
  • the sputtering target of the present invention is also characterized by having a Vickers hardness Hv of 200 or more and 600 or less, preferably 250 or more and 600 or less, measured under a load condition of 3 kgf. It was thought that the higher the Vickers hardness, the more particles were generated. It was confirmed that when Hv is 200 or more and 600 or less, particle generation is significantly suppressed.
  • raw material powders constituting the alloy phase and the non-magnetic phase are mixed using a zirconia ball mill at a rotation speed of 50 rpm to 150 rpm for 2 hours to 6 hours. It can be manufactured by a method comprising preparing a powder and sintering the mixed powder.
  • the raw material powder is stirred and mixed using a zirconia ball mill at a rotation speed of 50 rpm to 150 rpm, preferably 50 rpm to 100 rpm, more preferably 50 rpm to 75 rpm for 2 hours to 6 hours, It is preferably 3 hours or more and 5 hours or less.
  • Stirring and mixing using a zirconia ball mill is generally performed by rotating the mill at high speed to cause the zirconia balls to collide with the raw material powder at high speed, and grinding the raw material powder between the zirconia balls for a long period of time.
  • a homogeneous powder mixture is formed by applying strong mechanical energy to the powder to crush it and kneading the finely divided raw material powder.
  • the present inventors have found that when the raw material powder contains hard particles, the zirconia balls are worn and a trace amount of zirconia is mixed as an impurity.
  • We found the optimum mixing conditions to suppress the In the present invention by suppressing the rotation speed to a low speed and relatively gently colliding and stirring the time relatively short, even if the raw material powder contains hard nitride particles, wear of the zirconia balls is prevented. It was found that contamination of zirconia into the mixture can be suppressed.
  • the raw material powder that constitutes the alloy phase can be metal powder or Fe-based or Co-based atomized alloy powder.
  • the Fe powder a powder having an average particle diameter D50 of 1 ⁇ m or more and 10 ⁇ m or less, preferably 2 ⁇ m or more and 8 ⁇ m or less can be used. If the average particle size is too small, there is a risk of ignition and the concentration of unavoidable impurities may increase.
  • Co powder having an average particle diameter D50 of 1 ⁇ m or more and 10 ⁇ m or less, preferably 2 ⁇ m or more and 8 ⁇ m or less can be used. If the average particle size is too small, there is a risk of ignition and the concentration of unavoidable impurities may increase.
  • a powder having an average particle diameter D50 of 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 0.3 ⁇ m or more and 6 ⁇ m or less can be used. If the average particle size is too small, the concentration of unavoidable impurities may increase, and if the average particle size is too large, the non-magnetic material particles may not be uniformly dispersed.
  • a powder having an average particle size D50 of 0.1 ⁇ m or more and 30 ⁇ m or less, preferably 0.5 ⁇ m or more and 20 ⁇ m or less can be used. If the average particle size is too small, the concentration of unavoidable impurities may increase, and if the average particle size is too large, uniform dispersion may not be possible.
  • an atomized alloy powder having an average particle size D50 of 1 ⁇ m or more and 10 ⁇ m or less, preferably 2 ⁇ m or more and 8 ⁇ m or less can be used. If the average particle size is too small, the concentration of unavoidable impurities may increase, and if the average particle size is too large, the non-magnetic material particles may not be uniformly dispersed.
  • the raw material powder constituting the non-magnetic phase contains hard nitride powder having an average particle size D50 of 1 ⁇ m or more and 40 ⁇ m or less, preferably 2 ⁇ m or more and 35 ⁇ m or less.
  • hard nitride powders AlN , BN, Cr2N , Si3N4 , HfN, NbN, TaN, TiN, VN and any combination thereof are used. Cubic BN is used as BN. If the average particle size of the hard nitride powder is within the above range, a good dispersion state can be achieved.
  • the raw material powder constituting the non-magnetic phase further contains one or more non-magnetic materials selected from C, B 2 O 3 and SiO 2 having an average particle size D50 of 1 ⁇ m or more and 10 ⁇ m or less, preferably 1 ⁇ m or more and 8 ⁇ m or less. be able to. If the average particle size of the additional non-magnetic material powder is within the above range, a good dispersion state can be achieved.
  • the sintering conditions for the mixed powder are preferably a sintering temperature of 800°C to 1300°C, preferably 900°C to 1250°C, and a sintering pressure of 30 MPa to 120 MPa, preferably 50 MPa to 100 MPa.
  • the obtained elemental mapping image is binarized with the "surface processing" function attached to the EPMA device (JXA-8500F). Specifically, the elemental mapping image is displayed with the maximum number of maps being 9, an image to be binarized is selected, and the upper and lower limits are confirmed on the "change level” screen. Select “Constant subtraction” on the “Map calculation” screen, enter the lower limit value confirmed on the "Level change” screen in K and execute. Again, select “Constant division” on the “Map calculation” screen, and enter the value obtained by subtracting the lower limit value from the upper limit value confirmed on the "Level change” screen in K and execute. Change the "display mode” selection screen to the contents of Table 5 and execute. Change the contents of the "level change” screen to those shown in Table 6 and execute.
  • the obtained elemental mapping image in PNG format is analyzed with image analysis software (ImageJ 1.53e) to measure the average grain size of the nitride. Specifically, the average grain size of the nitride is measured by the following procedure. Open the elemental mapping image in PNG format with image analysis software (ImageJ 1.53e).
  • image analysis software imageJ 1.53e
  • the nitride is composed of the elements A and N (nitrogen)
  • the regions of the mapping images of the elements A and N are copied with 286 ⁇ 286 pixels and saved as New Image.
  • ImageJ 1.53e the Image Calculator of the image analysis software
  • mapping images other than the element N constituting the nitride are selected for Image 1 and Image 2, and all mapping images other than the element N constituting the nitride are synthesized with the Image Calculator. Enter the contents of the Image Calculator in Table 7 except for selecting that image as Image 1 of the Image Calculator in Table 7, and execute it, and check the locations where both the element N and the element other than N constituting the nitride are detected. Create a calculated file.
  • the above series of analyzes are performed with an image magnified 100 times, and if the average particle size obtained is below the criteria for each magnification shown in Table 11, 500 times, 1000 times, and 3000 times until the value is greater than the criteria. , 10,000 times, and so on.
  • the sintered body is processed to have a diameter of 153 mm and a thickness of 2 mm, and is bonded to a Cu backing plate having a diameter of 161 mm and a thickness of 4 mm with indium to obtain a sputtering target.
  • This sputtering target is attached to a magnetron sputtering apparatus, and after sputtering for 40 seconds in an Ar gas atmosphere with an output of 500 W and a gas pressure of 1 Pa, the number of particles adhering to the substrate is measured with a particle counter.
  • Examples 1 to 26 and Comparative Examples 1 to 15 Sputtering targets having the design compositions shown in Tables 12 and 13 were produced, and the Zr concentration, Vickers hardness, average grain size of the hard nitride non-magnetic phase, relative density and number of particles were measured.
  • Fe or Co constitutes the balance, so the contents are omitted.
  • Fe-51Pt-7Si 3 N 4 in Example 1 means 42Fe-51Pt-7Si 3 N 4 .
  • Fe powder with an average particle size D50 of 7 ⁇ m, Co powder with an average particle size D50 of 3 ⁇ m, and Pt powder with an average particle size D50 of 1 ⁇ m were used.
  • Cu powder with an average particle size D50 of 5 ⁇ m, Ag powder with an average particle size D50 of 4 ⁇ m, B powder with an average particle size D50 of 8 ⁇ m, Ge powder with an average particle size D50 of 10 ⁇ m, and average grains Cr powder with a diameter D50 of 15 ⁇ m, Ru powder with an average particle diameter D50 of 13 ⁇ m, and Rh powder with an average particle diameter D50 of 13 ⁇ m were used.
  • hexagonal BN powder (BN) with an average particle size D50 of 5 ⁇ m, B 2 O 3 powder with an average particle size D50 of 5 ⁇ m, C powder with an average particle size D50 of 5 ⁇ m, and average particle size D50 SiO2 powder with 1 ⁇ m was used.
  • each raw material powder weighed so as to have the design composition shown in Table 12 was put into a stirring mill together with 4 kg of zirconia balls, and stirred and mixed at a rotation speed of 100 rpm for 4 hours.
  • the mixed powder was sintered at the sintering temperature shown in Table 12 at a sintering pressure of 66 MPa. Blank columns in Table 12 indicate no addition.
  • each raw material powder weighed so as to have the design composition shown in Table 13 was put into a stirring mill together with 4 kg of zirconia balls, and stirred and mixed under the stirring conditions shown in Table 13.
  • the mixed powder was sintered at the sintering temperature shown in Table 13 at a sintering pressure of 66 MPa. Blank columns in Table 13 indicate no addition.
  • FIG. 1 shows the relationship between the Zr concentration and the number of particles
  • FIG. 2 shows the relationship between the Vickers hardness and the number of particles.
  • the number of particles when the Zr concentration is 2000 ppm or more, the number of particles is as large as 2000 or more, but when the Zr concentration is 1000 ppm or less, the number of particles is small, especially when the Zr concentration is 300 ppm or less, the number of particles is less than 400. I know it's less. Also, from Tables 14 to 15 and FIG. 2, it can be seen that the number of particles is as large as 2000 or more when the Vickers hardness Hv is 600 or more, but the number of particles is less than 400 when the Vickers hardness Hv is in the range of 200 to 600.
  • the average particle size of the hard nitride particles of the sputtering targets of Examples 1 to 26 could be measured at a magnification of 500 to 3000, but the average particle size of the hard nitride particles of the sputtering targets of Comparative Examples 1 to 15 was measured. Measurements required up to 10,000 magnification. From Tables 14 and 15, the average particle size of the hard nitrides of Examples 1 to 26 is in the range of 1.3 ⁇ m to 12.8 ⁇ m, and the average particle size of the hard nitrides of Comparative Examples 1 to 15 is 0.3 to 0.3 ⁇ m. It can be seen that the particles are fine particles in the range of 0.9 ⁇ m.
  • FIG. 3 is an SEM observation photograph (1000 magnification) of the structure of the sputtering target of Example 1
  • FIG. 4 is an SEM observation photograph (1000 magnification) of the structure of the sputtering target of Example 2
  • FIG. It is an SEM observation photograph (1000 magnification) of a tissue.
  • EPMA analysis confirms that black particles are hard nitride particles and white to gray are alloy phases. Comparing FIGS. 3 and 5, it can be seen that in Comparative Example 2 (FIG. 5), white alloy phases and black particles are more finely dispersed than in Example 1 (FIG. 3). From FIG. 4, it can be seen that the relatively large hard nitride particles and the alloy phase are homogeneously dispersed.
  • the sputtering targets manufactured by the manufacturing method of the present invention have relatively larger hard nitride particles than the sputtering targets of the comparative examples manufactured by the conventional method, but the non-magnetic phase and the alloy phase are homogeneously dispersed.

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  • Thin Magnetic Films (AREA)

Abstract

L'invention concerne : une cible de pulvérisation contenant du nitrure dur qui permet d'empêcher l'apparition d'un arc pendant la pulvérisation cathodique, provoquée par une inclusion de particules de zircone relativement alignées, et qui permet de supprimer la génération de particules pendant une formation de film ; et un procédé de production associé.　La cible de pulvérisation cathodique contenant du nitrure dur : comprend une phase d'alliage comprenant du Fe ou du Co et une phase non magnétique comprenant un nitrure dur choisi parmi AlN, BN, Cr2N, Si3N4, HfN, NbN, TaN, TiN, VN ou une quelconque combinaison de ces derniers ; et est caractérisée en ce qu'elle présente une concentration en impuretés de Zr, lorsque mesurée en tant que Zr métallique, qui est limitée à 1 000 ppm au plus et une dureté Vickers Hv s'inscrivant dans une plage de 200 à 600 lorsque mesurée sous une charge de 3 kgf.
PCT/JP2022/030289 2021-09-08 2022-08-08 Cible de pulvérisation contenant du nitrure dur WO2023037810A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008081841A1 (fr) * 2007-01-04 2008-07-10 Mitsui Mining & Smelting Co., Ltd. Cible de pulvérisation à base de cocrpt et son procédé de fabrication
JP2011208169A (ja) * 2010-03-28 2011-10-20 Mitsubishi Materials Corp 磁気記録膜形成用スパッタリングターゲットおよびその製造方法
JP2013194299A (ja) * 2012-03-21 2013-09-30 Kobelco Kaken:Kk 酸化物焼結体およびスパッタリングターゲット、並びにその製造方法
WO2014185266A1 (fr) * 2013-05-13 2014-11-20 Jx日鉱日石金属株式会社 Cible de pulvérisation utilisable en vue de la formation d'un film magnétique mince
WO2016140113A1 (fr) * 2015-03-04 2016-09-09 Ｊｘ金属株式会社 Cible de pulvérisation à base de matériau magnétique et son procédé de fabrication
WO2018047978A1 (fr) * 2016-09-12 2018-03-15 Ｊｘ金属株式会社 Cible de pulvérisation cathodique en matériau ferromagnétique
JP2019073798A (ja) * 2017-10-11 2019-05-16 三菱マテリアル株式会社 Ｚｎ−Ｂｉ含有酸化物スパッタリングターゲット、Ｚｎ−Ｂｉ含有酸化物スパッタリングターゲットの製造方法、及び、赤外光学用薄膜の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008081841A1 (fr) * 2007-01-04 2008-07-10 Mitsui Mining & Smelting Co., Ltd. Cible de pulvérisation à base de cocrpt et son procédé de fabrication
JP2011208169A (ja) * 2010-03-28 2011-10-20 Mitsubishi Materials Corp 磁気記録膜形成用スパッタリングターゲットおよびその製造方法
JP2013194299A (ja) * 2012-03-21 2013-09-30 Kobelco Kaken:Kk 酸化物焼結体およびスパッタリングターゲット、並びにその製造方法
WO2014185266A1 (fr) * 2013-05-13 2014-11-20 Jx日鉱日石金属株式会社 Cible de pulvérisation utilisable en vue de la formation d'un film magnétique mince
WO2016140113A1 (fr) * 2015-03-04 2016-09-09 Ｊｘ金属株式会社 Cible de pulvérisation à base de matériau magnétique et son procédé de fabrication
WO2018047978A1 (fr) * 2016-09-12 2018-03-15 Ｊｘ金属株式会社 Cible de pulvérisation cathodique en matériau ferromagnétique
JP2019073798A (ja) * 2017-10-11 2019-05-16 三菱マテリアル株式会社 Ｚｎ−Ｂｉ含有酸化物スパッタリングターゲット、Ｚｎ−Ｂｉ含有酸化物スパッタリングターゲットの製造方法、及び、赤外光学用薄膜の製造方法

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