WO2019203258A1 - Cible de pulvérisation d'alliage cu-ni - Google Patents

Cible de pulvérisation d'alliage cu-ni Download PDF

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WO2019203258A1
WO2019203258A1 PCT/JP2019/016435 JP2019016435W WO2019203258A1 WO 2019203258 A1 WO2019203258 A1 WO 2019203258A1 JP 2019016435 W JP2019016435 W JP 2019016435W WO 2019203258 A1 WO2019203258 A1 WO 2019203258A1
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sputtering target
alloy
alloy sputtering
twin
range
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PCT/JP2019/016435
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English (en)
Japanese (ja)
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加藤　慎司
謙介 井尾
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三菱マテリアル株式会社
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Priority to KR1020207023750A priority Critical patent/KR20200144088A/ko
Priority to CN201980022696.9A priority patent/CN111936660A/zh
Publication of WO2019203258A1 publication Critical patent/WO2019203258A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • 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
    • 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working

Definitions

  • the present invention relates to a Cu—Ni alloy sputtering target used for forming a thin film of Cu—Ni alloy containing Ni and the balance being Cu and inevitable impurities.
  • the Cu—Ni alloy described above is used as a wiring film for displays and the like because it is excellent in low reflection, heat resistance, and electrical characteristics as disclosed in Patent Document 1, for example. Further, as described in, for example, Patent Documents 2 to 4, it is also used as a base film for copper wiring. Furthermore, a Cu—Ni alloy containing 40 to 50 mass% of Ni is used as a thin film resistor for a strain gauge, for example, as shown in Patent Document 5 because of its low temperature coefficient of resistance. In addition, since this Cu—Ni alloy has a large electromotive force, it is used as a thin film thermocouple and a compensating conductor as shown in, for example, Patent Document 6-8. Furthermore, Cu—Ni alloys containing 22 mass% or less of Ni are also used as general electric resistors and low-temperature heating elements.
  • the thin film made of the Cu—Ni alloy as described above is formed by, for example, a sputtering method.
  • a Cu—Ni alloy sputtering target used for the sputtering method is conventionally manufactured by a melt casting method as shown in, for example, Patent Documents 9 and 10.
  • Patent Document 11 proposes a method for producing a sintered body of a Cu—Ni alloy.
  • JP 2017-005233 A Japanese Patent Laid-Open No. 05-251844 Japanese Patent Laid-Open No. 06-097616 JP 2010-199283 A Japanese Patent Laid-Open No. 04-346275 Japanese Patent Laid-Open No. 04-290245 JP-A-62-144074 Japanese Patent Laid-Open No. 06-104494 JP 2016-029216 A JP 2012-193444 A Japanese Patent Laid-Open No. 05-051662
  • the present invention has been made in view of the above circumstances, and provides a Cu—Ni alloy sputtering target capable of stably forming a Cu—Ni alloy film having a uniform film thickness and composition.
  • the purpose is to do.
  • the Cu—Ni alloy sputtering target of the present invention is a Cu—Ni alloy sputtering target containing Ni, with the balance being Cu and inevitable impurities, and the difference in orientation between adjacent crystal grains Is the total grain boundary length L, and the (111) plane and the (110) plane of the face-centered cubic crystal are the rotation axes. If the length of each grid point in the case of rotating is misorientation is confirmed three grain boundaries were the twin boundaries length L T, twin defined by L T / L ⁇ 100 The ratio is in the range of 35% to 65%.
  • the twin ratio specified as described above is 35% or more, the variation in the sputtering rate on the sputtering surface is reduced, and the uniform film thickness and composition are achieved.
  • Cu—Ni alloy film can be formed.
  • the twin rate is 65% or less, the occurrence of abnormal discharge during sputtering can be suppressed, splash and the like are reduced, and a Cu-Ni alloy film is stably formed with a uniform film thickness. can do.
  • the Ni content is preferably in the range of 16 mass% or more and 55 mass% or less, and the balance is preferably composed of Cu and inevitable impurities.
  • the Ni content is 16 mass% or more, a Cu—Ni alloy film having excellent corrosion resistance can be formed. Further, since the Ni content is 55 mass% or less, a Cu—Ni alloy film with low electrical resistance can be formed. Therefore, it is possible to form a Cu—Ni alloy film that is particularly suitable for applications requiring corrosion resistance and conductivity.
  • the average crystal grain size is preferably in the range of 5 ⁇ m to 100 ⁇ m. In this case, since the average crystal grain size is 100 ⁇ m or less, it is possible to sufficiently suppress the occurrence of abnormal discharge during sputtering film formation. Moreover, since the average crystal grain size is 5 ⁇ m or more, the manufacturing cost can be kept low.
  • a Cu—Ni alloy sputtering target capable of stably forming a Cu—Ni alloy film having a uniform film thickness and composition.
  • the Cu—Ni alloy sputtering target according to this embodiment is a Cu film used as a wiring film, a copper wiring base film, a strain gauge thin film resistor, a thin film thermocouple and a compensating conductor, a general electric resistor, a low temperature heating element, and the like. -Used when forming a Ni alloy thin film.
  • the Cu—Ni alloy sputtering target according to the present embodiment may be a rectangular flat plate type sputtering target having a rectangular sputtering surface or a disk type sputtering target having a circular sputtering surface.
  • a cylindrical sputtering target whose sputtering surface is a cylindrical surface may be used.
  • the Cu—Ni alloy sputtering target according to this embodiment has a composition containing Ni, with the balance being Cu and inevitable impurities. Since Ni and Cu form a complete solid solution as shown in the binary phase diagram of FIG. 1, the content of Ni can be appropriately set according to the required characteristics such as corrosion resistance and electrical resistance. preferable. In the Cu—Ni alloy sputtering target of this embodiment, the Ni content is in the range of 16 mass% or more and 55 mass% or less, and the balance is composed of Cu and inevitable impurities.
  • the length of the grain boundary formed between crystal grains in which the orientation difference between adjacent crystal grains is in the range of 5 ° to 180 °
  • the boundary length L is defined as the grain boundary length, which is an orientation difference in which three lattice points are confirmed when rotating with the (111) plane and the (110) plane of the face-centered cubic crystal as the rotation axis.
  • the twin ratio defined by L T / L ⁇ 100 is in the range of 35% to 65%.
  • the length of the grain boundary which is an orientation difference in which three lattice points are confirmed when the face-centered cubic (111) plane and the (110) plane are rotated as rotation axes” is “ ⁇ 3 (111 Is equivalent to “the length of the corresponding grain boundary”.
  • the twin ratio described above is calculated as follows.
  • the structure is observed with an EBSD device, the orientation difference between adjacent crystal grains is measured using analysis software, and the grain boundary whose orientation difference is in the range of 5 ° to 180 ° is extracted.
  • FIG. 2A is a diagram showing the result of grain boundary extraction, and the black line shows the grain boundary.
  • the length of the grain boundary thus extracted (black line in FIG. 2A) is measured, and the total grain boundary length L is calculated.
  • a grain boundary which is an orientation difference in which three lattice points are confirmed when rotating with the (111) plane and the (110) plane of the face-centered cubic crystal as a rotation axis is extracted as a twin grain boundary. .
  • FIG. 2B is a diagram showing the results of twin grain boundary extraction, and the black lines show twin grain boundaries.
  • extracted twin boundaries and measure the length of the (black lines in FIG. 2B), and calculates the twin boundaries length L T. Then, from the total grain boundary length L and twin boundaries length L T which is calculated as described above, twinning ratio defined by L T / L ⁇ 100 is calculated.
  • the average crystal grain size is in the range of 5 ⁇ m to 100 ⁇ m.
  • twin ratio the average crystal grain size, and the component composition are defined as described above in the Cu—Ni alloy sputtering target of the present embodiment.
  • twin ratio In the Cu—Ni alloy sputtering target, by reducing the crystal grain size, the difference in the sputtering rate is leveled, the sputtering rate is stabilized over the entire sputtering surface, and uniform film formation becomes possible.
  • making the crystal grain size finer than necessary leads to an increase in manufacturing cost and is difficult to realize industrially.
  • the twin ratio is high in the Cu—Ni alloy sputtering target, the sputtering rate is stabilized over the entire sputtering surface even if the crystal grain size is the same. Therefore, uniform film formation is possible without making the crystal grain size finer than necessary.
  • the twin ratio of the Cu—Ni alloy sputtering target according to the present embodiment is set in the range of 35% to 65%.
  • the lower limit of the twin rate is preferably 40% or more, more preferably 45% or more, while abnormal discharge during sputtering is further suppressed.
  • the upper limit of the twin ratio is preferably 60% or less, and more preferably 55% or less.
  • the average crystal grain size is preferably set to 100 ⁇ m or less.
  • the average crystal grain size is 5 ⁇ m or more.
  • the lower limit of the average crystal grain size is preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more.
  • the upper limit of the average crystal grain size is preferably 80 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the Ni content in the Cu—Ni alloy sputtering target is set according to the required characteristics of the formed Cu—Ni alloy film.
  • the Ni content in the Cu—Ni alloy sputtering target is preferably set to 16 mass% or more.
  • the Ni content in the Cu—Ni alloy sputtering target is preferably 55 mass% or less.
  • the specific resistance value of the Cu—Ni alloy sputtering target is 5 ⁇ 10 ⁇ 4 ⁇ cm or less.
  • the lower limit of the Ni content in the Cu—Ni alloy sputtering target is preferably 20 mass% or more, and more preferably 25 mass% or more.
  • the upper limit of the Ni content in the Cu—Ni alloy sputtering target is preferably 50 mass% or less, and preferably 45 mass% or less.
  • a method for manufacturing the Cu—Ni alloy sputtering target according to the present embodiment will be described.
  • a Cu—Ni alloy sputtering target is manufactured by a melt casting method or a powder sintering method. For this reason, below, the melt casting method and the manufacturing method by a powder sintering method are each demonstrated.
  • Cu raw material and Ni raw material are weighed so as to have a predetermined mixing ratio. It is preferable to use a Cu raw material having a purity of 99.99 mass% or more. Moreover, it is preferable to use a Ni raw material having a purity of 99.9 mass% or more. Specifically, oxygen-free copper is preferably used as the Cu material, and electrolytic Ni is preferably used as the Ni material.
  • the Cu raw material and Ni raw material weighed as described above are charged into a melting furnace and melted.
  • the Cu raw material and Ni raw material are dissolved in a vacuum or in an inert gas atmosphere (Ar, N 2, etc.).
  • the degree of vacuum is preferably 10 Pa or less.
  • the casting method is not particularly limited. In order to reduce the manufacturing cost, it is preferable to apply a continuous casting method, a semi-continuous casting method, or the like.
  • the hot rolling temperature is set in the range of 600 ° C. or higher and 1050 ° C. or lower.
  • the lower limit of the hot rolling temperature is preferably 650 ° C. or higher, and more preferably 700 ° C. or higher.
  • the upper limit of the hot rolling temperature is preferably 1000 ° C. or less, and more preferably 950 ° C. or less.
  • the total processing rate in the hot rolling step S02 is set to 70% or more.
  • the total processing rate in the hot rolling step S02 is preferably 75% or more, and more preferably 80% or more.
  • the processing rate per pass in the hot rolling step S02 is set to 15% or less.
  • the processing rate per pass in the hot rolling step S02 is preferably 14% or less, and more preferably 12% or less.
  • plastic processing step S03 Next, if necessary, the hot-rolled material is subjected to plastic working such as cold working or leveler processing to obtain a plastic working material. Also in this plastic working step S03, it is preferable to limit the working rate per pass to 15% or less.
  • heat treatment step S04 Next, heat treatment is performed on the hot-rolled material or the plastic processed material. If necessary, the plastic working step S03 and the heat treatment step S04 may be repeated.
  • the heat treatment temperature is preferably in the range of 800 ° C. to 1000 ° C.
  • the holding time at the heat treatment temperature is preferably in the range of 0.5 hour to 2 hours. By performing the final heat treatment under such conditions, the crystal grain size can be reduced.
  • the lower limit of the heat treatment temperature in the final heat treatment step S04 is preferably 820 ° C. or higher, and more preferably 850 ° C. or higher.
  • the upper limit of the heat treatment temperature in the final heat treatment step S04 is preferably 980 ° C.
  • the lower limit of the holding time of the final heat treatment step S04 is preferably 0.7 hours or more, and more preferably 0.8 hours or more.
  • the upper limit of the holding time of the final heat treatment step S04 is preferably 1.8 hours or less, and more preferably 1.5 hours or less.
  • Cu raw material and Ni raw material are weighed so as to have a predetermined mixing ratio. It is preferable to use a Cu raw material having a purity of 99.99 mass% or more. Moreover, it is preferable to use a Ni raw material having a purity of 99.9 mass% or more. Specifically, oxygen-free copper is preferably used as the Cu material, and electrolytic Ni is preferably used as the Ni material.
  • the Cu raw material and Ni raw material weighed as described above are filled in a crucible and heated to dissolve.
  • the crucible material ceramic refractories such as alumina, mullite, magnesia, zirconia, or carbon can be used.
  • it is placed in an alumina crucible and set in a gas atomizer.
  • Ar gas is injected while dropping molten metal from a nozzle, and gas atomized powder is produced.
  • the obtained gas atomized powder is classified by sieving to obtain a Cu—Ni alloy powder having a predetermined particle size.
  • the particle size of the Cu—Ni alloy powder is in the range of 5 ⁇ m to 300 ⁇ m.
  • the nozzle hole diameter is preferably in the range of 0.5 mm to 5.0 mm, and the Ar gas injection gas pressure is preferably in the range of 1 MPa to 10 MPa.
  • the obtained Cu—Ni alloy powder is pressurized and heated to obtain a sintered body having a predetermined shape.
  • a hot isostatic pressing method HIP
  • HP hot press method
  • a hot isostatic pressing method HIP
  • the twin ratio described above changes depending on the pressurizing pressure and sintering temperature in the sintering step S12.
  • the pressurization pressure in sintering process S12 is set in the range of 50 MPa or more and 150 MPa or less.
  • the lower limit of the pressure applied in the sintering step S12 is preferably 65 MPa or more, and more preferably 80 MPa or more.
  • the upper limit of the pressure applied in the sintering step S12 is preferably 135 MPa or less, and more preferably 120 MPa or less.
  • the sintering temperature in sintering process S12 is set in the range of 800 degreeC or more and 1200 degrees C or less.
  • the lower limit of the sintering temperature in the sintering step S12 is preferably 850 ° C. or higher, and more preferably 900 ° C. or higher.
  • the upper limit of the sintering temperature in the sintering step S12 is preferably 1150 ° C. or less, and more preferably 1100 ° C. or less.
  • the holding time at the sintering temperature in the sintering step S12 is preferably in the range of 1 hour to 6 hours.
  • the twin ratio is 35% or more, the variation in the sputtering rate on the sputtering surface is reduced, and a uniform film is formed.
  • a Cu—Ni alloy film having a thickness and composition can be formed.
  • the twin rate is 65% or less, the occurrence of abnormal discharge during sputtering can be suppressed, and a Cu—Ni alloy film can be stably formed.
  • the Ni content when the Ni content is 16 mass% or more, a Cu—Ni alloy film excellent in corrosion resistance can be formed. Further, when the Ni content is 55 mass% or less, a Cu—Ni alloy film with low electrical resistance can be formed. Therefore, it is possible to form a Cu—Ni alloy film that is particularly suitable for applications requiring corrosion resistance and conductivity.
  • the sputtering rate can be further stabilized over the entire sputtering surface, and abnormal discharge during sputtering film formation can be achieved. Can be further suppressed.
  • the average crystal grain size is 5 ⁇ m or more, an increase in manufacturing cost can be suppressed.
  • the hot rolling temperature in the hot rolling step S02 is in the range of 600 ° C. or higher and 1050 ° C. or lower, and the total processing rate is 70. % Or more, the above-mentioned twin ratio can be made 35% to 65%.
  • the heat treatment temperature is in the range of 800 ° C. to 1000 ° C.
  • the holding time at the heat treatment temperature is in the range of 0.5 hours to 2 hours, so the average crystal grain size is 100 ⁇ m. It can be as follows. Furthermore, since the working rate per pass is limited to 15% or less in the hot rolling step S02 and the plastic working step S03, variation in twin ratio can be suppressed.
  • the pressure applied in the sintering step S12 is set in the range of 50 MPa to 150 MPa, and the sintering in the sintering step S12 is performed. Since the temperature is in the range of 800 ° C. or more and 1200 ° C. or less, the above-described twin rate can be made 35% or more and 65% or less.
  • melt casting method shown in FIG. 3 and the powder sintering method shown in FIG. 4 have been described as examples of the manufacturing method of the Cu—Ni alloy sputtering target, but the present invention is not limited to this.
  • the manufacturing method There is no particular limitation on the manufacturing method as long as the twin rate is in the range of 35% to 65%.
  • Cu—Ni alloy sputtering targets of Invention Examples 1 to 10 and Comparative Examples 1 and 2 were produced by a melt casting method as follows. Oxygen-free copper having a purity of 99.99 mass% was prepared as a Cu raw material, and electrolytic Ni having a purity of 99.9% or more was prepared as a Ni raw material. This was weighed so as to have the composition shown in Table 1. The weighed Cu raw material and Ni raw material were charged into a vacuum melting furnace and melted under the condition of a vacuum degree of 10 Pa. The obtained molten metal was cast into a mold to prepare a Cu—Ni alloy ingot. Next, this Cu—Ni alloy ingot was subjected to hot rolling under the conditions shown in Table 1 and final heat treatment was performed. The heat treatment time was 1.5 hours. The obtained plate was machined to obtain a Cu—Ni alloy sputtering target having a width of 150 mm ⁇ length of 500 mm ⁇ thickness of 15 mm.
  • Cu—Ni alloy sputtering targets of Invention Examples 11 to 17 and Comparative Examples 11 and 12 were produced by a powder sintering method as follows. Prepare oxygen free copper with a purity of 99.99 mass% as a Cu raw material, and electrolytic Ni with a purity of 99.9% or more as a Ni raw material, put this in an alumina crucible and set it in a gas atomizer, and an injection temperature of 1550 ° C. By performing atomization under the conditions of a propelling gas pressure of 5 MPa and a nozzle diameter of 1.5 mm, Cu—Ni alloy powders having compositions and particle sizes shown in Table 2 were obtained.
  • the obtained Cu—Ni alloy powder was pressed and heated by the HIP method under the conditions shown in Table 2 to obtain a sintered body.
  • the obtained sintered body was machined to obtain a Cu—Ni alloy sputtering target having a width of 150 mm ⁇ a length of 500 mm ⁇ a thickness of 15 mm.
  • the component composition, twin ratio, average crystal grain size, abnormal discharge, and film uniformity were evaluated as follows. The evaluation results are shown in Tables 3 and 4.
  • Component composition A measurement sample was collected from the obtained Cu—Ni alloy sputtering target, and the Ni content was measured using an XRF apparatus (ZSX Primus II manufactured by Rigaku Corporation). About Cu and other components, it described as a remainder.
  • twin ratio Using the sputtering surface of the obtained Cu-Ni alloy sputtering target as the observation surface, the microstructure was observed using an EBSD device (TSL Solutions OIM Data Collection 5), and the orientation difference between adjacent crystal grains was determined using analysis software. Measured, grain boundaries whose orientation difference was in the range of 5 ° to 180 ° were extracted, and the total grain boundary length L was calculated. In addition, the grain boundary which is an orientation difference in which three lattice points are confirmed when rotating with the (111) plane and the (110) plane of the face-centered cubic crystal as the rotation axis, that is, the correspondence of ⁇ 3 (111) extract the grain boundaries as twin boundaries, were calculated twin boundaries length L T.
  • the corresponding grain boundary of ⁇ 3 (111) refers to a symmetric boundary having an orientation difference of 60 degrees on the (111) plane. Then, from the total grain boundary length L and twin boundaries length L T which is calculated as described above, it was calculated twinning ratio defined by L T / L ⁇ 100.
  • twin ratio as shown in FIG. 5, on the sputtering surface of the Cu—Ni alloy sputtering target, the intersection (1) where the diagonal lines intersect and the corners (2), (3), (4) on each diagonal line ) And (5) were measured for twin ratios, and the average value of twin ratios measured at 5 points and the difference between the maximum and minimum values were shown as variations in Tables 3 and 4. Corners (2), (3), (4), and (5) were within a range of 10% or less of the total diagonal length from the corners toward the inside.
  • the film thickness was evaluated as follows. A Cu—Ni alloy sputtering target was soldered to an oxygen-free copper backing plate, and this was mounted on a magnetron DC sputtering apparatus. A 100 mm square glass substrate was prepared, and sputtering film formation was performed on the surface of the glass substrate with a target film thickness of 100 nm under the following conditions. Distance between target and substrate: 60mm Ultimate vacuum: 5 ⁇ 10 ⁇ 5 Pa Ar gas pressure: 0.3 Pa Sputter output: DC 1000W
  • each film thickness was measured using a level difference measuring device.
  • the difference between the maximum value and the minimum value of the measured film thickness is shown in Tables 3 and 4 as “film thickness difference”. Corners (2), (3), (4), and (5) were within a range of 10% or less of the total diagonal length from the corners toward the inside.
  • composition was evaluated as follows.
  • a Cu—Ni alloy sputtering target was soldered to an oxygen-free copper backing plate, and this was mounted on a magnetron DC sputtering apparatus.
  • a 100 mm square glass substrate was prepared, and sputter deposition was performed three times on the surface of the glass substrate with a target film thickness of 300 nm under the following conditions.
  • Ultimate vacuum 5 ⁇ 10 ⁇ 5 Pa Ar gas pressure: 0.3 Pa
  • Sputter output DC 1000W
  • Ni concentration / (Ni concentration + Cu concentration) ⁇ 100 This is performed every three film formations, and the difference between the maximum value and the minimum value of the Ni normalized concentration is shown in Tables 3 and 4 as “composition difference”.
  • the twinning ratio was as low as 30%. For this reason, the film thickness difference and the composition difference are large, and a uniform film cannot be formed.
  • the twinning ratio was as high as 70%.
  • the average crystal grain size was 120 ⁇ m. For this reason, the film thickness difference is large and a uniform film cannot be formed. In addition, the number of abnormal discharges was relatively large.
  • the twin ratio is 35% or more and 65%.
  • the film thickness difference and the composition difference were relatively small, and a uniform film could be formed.
  • Examples 1 to 6 and 8 to 10 of the present invention in which the final heat treatment temperature is 1000 ° C. or less can make the average crystal grain size smaller than that of Example 7 of the present invention in which the final heat treatment temperature is 1100 ° C. became.
  • a Cu—Ni alloy sputtering target capable of stably forming a Cu—Ni alloy film having a uniform film thickness and composition.

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Abstract

Selon l'invention, une cible de pulvérisation d'alliage Cu-Ni comprend Ni, le reste étant constitué de Cu et d'impuretés inévitables, le rapport des macles défini par l'expression LT/LT × 100 se situant dans la plage de 35% à 65%, L étant la longueur totale du joint de grain considérée comme la longueur du joint de grain formé entre des cristaux pour lesquels l'écart d'orientation entre des grains cristallins adjacents se situe dans la plage de 5° à 180°; et LT étant la longueur du contour cristallin des macles considérée comme la longueur d'un joint de grain qui est un écart d'orientation pour lequel chacun de trois noeuds est confirmé lorsque le plan (111) et le plan (110) d'un cristal cubique à faces centrées sont mis en rotation autour d'un axe de rotation.
PCT/JP2019/016435 2018-04-17 2019-04-17 Cible de pulvérisation d'alliage cu-ni WO2019203258A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020207023750A KR20200144088A (ko) 2018-04-17 2019-04-17 Cu-Ni 합금 스퍼터링 타깃
CN201980022696.9A CN111936660A (zh) 2018-04-17 2019-04-17 Cu-Ni合金溅射靶

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