WO2022004354A1 - Cible de pulvérisation et procédé de fabrication associé - Google Patents

Cible de pulvérisation et procédé de fabrication associé Download PDF

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WO2022004354A1
WO2022004354A1 PCT/JP2021/022674 JP2021022674W WO2022004354A1 WO 2022004354 A1 WO2022004354 A1 WO 2022004354A1 JP 2021022674 W JP2021022674 W JP 2021022674W WO 2022004354 A1 WO2022004354 A1 WO 2022004354A1
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center
total
sputtering target
locations
gravity
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PCT/JP2021/022674
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English (en)
Japanese (ja)
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雄 鈴木
将平 大友
公義 野澤
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株式会社フルヤ金属
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Priority to JP2022533817A priority Critical patent/JPWO2022004354A1/ja
Priority to TW110124059A priority patent/TW202206628A/zh
Publication of WO2022004354A1 publication Critical patent/WO2022004354A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • 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
    • 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

Definitions

  • the present disclosure is for preventing foreign matter from adhering to the protective film or mask pattern surface of the mask blanks, which is the original plate of the mask used when performing EUV lithography using Extreme Ultra Violet (hereinafter referred to as EUV) light.
  • EUV Extreme Ultra Violet
  • the present invention relates to a sputtering target suitable for forming a pellicle film or the like.
  • an alloy material added to ruthenium is used because of its superiority in transmitting or absorbing EUV light and heat conduction, and a thin film is formed by using a sputtering method as a thin film forming method. Is formed.
  • Sputtering targets are disclosed (see, eg, Patent Document 1).
  • the content in the compound is preferably in the range of 3 to 75 atomic%, and particularly from the viewpoint of improving chemical resistance, 40 It is stated that it is desirable to have a range of ⁇ 75 atomic%.
  • Patent Document 1 since boron and yttrium are easily oxidized metals, if the content of these metals is high, an oxide layer is formed on the surface of the formed ruthenium compound film and the optical characteristics (for example, EUV). It is stated that the content in the compound is preferably in the range of 3 to 50 atomic% because the reflectance of light) may be deteriorated. Further, in Patent Document 1, among impurities, the oxygen content is 2000 ppm or less, the carbon content is 200 ppm or less, and both the oxygen and carbon contents are small, so that they are generated from the target at the time of film formation. It is stated to reduce particles.
  • the thickness of the film formed is extremely thin and the range of the film formed is relatively wide, so that the in-plane uniformity of the film thickness and the in-plane composition of the film are relatively wide. Uniformity is important. Therefore, it has been necessary to improve the density of the target and reduce the amount of oxygen in the sputtering target.
  • further miniaturization of particles that cause defects has progressed, and not only the above-mentioned particle source but also the material itself added to ruthenium may be scattered during film formation. I've become suspicious.
  • Sputtering targets have been manufactured by the dissolution method in order to reduce the amount of oxygen or improve the density.
  • ruthenium and the elements to be added are generally high melting point materials having a melting point of more than 1600 ° C., and dissolution is not easy.
  • various intermetallic compounds hereinafter referred to as IMC
  • IMC intermetallic compounds
  • cracks are likely to occur in the solidification process, and cracks occur when processing is performed after dissolution and solidification.
  • the difficulty of molding is high. Even if the target material can be molded, the IMC precipitates and coarsens during the solidification process, and the composition distribution in the in-plane direction of the target and in the cross-sectional direction (also referred to as the target thickness direction) deteriorates.
  • the in-plane composition distribution and the uniformity of the film thickness distribution of the formed film deteriorate depending on the location in the target.
  • hot-working is not possible because the IMC precipitates and becomes coarse and the problem of cracks or cracks occurs.
  • an object of the present disclosure is to provide a sputtering target capable of obtaining a uniform composition distribution in the in-plane direction and the film thickness direction of the film film, and a method for producing the same. ..
  • the present inventors have set the major axis of the dispersed particles in the sputtering target to a predetermined particle size, so that the composition of the film formed is the in-plane direction of the film and the in-plane direction of the film.
  • the sputtering target according to the present invention is any one selected from ruthenium as the first element and boron, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten as the second element.
  • the sputtering target of the alloy composed of has dispersed particles composed of two phases including an intermetallic compound phase composed of two kinds of elements, the first element and the second element.
  • the maximum major axis of the dispersed particles is 500 ⁇ m or less. Since it can be highly dispersed in the sputtering target by setting the particle size to a predetermined value, the composition of the film formed by using the target is uniform in the in-plane direction and the film thickness direction of the film. The composition distribution can be obtained.
  • the two phases are (1) a combination of the metal-to-metal compound phase and the metal ruthenium phase which is the metal phase of the first element, and (2) two kinds of the metal-to-metal phase. It includes a combination, or (3) a combination of the intermetallic compound phase and the metal phase of the second element.
  • the sputtering target according to the present invention includes ruthenium as the first element and any one selected from boron, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten as the second element.
  • the sputtering target of the alloy composed of the above the sputtering target has dispersed particles containing an intermetallic compound phase composed of two kinds of elements, the first element and the second element, and has a maximum major axis of the dispersed particles.
  • the relative integrated intensity of the second peak due to X-ray diffraction in the sputtering surface of the sputtering target is 60% or more with respect to the relative integrated intensity of the first peak. It is characterized in that there is at least one location.
  • (Condition 1) Inward direction of sputter plane: The sputtering target is a disk-shaped target having a center O and a radius r, and the measurement point is on a virtual cross line orthogonal to the center O as an intersection, and one point of the center O is the center.
  • the sputtering target includes a rectangle having a vertical length of L1 and a horizontal length of L2 (provided that a square in which L1 and L2 are equal to each other is included, or the rectangle has a length J.
  • L2 corresponds to length J
  • L1 corresponds to circumference K
  • length J and circumference K correspond to J> K.
  • the measurement point is a virtual cross line orthogonal to the center of gravity O as the intersection, and the virtual cross line is orthogonal to the side of the rectangle.
  • One location of the center of gravity O a total of two locations on the virtual cross line that are 0.25L1 in the vertical direction from the center of gravity O, two locations in total that are 0.25L2 in the horizontal direction from the center of gravity O, the center of gravity O
  • the relative integral intensity of the second peak due to X-ray diffraction in the sputtering surface of the sputtering target is 60 with respect to the relative integral intensity of the first peak. It is preferable that 40% or more of the portions are at least%. Since there are many regions where the difference between the relative integral strength of the second peak and the relative integral strength of the first peak is small, the degree of anisotropy of the structure is reduced, and the difference in sputtering rate during film formation can be reduced. It can be suppressed and a uniform film thickness can be obtained.
  • the composition of the sputtering target in the sputter plane inward direction and the target thickness direction in (Condition 3) or (Condition 4) has a difference of ⁇ 1.5 with respect to the reference composition. %, And the reference composition is preferably the average value of the total composition of 18 points measured according to (Condition 3) or (Condition 4).
  • (Condition 3) Inward direction of sputter plane: The sputtering target is a disk-shaped target having a center O and a radius r, and the measurement point is on a virtual cross line orthogonal to the center O as an intersection, and one point of the center O is the center.
  • Target thickness direction A cross section passing through any one of the virtual cross lines is formed, and the cross section is a rectangle with a vertical t (that is, a target thickness of t) and a horizontal 2r, and the measurement point is set.
  • points a, X, and b A total of 3 points 0.45 to up and down from the center X and the center X on the vertical crossing line passing through the center O, on the left and right sides of the point a on the cross section.
  • the sputtering target includes a rectangle having a vertical length of L1 and a horizontal length of L2 (provided that a square in which L1 and L2 are equal to each other is included, or the rectangle has a length J.
  • One location of the center of gravity O a total of two locations on the virtual cross line that are 0.25L1 in the vertical direction from the center of gravity O, two locations in total that are 0.25L2 in the horizontal direction from the center of gravity O, the center of gravity O There are a total of 9 locations, a total of 2 locations separated by a distance of 0.45 L1 in the vertical direction from the center of gravity O and a total of 2 locations separated by a distance of 0.45 L2 in the horizontal direction from the center of gravity O.
  • Target thickness direction Of the virtual cross lines, a cross section is formed that passes through a line parallel to either one of the vertical L1 and the horizontal L2, and when one side is the horizontal L2, the cross section is the vertical t (that is, the above-mentioned).
  • the target thickness is t), it is a rectangular shape with a horizontal L2, and the measurement points are the center X on the vertical crossing line passing through the center of gravity O and a total of three points (point a, X) 0.45 t above and below the center X.
  • Point, referred to as point b) a total of 2 points on the cross section separated from point a by 0.45 L2 toward the left and right sides, and a total of 2 points separated from point X toward the left and right sides by 0.45 L2.
  • a total of 9 points, a total of 2 points and a total of 2 points separated by 0.45 L2 from the point b toward the left and right sides, are set as measurement points.
  • composition deviation of the target By suppressing the composition deviation of the target, it is possible to suppress the difference in the sputtering rate at the time of film formation, and it is possible to suppress the composition deviation and the film thickness deviation of the film after the film formation. In addition, it is possible to suppress the mixing of particles caused by minute protrusions caused by the difference in sputtering rate.
  • the crystallite size of the first peak is preferably 400 ⁇ or less.
  • a homogeneous thin film can be formed by reducing the crystallite size.
  • the content of the second element is preferably 3 to 70 atomic%.
  • the corrosion resistance is improved and the reflectance that can be satisfied as EUV can be secured.
  • the sputtering target according to the present invention preferably has an oxygen content of 500 ppm or less.
  • the sputtering target according to the present invention preferably has a carbon content of 200 ppm or less.
  • HP discharge plasma sintering method
  • SPS discharge plasma sintering method
  • HIP hot isotropic pressure sintering method
  • a vacuum atmosphere of 50 Pa or less a nitrogen gas atmosphere containing 0 to 4 vol% or less of hydrogen gas, or hydrogen. It has a sintering step of sintering in an inert gas atmosphere containing 0 to 4 vol% or less of gas to obtain a sintered body, and the maximum major axis of the alloy powder obtained by the atomizing method is 500 ⁇ m or less. It is a feature.
  • the composition of the film formed by using the target is such that the in-plane direction of the film and the film are suppressed while suppressing the mixing of particles. A uniform composition distribution can be obtained even in the thickness direction.
  • the method for producing a sputtering target according to the present invention further includes a classification step of removing particles having a maximum major axis of more than 500 ⁇ m from the alloy powder obtained by the atomizing method between the atomizing step and the sintering step. Is preferable. Since a high-density sputtering target can be formed in the step of obtaining the sintered body, the composition of the film formed by using the target is uniform in the in-plane direction and the film thickness direction of the film. The composition distribution can be obtained.
  • the present disclosure can provide a sputtering target and a method for producing the same, which can obtain a uniform composition distribution in the in-plane direction and the film thickness direction of the film film.
  • the sputtering target according to the present embodiment includes ruthenium as the first element and any one selected from boron, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten as the second element.
  • the sputtering target of the alloy composed of the sputtering target has dispersed particles composed of two phases including an intermetallic compound phase composed of two kinds of elements, the first element and the second element, and is dispersed.
  • the maximum major axis of the particles is 500 ⁇ m or less.
  • the dispersed particles present in the sputtering target correspond to the constituent particles of the sintered body, for example, when the sputtering target is a sintered body.
  • the dispersed particles have a plurality of crystal grains.
  • the maximum major axis of the dispersed particles is 500 ⁇ m or less, preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 150 ⁇ m or less. If the maximum major axis of the dispersed particles is larger than 500 ⁇ m, the dispersed particles are biased in the sputtering target, and the composition shifts depending on the location of the sputtering target. When a film is formed using a sputtering target in which the composition is displaced, the composition is displaced in the in-plane direction and the film thickness direction of the film. Therefore, the maximum major axis of the dispersed particles should be 500 ⁇ m or less. preferable.
  • setting the maximum major axis to 500 ⁇ m or less means that particles having a major axis exceeding 500 ⁇ m are not included.
  • the maximum major axis is determined by measuring the distance from one end of the largest dispersed particle to the other based on the scale of the image in the SEM image analysis within the range of 1200 ⁇ m ⁇ 1500 ⁇ m.
  • the two phases are (1) a combination of an intermetallic compound phase and a metallic ruthenium phase which is the metal phase of the first element, (2) a combination of two types of intermetallic compound phases, or. (3) It includes a form which is a combination of an intermetal compound phase and a metal phase of a second element.
  • the number of phases is determined by the phase identified by X-ray diffraction.
  • the intermetallic compound formed at the grain boundaries is not included as a two-phase object.
  • the dispersed particles have two types of crystal grains corresponding to the two phases.
  • the grain boundary includes the boundary between the dispersed particles and the dispersed particles next to the dispersed particles, and the boundary between the crystal grains and the crystal grains next to the crystal grains.
  • Ru 2 AE phase, Ru AE phase and RuAE 2 phase any one of them, Ru 2 AE phase only, Ru 2 AE phase and Ru AE phase, Ru 2 AE phase and RuAE 2 form of a phase, RuAE phase only in the form, the form of the RuAE phase and RuAE 2 phase, the form of RuAE 2 phases only, RuAE 2 phases, among RuAE phase and Ru 2 AE phase, any one phase and the AE phase ( However, there are a form of a solid solution in which ruthenium is solid-dissolved in the second element) and a form of only the metal phase of the second element (provided that the solid solution in which ruthenium is solid-dissolved in the second element).
  • the "two-phase (1) is a combination of a metallic ruthenium phase is a metal phase of the intermetallic compound phase of a first element", Ru phase and Ru 2 AE phase, RuAE phase, the RuAE 2 phases Of these, it is in the form of any one phase.
  • "two phases are (2) a combination of two kinds of intermetallic compound phases” means a form of Ru 2 AE phase and RuAE phase, a form of Ru 2 AE phase and RuAE 2 phase, or a RuAE phase. It is a form with RuAE 2 phase.
  • the two phases are a combination of (3) an intermetal compound phase and a metal phase of the second element
  • one of the RuAE 2 phase, the RuAE phase, and the Ru 2 AE phase is one and the AE phase. It is a form of.
  • the cases can be classified according to the same idea.
  • the two phases appear due to two types of crystal grains with different compositions in the dispersed particles.
  • the case where there are three types of intermetallic compounds, Ru 2 AE, RuAE and RuAE 2 will be described as an example.
  • two-phase (1) combinations are the metallic ruthenium phase is a metal phase of the intermetallic compound phase of a first element
  • grain and Ru 2 AE phase Ru phases among RuAE phase and RuAE 2 phases
  • Any one phase of crystal grains is present in the dispersed particles.
  • the two phases are (2) a combination of two kinds of intermetallic compound phases
  • phase crystal grains and the RuAE 2 phase crystal grains are present in the dispersed particles, or the RuAE phase crystal grains and the RuAE 2 phase crystal grains are present in the dispersed particles.
  • a "two phase (3) is a combination of a metal phase of intermetallic phase and the second element" is, RuAE 2 phases, among RuAE phase and Ru 2 AE phase, of any one phase crystal grain And the crystal grains of the AE phase are present in the dispersed particles.
  • the sputtering target according to the present embodiment includes ruthenium as the first element and any one selected from boron, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten as the second element.
  • the sputtering target of the alloy composed of the sputtering target has dispersed particles containing an intermetallic compound phase composed of two kinds of elements, the first element and the second element, and the maximum major axis of the dispersed particles is large.
  • the relative integrated intensity of the second peak due to X-ray diffraction in the in-plane direction of the sputtering target is 60% or more of the relative integrated intensity of the first peak.
  • the sputtering target is a disk-shaped target having a center O and a radius r, and the measurement point is on a virtual cross line orthogonal to the center O as an intersection, and one point of the center O is the center. There are a total of 4 locations 0.45r away from O and a total of 4 locations 0.9r away from the center O, for a total of 9 locations.
  • Inward direction of sputtering surface The sputtering target includes a rectangle having a vertical length of L1 and a horizontal length of L2 (provided that a square in which L1 and L2 are equal to each other is included, or the rectangle has a length J.
  • One location of the center of gravity O a total of two locations on the virtual cross line that are 0.25L1 in the vertical direction from the center of gravity O, two locations in total that are 0.25L2 in the horizontal direction from the center of gravity O, the center of gravity O There are a total of 9 locations, a total of 2 locations separated by a distance of 0.45 L1 in the vertical direction from the center of gravity O and a total of 2 locations separated by a distance of 0.45 L2 in the horizontal direction from the center of gravity O.
  • the measurement range at 9 points is 10 mm ⁇ 10 mm, respectively.
  • the relative integral intensity of the second peak by X-ray diffraction in the sputter surface of the sputtering target is 60% or more with respect to the relative integral intensity of the first peak is determined based on the graph obtained by X-ray diffraction.
  • the peak and the second peak are selected, the relative integral strength of the first peak and the relative integral strength of the second peak are calculated using the waveform analysis software of X-ray diffraction, and the relative integral strength of the second peak is the first peak. It is determined whether or not it is 60% or more with respect to the relative integral strength.
  • the relative integral intensity of the second peak due to X-ray diffraction in the sputtering surface of the sputtering target is 60% or more, preferably 65% or more, preferably 70% or more with respect to the relative integral intensity of the first peak. It is more preferable to have.
  • (Condition 1) or (Condition 2) if the relative integrated intensity of the second peak in X-ray diffraction is less than 60% of the relative integrated intensity of the first peak, the film thickness varies. Therefore, it is preferable that the relative integral intensity of the second peak in X-ray diffraction is 60% or more with respect to the relative integral intensity of the first peak.
  • the relative integral intensity of the second peak due to X-ray diffraction in the sputtering surface of the sputtering target is relative to the relative integral intensity of the first peak. It is preferable that 40% or more of the portions are 60% or more, and more preferably 50% or more. Since there are many regions where the difference between the relative integral strength of the second peak and the relative integral strength of the first peak is small, the degree of anisotropy of the structure is reduced, and the difference in sputtering rate during film formation can be reduced. It can be suppressed and a uniform film thickness can be obtained.
  • the composition of the sputtering target in the sputter plane inward direction and the target thickness direction in (Condition 3) or (Condition 4) has a difference of ⁇ 1.5 with respect to the reference composition. %, And the reference composition is preferably the average value of the total composition of 18 points measured according to (Condition 3) or (Condition 4).
  • (Condition 3) Inward direction of sputter plane: The sputtering target is a disk-shaped target having a center O and a radius r, and the measurement point is on a virtual cross line orthogonal to the center O as an intersection, and one point of the center O is the center.
  • Target thickness direction A cross section passing through any one of the virtual cross lines is formed, and the cross section is a rectangle with a vertical t (that is, a target thickness of t) and a horizontal 2r, and the measurement point is set.
  • points a, X, and b A total of 3 points 0.45 to up and down from the center X and the center X on the vertical crossing line passing through the center O, on the left and right sides of the point a on the cross section.
  • the sputtering target includes a rectangle having a vertical length of L1 and a horizontal length of L2 (provided that a square in which L1 and L2 are equal to each other is included, or the rectangle has a length J.
  • One location of the center of gravity O a total of two locations on the virtual cross line that are 0.25L1 in the vertical direction from the center of gravity O, two locations in total that are 0.25L2 in the horizontal direction from the center of gravity O, the center of gravity O There are a total of 9 locations, a total of 2 locations separated by a distance of 0.45 L1 in the vertical direction from the center of gravity O and a total of 2 locations separated by a distance of 0.45 L2 in the horizontal direction from the center of gravity O.
  • Target thickness direction Of the virtual cross lines, a cross section is formed that passes through a line parallel to either one of the vertical L1 and the horizontal L2, and when one side is the horizontal L2, the cross section is the vertical t (that is, the above-mentioned).
  • the target thickness is t), it is a rectangular shape with a horizontal L2, and the measurement points are the center X on the vertical crossing line passing through the center of gravity O and a total of three points (point a, X) 0.45 t above and below the center X.
  • Point, referred to as point b) a total of 2 points on the cross section separated from point a by 0.45 L2 toward the left and right sides, and a total of 2 points separated from point X toward the left and right sides by 0.45 L2.
  • a total of 9 points, a total of 2 points and a total of 2 points separated by 0.45 L2 from the point b toward the left and right sides, are set as measurement points.
  • the composition of the sputtering target in the sputter plane inward direction and the target thickness direction in (Condition 3) or (Condition 4) has a difference of ⁇ 1. It is preferably within 5%, more preferably within ⁇ 1.25%, and even more preferably within ⁇ 1%.
  • the reference composition is the average value of the total composition of 18 points measured according to (Condition 3) or (Condition 4). If the difference is larger than ⁇ 1.5% with respect to the reference composition, the composition deviation is large depending on the location of the sputtering target.
  • composition deviation occurs also in the film thickness direction
  • the difference between the composition in the sputtering surface inward direction of the sputtering target and the composition in the target thickness direction is within ⁇ 1.5% with respect to the reference composition. Is preferable.
  • composition in (Condition 3) or (Condition 4), it is preferable that the measurement range at 9 points is 700 ⁇ m ⁇ 900 ⁇ m, respectively.
  • FIG. 1 is a schematic view showing a measurement point (hereinafter, abbreviated as a measurement point) in the direction in the sputtered surface of the disk-shaped target, with reference to FIG. 1 (Condition 1) and (Condition 3). ),
  • the measurement points in the sputtered surface inward direction of the sputtering target will be described.
  • the radius is preferably 25 to 225 mm, more preferably 50 to 200 mm.
  • the thickness of the target is preferably 3 to 30 mm, more preferably 5 to 26 mm. In this embodiment, more effect can be expected for a large target.
  • the sputtering target 200 is a disk-shaped target having a center O and a radius r.
  • the measurement points are on a virtual cross line (L) orthogonal to the center O as an intersection, and one point (S1) of the center O and a total of four points (S3, S5, S6 and S8) 0.45 r away from the center O. ) And a total of 4 locations (S2, S4, S7 and S9) 0.9r away from the center O, for a total of 9 locations.
  • FIG. 2 is a schematic view showing measurement points in the target thickness direction of the disc-shaped target shown in the BB cross section of FIG. 1, and the target thickness of the sputtering target of (Condition 3) with reference to FIG. The measurement points in the direction will be described.
  • the BB cross section of FIG. 1 is a rectangle having a length t (that is, a target thickness t) and a width 2r.
  • the measurement points are the center X (C1) on the vertical crossing line passing through the center O shown in FIG. , B point (C5)), a total of 2 points (C6, C7) 0.9r away from point a toward the left and right sides on the cross section, and from point X toward the left and right sides.
  • a total of 9 points, a total of 2 points (C2, C3) 0.9r apart and a total of 2 points (C8, C9) 0.9r away from point b toward the left and right sides, are set as measurement points. ..
  • FIG. 3 is a schematic view showing measurement points in the sputtered surface inward direction of the square plate-shaped target, and is a measurement point in the sputtered surface inward direction of the sputtering targets of (Condition 2) and (Condition 4) with reference to FIG. Will be explained.
  • the vertical length and the horizontal length are preferably 50 to 450 mm, more preferably 100 to 400 mm.
  • the thickness of the target is preferably 3 to 30 mm, more preferably 5 to 26 mm. In this embodiment, more effect can be expected for a large target.
  • the sputtering target 300 is a rectangular target having a vertical length of L1 and a horizontal length of L2 (including a square in which L1 and L2 are equal to each other).
  • the form which is L2 is shown.
  • the measurement point is a virtual cross line (Q) orthogonal to the center of gravity O as an intersection, and when the virtual cross line is orthogonal to the side of a rectangle (or a square), one point (P1) of the center of gravity O is on the virtual cross line.
  • FIG. 4 is a schematic view showing measurement points in the target thickness direction of the square plate-shaped target shown in the CC cross section of FIG. 3, and the target thickness of the sputtering target of (Condition 4) with reference to FIG. 4 is shown. The measurement points in the vertical direction will be described.
  • the CC cross section of FIG. 3 forms a cross section passing through a line parallel to the horizontal side, and the cross section is a rectangular shape having a vertical t (that is, the thickness of the target is t) and a horizontal L2, and is measured.
  • a total of three locations referred to as points a (D4), X (D1), and b (D5)), 0.45 tons above and below the center X and the center X on the vertical crossing line passing through the center of gravity O, said.
  • a total of 9 points (D3) and 2 points (D8, D9) separated from the point b toward the left and right sides by 0.45 L2 are used as measurement points.
  • FIG. 5 is a conceptual diagram for explaining a measurement point of a cylindrical target.
  • the side surface of the cylinder is the sputtering surface
  • the developed view is a rectangle (including a square). Therefore, (Condition 2) or (Condition 4) is the case of FIGS. 3 and 4.
  • the rectangle includes a rectangle having a cylindrical side surface having a length J and a perimeter K.
  • L2 corresponds to the length J
  • L1 corresponds to the perimeter K
  • the EE cross section and the DD development surface so that the cross sections are at both ends are considered. ..
  • the measurement points in the target thickness direction are considered in the EE cross section in the same manner as in FIG. That is, it is considered that the height J of the cylindrical material corresponds to L2 in FIG. 4 and the thickness of the cylindrical material corresponds to the thickness t in FIG. 4, and the measurement point is set. Further, the measurement points in the inward direction of the spatter surface are considered in the same manner as in FIG. 3 on the DD development surface. That is, it is considered that the height J of the cylindrical material corresponds to L2 in FIG.
  • the length of the waist circumference of the cylinder is preferably 100 to 350 mm, more preferably 150 to 300 mm.
  • the length of the cylinder is preferably 300 to 3000 mm, more preferably 500 to 2000 mm.
  • the thickness of the target is preferably 3 to 30 mm, more preferably 5 to 26 mm. In this embodiment, more effect can be expected for a large target.
  • the crystallite size of the first peak is preferably 400 ⁇ or less, more preferably 350 ⁇ or less, still more preferably 300 ⁇ or less. If the crystallite size of the first peak is larger than 400 ⁇ , the orientation of the crystallites will be biased, so that the sputter rate will differ depending on the location and the film thickness will differ. It is preferably 400 ⁇ or less.
  • the crystallite size is measured using waveform analysis software for X-ray diffraction.
  • the sputtering target according to the present embodiment preferably has a second element content of 3 to 70 atomic%, more preferably 5 to 65 atomic%, and even more preferably 10 to 60 atomic%. If the content is less than 3 atomic%, the reflectance of the film cannot be expected to improve when a thin film is formed using the target, and if the content is more than 70 atomic%, the chemical resistance is lowered due to the small amount of ruthenium. Even if a film is formed using a target, it is difficult to use the film, so the content is preferably 3 to 70 atomic%.
  • the boron content is preferably 25 to 65 atomic%, more preferably 30 to 60 atomic%.
  • the aluminum content is preferably 20 to 60 atomic%, more preferably 30 to 55 atomic%.
  • the titanium content is preferably 10 to 65 atomic%, more preferably 25 to 50 atomic%.
  • the zirconium content is preferably 15 to 65 atomic%, more preferably 20 to 50 atomic%.
  • the hafnium content is preferably 15 to 65 atomic%, more preferably 20 to 50 atomic%.
  • the content of vanadium is preferably 35 to 65 atomic%, more preferably 40 to 60 atomic%.
  • the content of niobium is preferably 15 to 60 atomic%, more preferably 20 to 50 atomic%.
  • the tantalum content is preferably 10 to 65 atomic%, more preferably 25 to 40 atomic%.
  • the chromium content is preferably 30 to 65 atomic%, more preferably 40 to 60 atomic%.
  • the molybdenum content is preferably 25 to 65 atomic%, more preferably 30 to 60 atomic%.
  • the content of tungsten is preferably 10 to 65 atomic%, more preferably 15 to 60 atomic%.
  • the sputtering target according to the present embodiment preferably has an oxygen content of 500 ppm or less, more preferably 400 ppm or less, and even more preferably 300 ppm or less. If the oxygen content is more than 500 ppm, the additive component in the target and oxygen combine to form an oxide, and when a thin film is formed using the target, particles may be mixed in the film. Since the sputter rate varies depending on the location and the film thickness varies, it is preferable that the oxygen content is 500 ppm or less.
  • the sputtering target according to the present embodiment preferably has a carbon content of 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less. If the carbon content is more than 200 ppm, the additive components in the target and carbon combine to form carbides, and when a thin film is formed using the target, particles may be mixed into the film or sputtering may occur. Since the rate varies depending on the location and the film thickness varies, it is preferable to use 200 ppm or less of carbon.
  • the filling rate of the sputtering target according to the present embodiment is preferably 80% or more, more preferably 95% or more, and even more preferably 98% or more.
  • the filling rate is preferably 80% or more, more preferably 95% or more, and even more preferably 98% or more.
  • the method for producing a sputtering target according to the present embodiment is selected from ruthenium as the first element and boron, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten as the second element.
  • a preparatory step for preparing a raw material in which the first element and the second element have a predetermined element ratio, and 1 ⁇ 10 Atomize to obtain an alloy powder by an atomizing method using the above raw materials in a vacuum atmosphere of -2 Pa or less, a nitrogen gas atmosphere containing 0 to 4 vol% or less of hydrogen gas, or an inert gas atmosphere containing 0 to 4 vol% or less of hydrogen gas.
  • the maximum major axis of the alloy powder obtained by the atomizing method is 500 ⁇ m or less.
  • This step is a step of producing a raw material (hereinafter, also simply referred to as “raw material”) used when producing an alloy powder of the first element and the second element in the second step.
  • the raw materials are a raw material for a ruthenium-boron alloy, a raw material for a ruthenium-aluminum alloy, a raw material for a ruthenium-titanium alloy, a raw material for a ruthenium-zyrosine alloy, a raw material for a ruthenium-hafnium alloy, and a raw material for a ruthenium-vanadium alloy.
  • the raw materials for producing powder to be produced in the first step are (1A) a form in which a single metal of a constituent element of an alloy target is prepared as a starting raw material, and these are mixed and used as a raw material, (2A) a starting raw material.
  • An alloy having the same composition as the alloy target is prepared and used as a raw material, or (3A) the alloy target and the constituent elements are the same or partially missing as the starting raw material, and the composition ratio is different from the desired composition ratio.
  • An example is an example in which the alloy is prepared and a single metal to be blended for adjusting to a desired composition is prepared and mixed to be used as a raw material.
  • Starting raw materials include ruthenium and boron, ruthenium and aluminum, ruthenium and titanium, ruthenium and zirconium, ruthenium and hafnium, ruthenium and vanadium, ruthenium and niobium, ruthenium and tantalum, ruthenium and chromium, ruthenium and molybdenum, or ruthenium and tungsten.
  • One of them is put into a melting device and melted to prepare a raw material. It is preferable to use a material having a small amount of impurities as the material of the device or container used for the dissolving device so that a large amount of impurities are not mixed in the raw material after the dissolution.
  • the melting temperature is 1400 to 2400 ° C as a raw material for a ruthenium-boron alloy, 1600 to 2400 ° C as a raw material for a ruthenium-aluminum alloy, 1700 to 2400 ° C as a raw material for a ruthenium-titanium alloy, and 1700 to 2400 ° C as a ruthenium.
  • the atmosphere in the melting device includes a vacuum atmosphere having a vacuum degree of 1 ⁇ 10 ⁇ 2 Pa or less, a nitrogen gas atmosphere containing 0 to 4 vol% or less of hydrogen gas, or an inert gas atmosphere containing 0 to 4 vol% or less of hydrogen gas. And.
  • the form of the raw material of the alloy powder may be an alloy grain or an alloy ingot, or a combination of the powder, the grain and the agglomerate, in addition to the three raw material forms described in (1A), (2A) and (3A) above. May be good.
  • the powder, the grain and the lump express the difference in the particle size, but in any case, the particle size is not particularly limited as long as it can be used in the powder production apparatus according to the second step. Specifically, since the raw material is melted in the powder manufacturing apparatus of the second step, there is no particular limitation as long as the size of the raw material can be supplied to the powder manufacturing apparatus.
  • This step is a step of producing an alloy powder of the first element and the second element.
  • the alloy powders of the first element and the second element are ruthenium-boron alloy powder, ruthenium-aluminum alloy powder, ruthenium-titanium alloy powder, ruthenium-zyrosine alloy powder, ruthenium-hafnium alloy powder, ruthenium-. It is a vanadium alloy powder, a ruthenium-niob alloy powder, a ruthenium-tantal alloy powder, a ruthenium-chromium alloy powder, a ruthenium-molybdenum alloy powder, or a ruthenium-tungsten alloy powder.
  • the raw materials produced in the first step are put into a powder production apparatus, melted to form a molten metal, and then gas is blown onto the molten metal to scatter the molten metal and quench and solidify to produce a powder. It is preferable to use a material having a small amount of impurities for the equipment and the container used for the powder manufacturing equipment so that a large amount of impurities are not mixed in the alloy powder of the first element and the second element after being melted.
  • the melting method a method that can cope with the following melting temperatures is selected.
  • the melting temperature is 1400 to 2400 ° C as a raw material for a ruthenium-boron alloy, 1600 to 2400 ° C as a raw material for a ruthenium-aluminum alloy, 1700 to 2400 ° C as a raw material for a ruthenium-titanium alloy, and 1700 to 2400 ° C as a ruthenium.
  • the atmosphere in the powder manufacturing apparatus is a vacuum atmosphere having a vacuum degree of 1 ⁇ 10 ⁇ 2 Pa or less, a nitrogen gas atmosphere containing 0 to 4 vol% or less of hydrogen gas, or an inert gas atmosphere containing 0 to 4 vol% or less of hydrogen gas. And so on.
  • the temperature of the molten metal at the time of spraying is preferably "each melting point + 100 ° C. or higher depending on the type of alloy of the first element and the second element", and "the first element and the second element It is more preferable to carry out at each melting point + 150 to 250 ° C. depending on the type of alloy. This is because if the temperature is too high, cooling during granulation is not sufficiently performed, it is difficult to form powder, and production efficiency is not good.
  • the temperature is too low, a problem that nozzle clogging at the time of injection is likely to occur tends to occur.
  • Nitrogen, argon, etc. are used as the gas for spraying, but the gas is not limited to this.
  • the diameter of the precipitated particles corresponding to the islands of the sea-island structure may be small, and that state is already obtained at the stage of alloy powder and is maintained even after sintering or when a target is formed. Therefore, the generation of the phase containing a large amount of additives generated when the sputtering target is produced by the melting method is suppressed by producing the alloy powder through this step, and the alloy powder produced through this step is used.
  • the rapidly cooled powder has an elemental ratio of the first element to the second element in the raw material prepared in the first step.
  • the maximum major axis of the powder obtained by the atomizing method is 500 ⁇ m or less, preferably 400 ⁇ m or less, and more preferably 300 ⁇ m or less. If the maximum major axis of the powder is larger than 500 ⁇ m, the density will be insufficient even if the third step of sintering is performed, and when a thin film is formed using the target, particles will be mixed in and the film thickness will vary. Therefore, it is preferable to set the maximum major axis of the powder to 500 ⁇ m or less.
  • setting the maximum major axis to 500 ⁇ m or less means that particles having a major axis exceeding 500 ⁇ m are not included.
  • the method for manufacturing a sputtering target according to the present embodiment preferably further includes a classification step of removing particles having a maximum major axis of more than 500 ⁇ m from the alloy powder obtained by the atomizing method between the atomizing step and the sintering step. ..
  • a classification step of removing particles having a maximum major axis of more than 500 ⁇ m from the alloy powder obtained by the atomizing method between the atomizing step and the sintering step.
  • This step is a step of obtaining a target sintered body from the powder obtained in the second step.
  • sintering is performed by a hot press method (HP), a discharge plasma sintering method (SPS), or a hot isotropic pressure sintering method (HIP). Sintering is performed using the alloy powder of the first element and the second element obtained in the second step or the alloy powder classified in the classification step. It is preferable that any of the powders shown above is packed in a mold, the powder is sealed with a mold and a punch or the like with a preliminary pressure of 10 to 30 MPa, and then sintered.
  • HP hot press method
  • SPS discharge plasma sintering method
  • HIP hot isotropic pressure sintering method
  • the sintering temperature is preferably 1100 to 2000 ° C., and the pressing force is preferably 40 to 196 MPa.
  • the sintering temperature is 1150 to 1300 ° C for the ruthenium-boron alloy powder, 1150 to 1500 ° C for the ruthenium-aluminum alloy powder, 1150 to 1600 ° C for the ruthenium-titanium alloy powder, and the ruthenium-zirconium alloy.
  • the atmosphere in the sintering apparatus is a vacuum atmosphere having a vacuum degree of 50 Pa or less, a nitrogen gas atmosphere containing 4 vol% or less of hydrogen gas, or an inert gas atmosphere containing 4 vol% or less of hydrogen gas. It is preferable that hydrogen gas is contained in an amount of 0.1 vol% or more.
  • the method of composition analysis in (Condition 3) or (Condition 4) is energy dispersive X-ray spectroscopy (EDS), high frequency inductively coupled plasma emission spectroscopy (ICP), or fluorescent X-ray analysis. XRF) and the like, but composition analysis by EDS is preferable.
  • EDS energy dispersive X-ray spectroscopy
  • ICP high frequency inductively coupled plasma emission spectroscopy
  • XRF fluorescent X-ray analysis.
  • composition analysis by EDS is preferable.
  • Example 1 The Ru raw material with a purity of 3N5up and the Nb raw material with a purity of 3N are put into a powder manufacturing apparatus, and then the inside of the powder manufacturing apparatus is adjusted to a vacuum atmosphere of 5 ⁇ 10 -3 Pa or less, and the Ru raw material is used at a melting temperature of 1900 ° C.
  • the Nb raw material is melted to form a molten metal, and then argon gas is sprayed onto the molten metal to scatter the molten metal to quench and solidify, and the Ru-20 atomic% Nb powder having a maximum major axis of 500 ⁇ m or less (in this case, Ru is 80 atoms). Although it is% Ru, the description of the atomic percentage of Ru is omitted.
  • the Ru-20 atomic% Nb powder having a maximum major axis of 500 ⁇ m or less was prepared by classification. Then, Ru-20 atomic% Nb powder was filled in a carbon mold for discharge plasma sintering (hereinafter, also referred to as SPS sintering). Next, the alloy powder was sealed with a mold and a punch by prepressing 30 MPa, and the mold filled with the alloy powder was installed in an SPS device (model number: SPS-825, manufactured by SPS Syntex).
  • the sintering was carried out under the conditions of the sintering temperature of 1250 ° C., the pressing force of 55 MPa, and the atmosphere in the sintering apparatus being a vacuum atmosphere of 20 Pa or less.
  • the Ru-20 atomic% Nb sintered body was processed using a grinding machine, a lathe, or the like to prepare a ⁇ 50.8 mm ⁇ 5 mmt Ru-20 atomic% Nb target of Example 1.
  • Example 1 (Comparative Example 1) In Example 1, instead of spraying argon gas on the molten metal to scatter the molten metal and quenching and solidifying to prepare Ru-20 atomic% Nb powder having a maximum major axis of 500 ⁇ m or less, argon gas is sprayed on the molten metal to spray the molten metal.
  • a Ru-20 atomic% Nb sintered body was obtained in the same manner as in Example 1 except that the Ru-20 atomic% Nb powder having a maximum major axis larger than 500 ⁇ m was prepared by scattering and quenching and solidifying.
  • the Ru-20 atomic% Nb powder having a maximum major axis larger than 500 ⁇ m was prepared by classification.
  • Comparative Example 2 Using pure Ru powder with a particle size of 100 ⁇ m or less and a purity of 3N5up and Nb powder with a particle size of 100 ⁇ m or less and a purity of 3N5up, adjust the amount of each powder to Ru-20 atomic% Nb and mix. gone. Then, in the same manner as in Examples, a Ru-20 atomic% Nb sintered body was produced. The sintered Ru-20 atomic% Nb sintered body was processed using a grinding machine, a lathe, or the like to prepare a ⁇ 50.8 mm ⁇ 5 mmt Ru-20 atomic% Nb target of Comparative Example 2.
  • Example 1 Comtent rate survey by EDS
  • the composition analysis of the Nb content of S1 to S9 in FIG. 1 and the Nb content of C1 to C9 in FIG. 2 was performed by energy dispersive X-ray spectroscopy (EDS). rice field.
  • the measurement range was 700 ⁇ m ⁇ 900 ⁇ m.
  • the measurement results are shown in Tables 2 to 5. From Table 2, the average value of the Nb content of S1 to S9 in Example 1 is 19.95%, and the average of the Nb content of each point of S1 to S9 and the Nb content of S1 to S9. The difference from the value was 0.41 at the maximum and 0.03 at the minimum in Example 1.
  • the average value of the Nb content of C1 to C9 in Example 1 is 20.04%, and the average of the Nb content of each point of C1 to C9 and the Nb content of C1 to C9.
  • the difference from the value was 0.52 at the maximum and 0.03 at the minimum in Example 1.
  • the target of Example 1 had a small deviation in composition due to a difference in location in both the in-plane direction of the spatter surface and the thickness direction of the target.
  • the average value of the Nb content of S1 to S9 and C1 to C9 in Example 1 is 19.99%, which is the same as the Nb content of each point of S1 to S9 and C1 to C9.
  • the difference between the average values of the Nb contents of S1 to S9 and C1 to C9 was 0.47 at the maximum and 0.00 at the minimum in Example 1.
  • the deviation of the composition at each point was small, that is, the deviation of the composition due to the difference in the location in the in-plane direction and the thickness direction of the target was small.
  • the average value of the Nb content of S1 to S9 in Comparative Example 2 is 20.00%, and the Nb content of each point of S1 to S9 and the Nb content of S1 to S9.
  • the difference from the average value was 0.98 at the maximum and 0.25 at the minimum.
  • the average value of the Nb content of C1 to C9 in Comparative Example 2 is 20.24%, and the average of the Nb content of each point of C1 to C9 and the Nb content of C1 to C9.
  • the difference from the value was 1.03 at the maximum and 0.06 at the minimum in Comparative Example 2.
  • the target of Comparative Example 2 had a small deviation in composition due to the difference in location in both the in-plane direction of the spatter surface and the thickness direction of the target.
  • the average value of the contents of S1 to S9 and C1 to C9Nb in Comparative Example 2 is 20.12%, and the content of Nb at each point of S1 to S9 and C1 to C9 and S1 to S1 to C9.
  • the difference between the average values of the Nb contents of S9 and C1 to C9 was 1.10 at the maximum and 0.18 at the minimum in Comparative Example 2.
  • the target of Comparative Example 2 had a small difference in composition at each point, that is, the difference in composition due to the difference in location in the in-plane direction and the thickness direction of the target was small.
  • the relative integral strength of the second peak is lower than 60% with respect to the relative integral strength of the first peak, and the sputtering target of Comparative Example 2 has a strong orientation in the (101) direction and a high degree of anisotropy. It was confirmed that. When a thin film was formed using this target, the sputtering rate differed from place to place, resulting in variations in film thickness.
  • Example 1 The oxygen and carbon contents of the targets of Example 1 and Comparative Example 2 were measured using a mass spectrometer (model number: Element GD, manufactured by Thermo Fisher Scientific). The measurement results are shown in Table 7.
  • the oxygen content of Example 1 was 43 ppm, the carbon content was 9 ppm, and the oxygen and carbon contents were low. Therefore, it can be dispersed in the sputtering target while suppressing the oxidation and carbonization of the additive element, and the composition of the film formed by using this target is adjusted with respect to the in-plane direction and the film thickness direction of the film. Was able to obtain a uniform composition distribution. In addition, it was possible to reduce the mixing of particles and suppress the variation in film thickness.
  • the oxygen content of Comparative Example 2 was 695 ppm, the carbon content was 13 ppm, and the oxygen content was high. For this reason, if the target is heated during film formation, oxygen may be combined with the additive components in the target to form an oxide. Therefore, when a thin film is formed using the target, The sputter rate was different depending on the location, and the film thickness varied.
  • the filling factors of the targets of Example 1, Comparative Example 1 and Comparative Example 2 were calculated using the Archimedes method. The calculation results are shown in Table 8.
  • the filling factor was a value obtained by dividing (measured density of the sintered body measured by the Archimedes method) by (theoretical density of the sintered body) and then multiplying by 100 in order to convert it into a percentage.
  • the filling rate of Example 1 was 99.7%, and a sputtering target having a high filling rate and few voids was obtained.
  • the filling rate of Comparative Example 1 was 75.2%, and a sputtering target having a low filling rate and many voids was obtained.
  • the filling rate of Comparative Example 2 was 99.9%, and a sputtering target having a high filling rate and few voids was obtained.
  • Example 1 From the results of Example 1 and Comparative Examples 1 to 3, in Example 1, the maximum major axis of the dispersed particles, the composition deviation, the ratio of the second peak relative integrated intensity to the first peak relative integrated intensity, and the oxygen content. It was a value that satisfied all of the amount, carbon content and filling rate. Therefore, it was possible to form a thin film having a small variation in the target Nb concentration. In addition, since it is possible to suppress the mixing of particles and the sputter rate is unlikely to differ depending on the location, it is possible to form a thin film with little deviation in film thickness and composition.
  • Comparative Example 2 since the ratio of the relative integral strength of the second peak to the relative integral strength of the first peak is small and the oxygen content is high, the film thickness is formed when the film is formed using the sputtering target. Has become uneven. In Comparative Example 3, since the dissolved ruthenium was too hard, cracks occurred during grinding and cutting, and it could not be produced.

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Abstract

La présente invention vise à fournir : une cible de pulvérisation qui permet d'obtenir une distribution compositionnelle uniforme dans la direction dans le plan et dans la direction de l'épaisseur du film par rapport à la structure compositionnelle d'un film déposé ; et un procédé de fabrication de la cible de pulvérisation. La cible de pulvérisation selon la présente invention est un alliage formé à partir d'un premier élément qui est du ruthénium et d'un second élément qui est un élément sélectionné parmi le bore, l'aluminium, le titane, le zirconium, le hafnium, le vanadium, le niobium, le tantale, le chrome, le molybdène et le tungstène. La cible de pulvérisation comprend des particules dispersées chacune formée de deux phases comprenant une phase de composé intermétallique comprenant les deux types d'éléments qui sont le premier élément et le second élément. L'axe principal maximal des particules dispersées n'est pas supérieur à 500 µm.
PCT/JP2021/022674 2020-06-30 2021-06-15 Cible de pulvérisation et procédé de fabrication associé WO2022004354A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004001092A1 (fr) * 2002-06-24 2003-12-31 Nikko Materials Company, Limited Cible de pulverisation alru et son procede de preparation
WO2006134743A1 (fr) * 2005-06-16 2006-12-21 Nippon Mining & Metals Co., Ltd. Cible de pulvérisation d’un alliage de ruthénium
WO2007097396A1 (fr) * 2006-02-22 2007-08-30 Nippon Mining & Metals Co., Ltd. Cible de pulverisation frittee faite de metaux a temperatures de fusion elevees
CN104032270A (zh) * 2014-06-12 2014-09-10 贵研铂业股份有限公司 一种大尺寸钌基合金溅射靶材及其制备方法
CN106756826A (zh) * 2016-11-25 2017-05-31 东莞市联洲知识产权运营管理有限公司 一种高纯度钽钌合金靶材及其制备方法
CN108754436A (zh) * 2018-06-25 2018-11-06 河南科技大学 一种高纯钽钌合金靶材的真空热压烧结制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004001092A1 (fr) * 2002-06-24 2003-12-31 Nikko Materials Company, Limited Cible de pulverisation alru et son procede de preparation
WO2006134743A1 (fr) * 2005-06-16 2006-12-21 Nippon Mining & Metals Co., Ltd. Cible de pulvérisation d’un alliage de ruthénium
WO2007097396A1 (fr) * 2006-02-22 2007-08-30 Nippon Mining & Metals Co., Ltd. Cible de pulverisation frittee faite de metaux a temperatures de fusion elevees
CN104032270A (zh) * 2014-06-12 2014-09-10 贵研铂业股份有限公司 一种大尺寸钌基合金溅射靶材及其制备方法
CN106756826A (zh) * 2016-11-25 2017-05-31 东莞市联洲知识产权运营管理有限公司 一种高纯度钽钌合金靶材及其制备方法
CN108754436A (zh) * 2018-06-25 2018-11-06 河南科技大学 一种高纯钽钌合金靶材的真空热压烧结制备方法

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