WO2014125897A1 - PULVÉRISATION DE CIBLE CONTENANT DU Co OU DU Fe - Google Patents

PULVÉRISATION DE CIBLE CONTENANT DU Co OU DU Fe Download PDF

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WO2014125897A1
WO2014125897A1 PCT/JP2014/051494 JP2014051494W WO2014125897A1 WO 2014125897 A1 WO2014125897 A1 WO 2014125897A1 JP 2014051494 W JP2014051494 W JP 2014051494W WO 2014125897 A1 WO2014125897 A1 WO 2014125897A1
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particles
diameter
powder
metal
target
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PCT/JP2014/051494
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English (en)
Japanese (ja)
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荒川　篤俊
英生 高見
中村　祐一郎
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Jx日鉱日石金属株式会社
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Priority to JP2015500172A priority Critical patent/JP6332869B2/ja
Priority to SG11201503676WA priority patent/SG11201503676WA/en
Priority to CN201480003726.9A priority patent/CN104903488B/zh
Publication of WO2014125897A1 publication Critical patent/WO2014125897A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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

Definitions

  • the present invention relates to a magnetic material sputtering target used to form a magnetic thin film of a magnetic recording medium, in particular, a granular film in a magnetic recording medium of a hard disk adopting a perpendicular magnetic recording method, and causes the generation of particles during sputtering.
  • the present invention relates to a non-magnetic material particle-dispersed magnetic material sputtering target containing Co or Fe as a main component, which can suppress abnormal discharge of the non-magnetic material.
  • a material based on Co, Fe, and Ni, which are ferromagnetic metals, is used for a recording layer of a hard disk that employs a perpendicular magnetic recording system.
  • composite materials composed of a ferromagnetic alloy such as Co—Cr, Co—Pt, Co—Cr—Pt, Fe—Pt, and the like, which are mainly composed of Co and Fe, and a nonmagnetic inorganic material are often used.
  • the magnetic thin film of such a magnetic recording medium such as a hard disk is often produced by sputtering a ferromagnetic material sputtering target containing the above material as a component because of its high productivity.
  • a melting method or a powder metallurgy method can be considered as a method for producing such a sputtering target for a magnetic recording medium. Which method is used depends on the required characteristics, so it cannot be generally stated, but the sputtering target made of a ferromagnetic alloy and non-magnetic inorganic particles used for the recording layer of a perpendicular magnetic recording hard disk is Generally, it is produced by a powder metallurgy method. This is because the inorganic particles need to be uniformly dispersed in the alloy substrate, and thus it is difficult to produce by the melting method.
  • Patent Document 1 As a powder metallurgy method, for example, in Patent Document 1, mixed powder obtained by mixing Co powder, Cr powder, TiO 2 powder, and SiO 2 powder and Co spherical powder are mixed by a planetary motion mixer, and this mixing is performed.
  • Patent Document 2 proposes a method of forming a powder by hot pressing to obtain a sputtering target for a magnetic recording medium. It can be seen that the target structure in this case has a spherical phase (B) in the phase (A) which is a metal substrate in which inorganic particles are uniformly dispersed (see FIG. 1 of Patent Document 2).
  • Such a structure is good in terms of improving leakage magnetic flux, but cannot be said to be a suitable sputtering target for a magnetic recording medium from the viewpoint of suppressing generation of particles during sputtering.
  • Patent Document 2 discloses a sputtering target for forming a magnetic recording medium thin film by mixing Co—Cr binary alloy powder, Pt powder, and SiO 2 powder and hot-pressing the obtained mixed powder. A method has been proposed. Although the target structure in this case is not shown in the figure, a Pt phase, a SiO 2 phase, and a Co—Cr binary alloy phase can be seen, and a diffusion layer can be observed around the Co—Cr binary alloy phase. It is described. Such a structure is not a suitable sputtering target for magnetic recording media.
  • Patent Document 3 proposes a sputtering target composed of a matrix phase of Co and Pt and a metal oxide phase having an average particle size of 0.05 ⁇ m or more and less than 7.0 ⁇ m, which suppresses the growth of crystal grains, Proposals have been made to increase the film formation efficiency by obtaining a magnetic permeability and high density target.
  • Patent Document 4 discloses that the average particle diameter of the particles formed by the oxide phase is 3 ⁇ m or less
  • Patent Document 5 discloses that the silica particles or titania particles are in a cross section perpendicular to the main surface of the sputtering target.
  • the non-magnetic material such as SiO 2 , Cr 2 O 3 , or TiO 2 contained is an insulator, so abnormal discharge It is the cause. Due to this abnormal discharge, generation of particles during sputtering becomes a problem.
  • an object of the present invention is to suppress abnormal discharge of the nonmagnetic material while maintaining a high PTF, and to reduce the generation of particles during sputtering caused by abnormal discharge.
  • the probability of abnormal discharge has been reduced by reducing the particle size of the non-magnetic material particles.
  • the allowable particle level has become stricter.
  • An object of the present invention is to provide a non-magnetic material particle-dispersed ferromagnetic material sputtering target that is further improved.
  • the present inventors have conducted intensive research. As a result, by adjusting the structure of the target (non-magnetic material particles) structure, abnormal discharge due to the non-magnetic material during sputtering does not occur, It has been found that a target with less generation of particles can be obtained.
  • a sintered sputtering target made of a material in which non-magnetic material particles are dispersed in a magnetic material containing Co or Fe,
  • the structure observed on the polished surface in the target is composed of nonmagnetic material particles having an average particle size of 1.8 ⁇ m or less, and a metal phase and metal particles containing Co or Fe in which the nonmagnetic material particles are dispersed,
  • the maximum value of the distance between any two points on the outer periphery of the non-magnetic material particle is the maximum diameter
  • the minimum value of the distance between the two lines when the particle is sandwiched between two parallel straight lines is the minimum diameter.
  • the nonmagnetic material particles having a difference between the maximum diameter and the minimum diameter of 0.7 ⁇ m or less account for 60% or more of the nonmagnetic material particles in the structure observed on the polished surface in the target,
  • the maximum value of the distance between any two points on the outer periphery of the metal grain is the maximum diameter
  • the minimum value of the distance between the two straight lines when the metal grain is sandwiched between two parallel straight lines is the minimum diameter.
  • an average of one or more metal particles having a maximum diameter and a minimum diameter of 30 ⁇ m or more are present in a 1 mm 2 field of view.
  • the non-magnetic material particles are B 2 O 3 , CoO, Co 3 O 4 , MnO, Mn 3 O 4 , SiO 2 , SnO 2 , TiO 2 , Ti 2 O 3 , Cr 2 O 3 , Ta 2 O. 5.
  • the sputtering target according to 1) above which is one or more oxides selected from WO 2 , WO 3 , and ZrO 2 , and contains 0.5 to 20 mol% of these.
  • the non-magnetic material particle dispersion type magnetic material sputtering target of the present invention thus adjusted maintains a high PTF, does not cause abnormal discharge due to the non-magnetic material during sputtering, and provides a target with less generation of particles. . Thereby, it has the outstanding effect that the cost improvement effect by a yield improvement can be acquired.
  • FIG. 1 is a diagram (photograph) showing a Co—Pt—Cr—SiO 2 —TiO 2 —Cr 2 O 3 target structure of Example 1.
  • FIG. It is a figure (enlarged photograph of FIG. 1) which shows the structure
  • FIG. 3 is a view obtained by performing image analysis processing (binarization processing) on FIG. 2 in order to clarify the outline of nonmagnetic material particles.
  • 4 is a diagram (photograph) showing a Co—Pt—Ru—Ta—SiO 2 —TiO 2 —CoO—B 2 O 3 target structure of Example 2.
  • FIG. It is a figure (enlarged photograph of FIG. 4) which shows the structure
  • the sputtering target of the present invention is a sintered sputtering target made of a material in which non-magnetic material particles are dispersed in a magnetic material containing Co or Fe, and the structure observed on the polished surface of the target is an average grain.
  • Non-magnetic material particles having a diameter of 1.8 ⁇ m or less, a metal phase containing Co or Fe in which the non-magnetic material particles are dispersed, and metal particles are included. It is because generation
  • the inventors of the present application have previously found that it is desirable that the shape of the non-magnetic material particles is a perfect sphere, and that at least a shape close to that is an effective means for preventing the generation of particles (Patent Document) 6).
  • Patent Document 6 In other words, in order to improve the magnetic properties, a certain amount of oxide (non-magnetic material) needs to be present, but if it is irregularly shaped, the location of the oxide in a certain area of the target surface A difference occurs in the distribution in a place where no oxide is present, and segregation is likely to occur. As long as it is a true sphere or an oxide particle close to a true sphere, segregation is reduced because the shape of the particles is uniform, and it has been found that particle generation can be effectively suppressed.
  • the maximum value of the distance between any two points on the outer periphery of the non-magnetic material particles observed on the polished surface in the target is the maximum diameter
  • the particles are represented by two parallel straight lines
  • the minimum value of the distance between the two straight lines when the gap is sandwiched is the minimum diameter
  • the difference between the maximum diameter and the minimum diameter is 0.7 ⁇ m or less.
  • the present invention has found further new findings in the above knowledge, and not only the form of the non-magnetic material particles but also the form of the metal particles containing Co or Fe can be used to suppress abnormal discharge and further increase the generation of particles. It can be greatly suppressed. That is, the maximum value of the distance between any two points on the outer periphery of the metal grain observed on the polished surface in the target is the maximum diameter, and the distance between the two straight lines when the metal grain is sandwiched between two parallel straight lines the minimum value when the smallest diameter the distance, its average maximum diameter and the minimum diameter of the sum 30 ⁇ m or more metal grains in 1 mm 2 field of view one or more, and preferably an average of 3 or more, more preferably an average 5 It is characterized by the presence of more than one.
  • any five locations within the target surface are observed with a microscope, and the number of metal particles whose sum of the maximum diameter and the minimum diameter within a 1 mm 2 visual field at each location is 30 ⁇ m or more is counted. The average number is obtained from the total.
  • the maximum value of the distance between any two points on the outer periphery of the metal particle is the maximum diameter
  • the minimum value of the distance between the two lines when the metal particle is sandwiched between two parallel lines is the minimum diameter
  • the sum of the maximum diameter and the minimum diameter is 30 ⁇ m or more and there is an average of 1 or more in a 1 mm 2 field of view
  • the leakage magnetic flux increases.
  • the promotion of ionization of the inert gas proceeds efficiently, and a stable discharge can be obtained.
  • the maximum value of the distance between any two points on the outer periphery of the metal grain is the maximum diameter
  • the minimum value of the distance between the two lines when the metal grain is sandwiched between two parallel straight lines is the minimum diameter.
  • the sum of the maximum diameter and the minimum diameter is smaller than 30 ⁇ m, or when the presence of metal particles of 30 ⁇ m or more is less than 1 on average within 1 mm 2 field of view, the above effect is hardly obtained.
  • the sum of the maximum diameter and the minimum diameter is 50 ⁇ m or more, the above effect appears even more strongly.
  • the sum of the maximum diameter and the minimum diameter exceeds 300 ⁇ m, the distribution of the oxide particles is biased. May occur.
  • the ferromagnetic material sputtering target of the present invention is particularly effective for Co-based alloys such as Co-Cr based alloys, Co-Pt based alloys, Co-Cr-Pt based alloys or Fe based alloys such as Fe-Pt based alloys.
  • the present invention can be applied to already known ferromagnetic materials, and the mixing ratio of components required as a magnetic recording medium can be appropriately adjusted according to the purpose.
  • the Co-based alloy a sputtering target in which Cr is 0 mol% or more and 15 mol% or less, Pt is 5 mol% or more and 30 mol% or less, and the balance is made of Co and unavoidable impurities except for a nonmagnetic material.
  • Fe-based alloy a sputtering target in which Pt is more than 0 mol% and not more than 60 mol%, and the remainder is made of Fe and inevitable impurities except for a nonmagnetic material can be used.
  • These component compositions show a suitable numerical range for utilizing the characteristics as a ferromagnetic material, and needless to say, they can be applied to other numerical values.
  • Nonmagnetic materials to be added to the ferromagnetic material are B 2 O 3 , CoO, Co 3 O 4 , MnO, Mn 2 O 3 , SiO 2 , TiO 2 , Ti 2 O 3 , Cr 2 O 3 , Ta 2.
  • One or more oxides selected from O 5 , WO 2 , WO 3 , and ZrO 2 , and usually 0.5 to 20 mol% of these are contained in the target. These oxides can be arbitrarily selected and added according to the type of ferromagnetic film required. The said addition amount is an effective amount for exhibiting the effect of addition.
  • 0.5 to 12 mol% of one or more elements selected from Mg, Al, Si, Mn, Nb, Mo, Ru, Pd, Ta, W, and B may be added. It can. These are elements added as necessary in order to improve the characteristics as a magnetic recording medium.
  • the said addition amount is an effective amount for exhibiting the effect of addition.
  • the structure of the sputtering target of the present invention is composed of non-magnetic material particles and a metal phase and metal particles containing Co or Fe in which the non-magnetic material particles are dispersed, and the metal particles are composed of Co or Fe. Is preferred.
  • the metal grains have a maximum magnetic permeability higher than that of metal bases having different compositions (metal phases in which non-magnetic material particles are dispersed), and have a structure in which the metal grains are separated from each other by surrounding structures made of the metal base.
  • the reason why the leakage magnetic field improves is not necessarily clear at the present time, but a dense part and a sparse part are generated in the magnetic flux inside the target, compared with a structure having a uniform magnetic permeability. This is because the magnetostatic energy increases, and it is considered that it is advantageous in terms of energy to leak the magnetic flux outside the target.
  • the sputtering target of the present invention can be produced by powder metallurgy.
  • powder metallurgy metal raw material powders such as Co, Cr, Pt and Fe, non-magnetic material raw material powders such as SiO 2 and, if necessary, additive metal powders such as Ru are prepared, except for metal coarse powder described later.
  • the particle size of the raw material it is desirable to use metal powder having an average particle diameter of 10 ⁇ m or less and non-magnetic material powder of 5 ⁇ m or less.
  • the non-magnetic material raw powder is more likely to be as spherical as possible to achieve the microstructure of the present invention.
  • the particle size of the powder can be measured with a laser diffraction particle size distribution analyzer (HORIBA LA-920).
  • these metal powders and alloy powders are weighed so as to have a desired composition, and mixed by pulverization using a known method such as a ball mill.
  • a ball mill In order to shorten the mixing time and increase the productivity, it is preferable to use a high energy ball mill.
  • the metal raw material powder it is preferable to mix a small amount of at least one component metal coarse powder having a particle size in the range of 50 ⁇ m to 300 ⁇ m.
  • the metal particles become flat and the difference between the major axis and the minor axis increases.
  • the metal particles can be spherical or flat (strip-shaped), but each of the spherical or flat metal particles has advantages and disadvantages depending on the shape. It is desirable to select this shape according to the intended use of the target. Specifically, when the target material is produced by the sintering method in the spherical shape, holes are less likely to be generated at the interface between the metal substrate (A) and the phase (B), and the target density can be increased. In addition, since the spherical surface area is smaller in the same volume, the diffusion of the metal element is less likely to proceed between the metal substrate (A) and the phase (B) when the target material is sintered.
  • the spherical shape here represents a solid shape including a true sphere, a pseudo-true sphere, an oblate (spheroid), and an artificial oblate. In either case, the difference between the major axis and the minor axis is 0 to 50%.
  • the metal particles when the metal particles are made flat, it has the effect of preventing the metal particles from detaching from the surrounding metal substrate (A) at the time of sputtering due to the wedge effect. Further, by destroying the spherical shape, it is possible to reduce the bias of the erosion speed that is likely to occur in the spherical shape, and it is possible to suppress the generation of particles due to the boundary having different erosion speeds.
  • the maximum value of the distance between any two points on the outer periphery of the nonmagnetic material particles in the structure observed on the polished surface in the target is the maximum diameter, and is parallel.
  • the minimum value of the distance between two straight lines when the same particle is sandwiched between two straight lines is defined as the minimum diameter
  • the difference between the maximum diameter and the minimum diameter is 0.7 ⁇ m or less.
  • the maximum diameter and the minimum diameter are calculated by projecting a microscope image of the polished surface in the target on a PC and using image processing analysis software.
  • image processing analysis software Keyence Corporation shape analysis software (VK-Analyzer VK-H1A1) was used.
  • the mixed powder obtained as described above is sintered using a hot press or a hot isostatic press.
  • a hot press or a hot isostatic press find the conditions for non-magnetic material particles to become spherical and the conditions for metal particles to be flat by setting the mixing conditions and sintering conditions for the above raw materials, and fix the manufacturing conditions.
  • a sintered body target in which such non-magnetic material particles and metal particles are always dispersed can be obtained.
  • Example 1 As the metal raw material powder, Co powder having an average particle diameter of 4 ⁇ m, Cr powder having an average particle diameter of 5 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, and TiO 2 powder having an average particle diameter of 1.2 ⁇ m as the nonmagnetic material powder, an average particle diameter of 0 A spherical SiO 2 powder having a thickness of 7 ⁇ m and a Cr 2 O 3 powder having an average particle diameter of 1 ⁇ m were prepared. Moreover, Co coarse powder adjusted so that a particle size might be in the range of 50 micrometers or more and 150 micrometers or less was prepared, and the ratio of Co powder with an average particle diameter of 4 micrometers and the said Co coarse powder was set to 7: 3 by weight ratio. These powders were weighed 2000 g with the following composition ratio. Composition: 69Co-18Pt-2Cr-5SiO 2 -2TiO 2 -4Cr 2 O 3 (mol%)
  • the Co coarse powder was removed, and the weighed powder was enclosed in a ball mill pot with a capacity of 10 liters together with a tungsten alloy ball as a grinding medium, and rotated and mixed for 120 hours. Thereafter, Co coarse powder was additionally added to the ball mill pot and mixed for 1 hour.
  • the mixed powder thus obtained was filled in a carbon mold and hot-pressed in a vacuum atmosphere under conditions of a temperature of 1100 ° C., a holding time of 2 hours, and a pressure of 30 MPa to obtain a sintered body. . Further, this was cut with a lathe to obtain a disk-shaped target having a diameter of 180 mm and a thickness of 5 mm.
  • the average leakage magnetic flux density of the target As a result of measuring the average leakage magnetic flux density of the target thus obtained, it was 30%.
  • the measurement of leakage magnetic flux was carried out in accordance with ASTM F2086-01 (Standard Test Method for Pass Flow Through Flux of Crystal Circular Magnetic Sputtering Targets, Method 2). Specifically, the magnetic flux leakage density measured by fixing the center of the target and rotating it at 0 degrees, 30 degrees, 60 degrees, 90 degrees, and 120 degrees is divided by the value of the reference field defined by ASTM. , Multiplied by 100 and expressed as a percentage. And the result averaged about these 5 points
  • FIG. 2 shows an enlarged view of FIG. 1 in order to observe the non-magnetic material particles.
  • the maximum value of the distance between any two points on the outer periphery of the nonmagnetic material particle is the maximum diameter
  • the minimum value of the distance between the two lines when the particle is sandwiched between two parallel lines is the minimum diameter.
  • 85% of the oxide particles having a difference between the maximum diameter and the minimum diameter of 0.7 ⁇ m or less were present in the microscopic field, and the average particle diameter was 0.75 ⁇ m.
  • a microscopic image is projected on a PC screen, and image analysis processing (binarization processing) is performed. These were calculated after clarifying the outline of the particle (black part).
  • this target was attached to a DC magnetron sputtering apparatus, and sputtering was performed.
  • the sputtering conditions were a sputtering power of 1.2 kW, an Ar gas pressure of 1.5 Pa, and after performing 2 kWhr pre-sputtering, sputtering was performed on a 4-inch diameter silicon substrate with a target film thickness of 1000 nm.
  • the number of particles adhering to the substrate was measured with a particle counter. At this time, the number of particles on the silicon substrate was four. Even when sputtering is not performed, the number of particles on the silicon substrate may be counted as 0 to 5 when measured with a particle counter. Therefore, it can be said that the number of particles in this embodiment is at an extremely small level. .
  • a powder, a spherical SiO 2 powder having an average particle size of 0.7 ⁇ m, a CoO powder having an average particle size of 0.8 ⁇ m, and a B 2 O 3 powder having an average particle size of 5 ⁇ m were prepared.
  • Co coarse powder adjusted to have a particle size in the range of 50 ⁇ m to 300 ⁇ m was prepared, and the ratio of Co powder having an average particle size of 4 ⁇ m to the Co coarse powder was set to 7: 3 by weight. These powders were weighed 2000 g with the following composition ratio.
  • the Co coarse powder was removed, and the weighed powder was enclosed in a ball mill pot with a capacity of 10 liters together with a tungsten alloy ball as a grinding medium, and rotated and mixed for 120 hours. Thereafter, Co coarse powder was additionally added to the ball mill pot and mixed for 1 hour.
  • the mixed powder thus obtained was filled into a carbon mold and hot-pressed in a vacuum atmosphere under the conditions of a temperature of 1000 ° C., a holding time of 2 hours, and a pressure of 30 MPa to obtain a sintered body. . Further, this was cut with a lathe to obtain a disk-shaped target having a diameter of 180 mm and a thickness of 5 mm.
  • the average leakage magnetic flux density of the target of Example 2 was 28%.
  • the surface of the target is polished and the structure is observed with a microscope, it can be seen that metal particles are scattered in the structure in which the nonmagnetic material particles are dispersed in the metal phase as shown in FIG.
  • an average of 19 metal grains having a sum of the maximum diameter and the minimum diameter of 30 ⁇ m or more were confirmed in a 1 mm 2 visual field.
  • FIG. 5 shows an enlarged view of FIG. 4 in order to observe the non-magnetic material particles.
  • the ratio of the non-magnetic material particles having a difference between the maximum diameter and the minimum diameter of 0.7 ⁇ m or less evaluated in the same manner as in Example 1 was 64%, and the average particle diameter was 1.26 ⁇ m.
  • this target was attached to a DC magnetron sputtering apparatus, and sputtering was performed.
  • the sputtering conditions were the same as in Example 1.
  • the sputtering power was 1.2 kW
  • the Ar gas pressure was 1.5 Pa
  • sputtering was performed on a 4-inch diameter silicon substrate with a target film thickness of 1000 nm.
  • the number of particles adhering to the substrate was measured with a particle counter. At this time, the number of particles on the silicon substrate was four.
  • Co coarse powder adjusted to have a particle size in the range of 50 ⁇ m to 300 ⁇ m was prepared, and the ratio of Co powder having an average particle size of 4 ⁇ m to the Co coarse powder was set to 7: 3 by weight. These powders were weighed 2000 g with the following composition ratio.
  • the Co coarse powder was removed, and the weighed powder was enclosed in a ball mill pot with a capacity of 10 liters together with a tungsten alloy ball as a grinding medium, and rotated and mixed for 120 hours. Thereafter, Co coarse powder was additionally added to the ball mill pot and mixed for 1 hour.
  • the mixed powder thus obtained was filled into a carbon mold and hot-pressed in a vacuum atmosphere under the conditions of a temperature of 1000 ° C., a holding time of 2 hours, and a pressure of 30 MPa to obtain a sintered body. . Further, this was cut with a lathe to obtain a disk-shaped target having a diameter of 180 mm and a thickness of 5 mm.
  • the average leakage magnetic flux density of the target of Example 3 was 31%.
  • the surface of the target is polished and the structure is observed with a microscope, it can be seen that metal particles are scattered in the structure in which the nonmagnetic material particles are dispersed in the metal phase.
  • an average of 18 metal particles having a sum of the maximum diameter and the minimum diameter of 30 ⁇ m or more were confirmed in a 1 mm 2 field of view.
  • the proportion of non-magnetic material particles having a difference between the maximum diameter and the minimum diameter evaluated in the same manner as in Example 1 of 0.7 ⁇ m or less was 60%, and the average particle diameter was 1.16 ⁇ m.
  • this target was attached to a DC magnetron sputtering apparatus, and sputtering was performed.
  • the sputtering conditions were the same as in Example 1.
  • the sputtering power was 1.2 kW
  • the Ar gas pressure was 1.5 Pa
  • sputtering was performed on a 4-inch diameter silicon substrate with a target film thickness of 1000 nm.
  • the number of particles adhering to the substrate was measured with a particle counter. At this time, the number of particles on the silicon substrate was five.
  • Example 4 Fe powder having an average particle diameter of 4 ⁇ m, Pt powder having an average particle diameter of 3 ⁇ m, Fe—B powder having an average particle diameter of 7 ⁇ m, and spherical SiO 2 powder having an average particle diameter of 0.8 ⁇ m were prepared as metal raw material powders.
  • coarse Fe powder adjusted to have a particle size in the range of 50 ⁇ m to 300 ⁇ m was prepared, and the ratio of Fe powder with an average particle size of 4 ⁇ m to the coarse Fe powder was 8: 2. These powders were weighed 2000 g with the following composition ratio.
  • the Fe coarse powder was removed, and the weighed powder was enclosed in a ball mill pot with a capacity of 10 liters together with a tungsten alloy ball as a grinding medium, and rotated and mixed for 120 hours. Thereafter, Fe coarse powder was additionally added to the ball mill pot and mixed for 1 hour.
  • the mixed powder thus obtained was filled in a carbon mold and hot-pressed in a vacuum atmosphere under the conditions of a temperature of 1300 ° C., a holding time of 2 hours, and a pressure of 30 MPa to obtain a sintered body. . Further, this was cut with a lathe to obtain a disk-shaped target having a diameter of 180 mm and a thickness of 5 mm.
  • the average leakage magnetic flux density of the target of Example 4 was 61%.
  • the surface of the target is polished and the structure is observed with a microscope, it can be seen that metal particles are scattered in the structure in which the nonmagnetic material particles are dispersed in the metal phase.
  • an average of four metal particles having a maximum diameter and a minimum diameter of 30 ⁇ m or more were confirmed in a 1 mm 2 field of view.
  • the ratio of the nonmagnetic material particles having a difference between the maximum diameter and the minimum diameter of 0.7 ⁇ m or less evaluated in the same manner as in Example 1 was 65%, and the average particle diameter was 1.29 ⁇ m.
  • this target was attached to a DC magnetron sputtering apparatus, and sputtering was performed.
  • the sputtering conditions were the same as in Example 1.
  • the sputtering power was 1.2 kW
  • the Ar gas pressure was 1.5 Pa
  • sputtering was performed on a 4-inch diameter silicon substrate with a target film thickness of 1000 nm.
  • the number of particles adhering to the substrate was measured with a particle counter. At this time, the number of particles on the silicon substrate was six.
  • Co powder with an average particle size of 4 ⁇ m, Cr powder with an average particle size of 5 ⁇ m, Pt powder with an average particle size of 3 ⁇ m, TiO 2 powder with an average particle size of 1.2 ⁇ m as an oxide powder, Average particle size of 0.7 ⁇ m Core-like SiO 2 powder and Cr 2 O 3 powder having an average particle diameter of 1 ⁇ m were prepared. Then, 2000 g of these powders were weighed at the following composition ratio. Composition: 69Co-18Pt-2Cr-5SiO 2 -2TiO 2 -4Cr 2 O 3 (mol%)
  • the weighed powder was enclosed in a ball mill pot with a capacity of 10 liters together with a tungsten alloy ball as a grinding medium, and rotated and mixed for 120 hours.
  • the mixed powder thus obtained was filled into a carbon mold and hot-pressed in the same manner as in Example 1 in a vacuum atmosphere at a temperature of 1100 ° C., a holding time of 2 hours, and a pressure of 30 MPa.
  • a sintered body was obtained. Further, this was cut with a lathe to obtain a disk-shaped target having a diameter of 180 mm and a thickness of 5 mm.
  • the average leakage magnetic flux density of the target of Comparative Example 1 was 18%.
  • metal particles having a maximum diameter and a minimum diameter of 30 ⁇ m or more evaluated in the same manner as in Example 1 were not averaged in a 1 mm 2 field of view.
  • the ratio of the non-magnetic material particles having a difference between the maximum diameter and the minimum diameter of 0.7 ⁇ m or less evaluated in the same manner as in Example 1 was 89%, and the average particle diameter was 0.71 ⁇ m.
  • this target was attached to a DC magnetron sputtering apparatus, and sputtering was performed.
  • the sputtering conditions were a sputtering power of 1.2 kW and an Ar gas pressure of 1.5 Pa. However, since a stable discharge was not obtained, the sputtering power was 1.7 kW and the Ar gas pressure was 2.8 Pa.
  • sputtering was performed on a 4-inch diameter silicon substrate with a target film thickness of 1000 nm. The number of particles adhering to the substrate was measured with a particle counter. At this time, the number of particles on the silicon substrate was nine.
  • Co powder with an average particle size of 4 ⁇ m, Cr powder with an average particle size of 5 ⁇ m, Pt powder with an average particle size of 3 ⁇ m, TiO 2 powder with an average particle size of 1.2 ⁇ m as an oxide powder, Average particle size of 0.7 ⁇ m Core-like SiO 2 powder and Cr 2 O 3 powder having an average particle diameter of 1 ⁇ m were prepared. Further, Co coarse powder adjusted to have a particle size in the range of 50 ⁇ m to 300 ⁇ m was prepared, and the ratio of Co powder having an average particle size of 4 ⁇ m to the Co coarse powder was set to 7: 3 by weight. These powders were weighed 2000 g with the following composition ratio. Composition: 69Co-18Pt-2Cr-5SiO 2 -2TiO 2 -4Cr 2 O 3 (mol%)
  • the coarse Co powder was removed, and the weighed powder was enclosed in a ball mill pot with a capacity of 10 liters together with a tungsten alloy ball as a grinding medium, and rotated and mixed for 70 hours. Thereafter, Co coarse powder was additionally added to the ball mill pot and mixed for 1 hour.
  • the mixed powder thus obtained was filled in a carbon mold and hot-pressed in a vacuum atmosphere under conditions of a temperature of 1100 ° C., a holding time of 2 hours, and a pressure of 30 MPa to obtain a sintered body. . Further, this was cut with a lathe to obtain a disk-shaped target having a diameter of 180 mm and a thickness of 5 mm.
  • the average leakage magnetic flux density of the target of Comparative Example 2 was 29%.
  • an average of 36 metal grains having a maximum diameter and a minimum diameter of 30 ⁇ m or more evaluated in the same manner as in Example 1 were confirmed in a 1 mm 2 field of view.
  • the ratio of the nonmagnetic material particles having a difference between the maximum diameter and the minimum diameter of 0.7 ⁇ m or less evaluated in the same manner as in Example 1 was 54%, and the average particle diameter was 1.87 ⁇ m.
  • this target was attached to a DC magnetron sputtering apparatus, and sputtering was performed.
  • the sputtering conditions were the same as in Example 1.
  • the sputtering power was 1.2 kW
  • the Ar gas pressure was 1.5 Pa
  • sputtering was performed on a 4-inch diameter silicon substrate with a target film thickness of 1000 nm.
  • the number of particles adhering to the substrate was measured with a particle counter. At this time, the number of particles on the silicon substrate was as large as 28.
  • the present invention adjusts the structure of the sputtering target, particularly the shape of the nonmagnetic material particles and metal particles, thereby improving the leakage magnetic field during sputtering and suppressing abnormal discharge due to the nonmagnetic material.
  • a stable discharge can be obtained when sputtering with a magnetron sputtering apparatus.
  • the magnetic recording medium has an excellent effect of suppressing the abnormal discharge of the nonmagnetic material, reducing the generation of particles during sputtering caused by the abnormal discharge, and obtaining the cost improvement effect by improving the yield. It is useful as a ferromagnetic sputtering target used for forming a magnetic thin film, particularly a hard disk drive recording layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Powder Metallurgy (AREA)
  • Thin Magnetic Films (AREA)

Abstract

L'invention concerne une structure observée sur la surface polie dans cette cible de pulvérisation frittée, conçue à partir de particules métalliques et d'une phase métallique dans laquelle des particules de matériau non magnétiques, avec un diamètre de particule moyen de 1,8 µm ou moins, sont dispersées et qui contient du Co ou du Fe. En définissant le diamètre maximal comme la plus grande valeur de la distance entre deux points quelconques sur la périphérie externe d'une particule de matériau non magnétique et le diamètre minimal comme la plus petite valeur de la distance entre deux lignes parallèles, lorsque les lignes enserrent la même particule, des particules de matériau non magnétique dans lesquelles la différence entre le diamètre maximal et le diamètre minimal est inférieure ou égale à 0,7 μm constituent 60 % ou plus des particules de matériau non magnétique dans la structure observée sur la surface polie de la cible; et, en définissant le diamètre maximal comme la plus grande valeur de la distance entre deux points quelconques sur la périphérie externe d'une particule métallique et le diamètre minimal comme la valeur la plus petite de la distance entre deux lignes parallèles, lorsque ces lignes enserrent la particule métallique, il existe, dans un champ de vision de 1 mm2, en moyenne 1 particule métallique ou plus, pour lesquelles la somme de la valeur maximale et de la valeur minimale est de 30 μm ou plus. Cette cible de pulvérisation peut supprimer la décharge anormale provoquée par les matériaux non magnétiques, qui entraînent la génération de particules pendant la pulvérisation.
PCT/JP2014/051494 2013-02-15 2014-01-24 PULVÉRISATION DE CIBLE CONTENANT DU Co OU DU Fe WO2014125897A1 (fr)

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JP2015500172A JP6332869B2 (ja) 2013-02-15 2014-01-24 Ｃｏ又はＦｅを含有するスパッタリングターゲット
SG11201503676WA SG11201503676WA (en) 2013-02-15 2014-01-24 SPUTTERING TARGET CONTAINING Co OR Fe
CN201480003726.9A CN104903488B (zh) 2013-02-15 2014-01-24 含有Co或Fe的溅射靶

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CN105056926A (zh) * 2015-07-24 2015-11-18 武汉纺织大学 一种新型TiO2/WO3包覆的磁性纳米复合粒子及其制备方法和用途
KR20180054596A (ko) * 2015-09-18 2018-05-24 산요오도꾸슈세이꼬 가부시키가이샤 스퍼터링 타겟재
US10837101B2 (en) 2016-03-31 2020-11-17 Jx Nippon Mining & Metals Corporation Ferromagnetic material sputtering target
WO2021085410A1 (fr) * 2019-11-01 2021-05-06 田中貴金属工業株式会社 Cible de pulvérisation pour support d'enregistrement magnétique à assistance thermique
JP2021123782A (ja) * 2020-02-07 2021-08-30 Ｊｘ金属株式会社 スパッタリングターゲット、磁性膜、及びスパッタリングターゲット作製用の原料混合粉末

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TWI702294B (zh) * 2018-07-31 2020-08-21 日商田中貴金屬工業股份有限公司 磁氣記錄媒體用濺鍍靶
JP2024010347A (ja) * 2022-07-12 2024-01-24 田中貴金属工業株式会社 Ｃｏ－Ｃｒ－Ｐｔ－酸化物系スパッタリングターゲット

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WO2012011294A1 (fr) * 2010-07-20 2012-01-26 Jx日鉱日石金属株式会社 Cible de pulvérisation de matériau ferromagnétique présentant une faible production de particules

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Publication number Priority date Publication date Assignee Title
CN105056926A (zh) * 2015-07-24 2015-11-18 武汉纺织大学 一种新型TiO2/WO3包覆的磁性纳米复合粒子及其制备方法和用途
KR20180054596A (ko) * 2015-09-18 2018-05-24 산요오도꾸슈세이꼬 가부시키가이샤 스퍼터링 타겟재
KR102620685B1 (ko) 2015-09-18 2024-01-02 산요오도꾸슈세이꼬 가부시키가이샤 스퍼터링 타겟재
US10837101B2 (en) 2016-03-31 2020-11-17 Jx Nippon Mining & Metals Corporation Ferromagnetic material sputtering target
WO2021085410A1 (fr) * 2019-11-01 2021-05-06 田中貴金属工業株式会社 Cible de pulvérisation pour support d'enregistrement magnétique à assistance thermique
JP2021123782A (ja) * 2020-02-07 2021-08-30 Ｊｘ金属株式会社 スパッタリングターゲット、磁性膜、及びスパッタリングターゲット作製用の原料混合粉末
JP7317741B2 (ja) 2020-02-07 2023-07-31 Ｊｘ金属株式会社 スパッタリングターゲット、磁性膜、及びスパッタリングターゲット作製用の原料混合粉末

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MY178171A (en) 2020-10-06
CN104903488A (zh) 2015-09-09
TWI608114B (zh) 2017-12-11
CN104903488B (zh) 2018-02-16
JP2017137570A (ja) 2017-08-10
MY185389A (en) 2021-05-17
SG11201503676WA (en) 2015-06-29

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