CN111936660A - Cu-Ni alloy sputtering target - Google Patents

Cu-Ni alloy sputtering target Download PDF

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CN111936660A
CN111936660A CN201980022696.9A CN201980022696A CN111936660A CN 111936660 A CN111936660 A CN 111936660A CN 201980022696 A CN201980022696 A CN 201980022696A CN 111936660 A CN111936660 A CN 111936660A
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alloy
sputtering target
alloy sputtering
twin
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加藤慎司
井尾谦介
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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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
    • 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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Vapour Deposition (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention provides a Cu-Ni alloy sputtering target comprising Ni and the balance consisting of Cu and unavoidable impurities, wherein the Cu-Ni alloy sputtering target is adjacent to the Cu-Ni alloy sputtering targetThe length of a grain boundary formed between crystal grains having a difference in orientation between crystal grains in the range of 5 ° to 180 ° is defined as a total grain boundary length L, and the length of a grain boundary in which a difference in orientation of 3 lattice points is observed when the (111) plane and the (110) plane of a face-centered cubic lattice are rotated as rotation axes is defined as a twin crystal boundary length LTWhen is driven by LTThe twin ratio defined by/L x 100 is in the range of 35% or more and 65% or less.

Description

Cu-Ni alloy sputtering target
Technical Field
The present invention relates to a Cu — Ni alloy sputtering target used when forming a thin film of a Cu — Ni alloy containing Ni and the balance consisting of Cu and unavoidable impurities.
The present application claims priority based on patent application No. 2018-079126 filed in japanese application at 17.4.2018, and the contents of which are incorporated herein by reference.
Background
For example, as shown in patent document 1, the Cu — Ni alloy is excellent in low reflection, heat resistance, and electrical characteristics, and thus can be used as a wiring film for displays and the like. Further, as described in patent documents 2 to 4, for example, the film can be used as a base film of a copper wiring.
Further, since a Cu — Ni alloy containing 40 to 50 mass% of Ni has a small temperature coefficient of resistance, it can be used as a thin film resistance element for a strain gauge as shown in patent document 5, for example.
Further, since the Cu — Ni alloy has a large electromotive force, it can be used as a thin film thermocouple and a compensation lead wire, as shown in patent documents 6 to 8, for example.
Further, even in a Cu-Ni alloy containing not more than 22 mass% of Ni, it can be used as a general resistance element, a low-temperature heating element, or the like.
The thin film composed of the Cu — Ni alloy as described above is formed by, for example, a sputtering method. For example, as shown in patent documents 9 and 10, a Cu — Ni alloy sputtering target used in a conventional sputtering method is produced by a fusion casting method.
Further, patent document 11 proposes a method for producing a sintered body of a Cu — Ni alloy.
Patent document 1: japanese patent laid-open publication No. 2017-005233
Patent document 2: japanese laid-open patent publication No. H05-251844
Patent document 3: japanese laid-open patent publication No. H06-097616
Patent document 4: japanese laid-open patent application No. 2010-199283
Patent document 5: japanese laid-open patent publication No. H04-346275
Patent document 6: japanese laid-open patent publication No. H04-290245
Patent document 7: japanese laid-open patent publication No. 62-144074
Patent document 8: japanese laid-open patent publication No. H06-104494
Patent document 9: japanese patent laid-open publication No. 2016-029216
Patent document 10: japanese laid-open patent publication No. 2012 and 193444
Patent document 11: japanese laid-open patent publication No. H05-051662
In the Cu — Ni alloy film, if variations occur in film thickness and composition, variations occur in properties such as resistance in the film. Therefore, it is required to form a Cu — Ni alloy film having a uniform film thickness and composition.
Further, when the grain size of the Cu — Ni alloy sputtering target is coarsened, abnormal discharge is likely to occur, and thus sputtering deposition cannot be stably performed.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a Cu — Ni alloy sputtering target capable of stably forming a Cu — Ni alloy film having a uniform film thickness and composition.
In order to solve the above problems, a Cu — Ni alloy sputtering target of the present invention includes Ni, and the balance is made up of Cu and unavoidable impurities, and is characterized in that the length of a grain boundary formed between crystal grains having a misorientation between adjacent crystal grains in a range of 5 ° to 180 ° is defined as a total grain boundary length L, and when (111) plane and (110) plane of a face-centered cubic lattice are rotated as a rotation axisThe lengths of the grain boundaries in which the misorientation of 3 lattice points was confirmed were each the twin crystal boundary length LTWhen is driven by LTThe twin ratio defined by/L x 100 is set in the range of 35% or more and 65% or less.
According to the Cu — Ni alloy sputtering target having such a structure, since the twin ratio is set to 35% or more as described above, variation in the sputtering rate on the sputtering surface is reduced, and a Cu — Ni alloy film having a uniform film thickness and composition can be formed.
Further, since the twin ratio is set to 65% or less, it is possible to suppress the occurrence of abnormal discharge during sputtering and reduce spatters and the like, and to stably form a Cu — Ni alloy film with a uniform film thickness.
In the Cu — Ni alloy sputtering target of the present invention, the composition is preferably such that the Ni content is set in the range of 16 mass% or more and 55 mass% or less, and the remainder is composed of Cu and unavoidable impurities.
In this case, since the Ni content is 16 mass% or more, a Cu — Ni alloy film having excellent corrosion resistance can be formed. Since the Ni content is 55 mass% or less, a Cu — Ni alloy film with low resistance can be formed. Therefore, a Cu — Ni alloy film particularly suitable for applications requiring corrosion resistance and electrical conductivity can be formed.
In the Cu — Ni alloy sputtering target of the present invention, the average crystal grain size is preferably set in the range of 5 μm to 100 μm.
In this case, the average crystal grain size is set to 100 μm or less, and therefore, the occurrence of abnormal discharge during sputtering film formation can be sufficiently suppressed. Further, since the average crystal grain diameter is set to 5 μm or more, the manufacturing cost can be kept low.
According to the present invention, a Cu — Ni alloy sputtering target capable of stably forming a Cu — Ni alloy film having a uniform film thickness and composition can be provided.
Drawings
Fig. 1 is a binary state diagram of Cu and Ni.
Fig. 2A is a schematic diagram showing an example of the measurement result of the twin crystal ratio of the Cu — Ni alloy sputtering target of the present embodiment.
Fig. 2B is a schematic diagram showing an example of the measurement result of the twin crystal ratio of the Cu — Ni alloy sputtering target of the present embodiment.
Fig. 3 is a flowchart showing an example of the method for producing the Cu — Ni alloy sputtering target according to the present embodiment.
Fig. 4 is a flowchart showing an example of the method for producing the Cu — Ni alloy sputtering target according to the present embodiment.
FIG. 5 is an explanatory view showing the measurement position of the twin crystal ratio on the sputtering surface of the Cu-Ni alloy sputtering target in the examples.
FIG. 6 is an explanatory diagram showing the measurement positions of the film thicknesses of Cu-Ni alloy films in examples.
Detailed Description
Hereinafter, a Cu — Ni alloy sputtering target according to an embodiment of the present invention will be described.
The Cu — Ni alloy sputtering target of the present embodiment is used for forming a Cu — Ni alloy thin film used as a wiring film, an underlayer of a copper wiring, a thin film resistance element for a strain gauge, a thin film thermocouple, a compensation wire, a general resistance element, a low-temperature heating element, or the like.
The Cu — Ni alloy sputtering target of the present embodiment may be a rectangular flat plate sputtering target having a rectangular sputtering surface or a circular plate sputtering target having a circular sputtering surface. Alternatively, a cylindrical sputtering target having a cylindrical sputtering surface may be used.
The Cu — Ni alloy sputtering target of the present embodiment is formed to contain Ni and have a composition in which the remainder is composed of Cu and unavoidable impurities. As shown in the binary state diagram of fig. 1, Ni and Cu form a complete solid solution, and therefore the Ni content is preferably set as appropriate in accordance with the characteristics such as the required corrosion resistance and electric resistance.
The Cu — Ni alloy sputtering target of the present embodiment has a composition in which the Ni content is set to be in a range of 16 mass% to 55 mass%, and the remainder is composed of Cu and unavoidable impurities.
Then, in the Cu — Ni alloy sputtering target of the present embodiment, the adjacent crystal grains are formedThe length of a grain boundary formed between crystal grains having a difference in orientation between them in the range of 5 ° to 180 ° is defined as a total grain boundary length L, and the length of a grain boundary in which a difference in orientation of 3 lattice points is observed when the (111) plane and the (110) plane of a face-centered cubic lattice are rotated as axes of rotation is defined as a twin crystal boundary length LTWhen is driven by LTThe twin ratio defined by/L x 100 is set in the range of 35% or more and 65% or less. The meaning of "the length of the grain boundary in which the misorientation of 3 lattice points is observed when the (111) plane and the (110) plane of the face-centered cubic lattice rotate as the rotation axis" is the same as the meaning of "the length of the double site grain boundary of Σ 3 (111)".
The twin ratio described above is calculated in the following manner. The structure was observed by an EBSD apparatus, and the difference in orientation between adjacent crystal grains was measured by using analysis software, and grain boundaries having a difference in orientation in the range of 5 ° or more and 180 ° or less were extracted. Fig. 2A is a graph showing the extraction result of the grain boundaries, and the black lines show the grain boundaries. The length of the grain boundary thus extracted (black line in fig. 2A) was measured, and the total grain boundary length L was calculated.
Next, when the (111) plane and the (110) plane of the face-centered cubic lattice were rotated as rotation axes, a grain boundary in which the orientation difference of 3 lattice points was observed was extracted as a twin crystal boundary. When the (111) plane and the (110) plane of the face-centered cubic lattice are rotated as rotation axes, the grain boundaries where the misorientation of 3 lattice points is observed represent the double-site grain boundaries of Σ 3 (111). Fig. 2B is a graph showing the extraction result of the twin crystal boundaries, and the black lines show the twin crystal boundaries. The length of the thus extracted twin crystal boundary (black line in fig. 2B) was measured, and the twin crystal boundary length L was calculatedT。
Then, the total grain boundary length L and the twin grain boundary length L calculated in the above mannerTCalculate the sum of LTTwin ratio defined by/L × 100.
In the Cu — Ni alloy sputtering target of the present embodiment, the average crystal grain size is set to be in the range of 5 μm to 100 μm.
The reason why the twin ratio, the average crystal grain diameter, and the composition of the components are defined as described above in the Cu — Ni alloy sputtering target of the present embodiment will be described below.
(twin ratio)
In a Cu-Ni alloy sputtering target, the grain size is made fine, so that the difference in sputtering rate is averaged, and the sputtering rate of the entire sputtering surface is stabilized, thereby enabling uniform film formation. However, excessive miniaturization of the crystal grain diameter leads to an increase in manufacturing cost, and thus is industrially difficult to achieve.
In a Cu-Ni alloy sputtering target, when the twin ratio is high, the sputtering rate of the entire sputtering surface is stable even if the crystal grain diameter is the same. Therefore, uniform film formation can be achieved without excessively refining the crystal grain size.
In the Cu — Ni alloy sputtering target, when the twin crystal ratio is less than 35%, the sputtering rate of the entire sputtering surface may not be stabilized. On the other hand, when the twin ratio exceeds 65%, there is a concern that abnormal discharge may occur during sputtering.
Therefore, the twin ratio of the Cu — Ni alloy sputtering target of the present embodiment is set to be in the range of 35% to 65%.
The lower limit of the twin ratio is preferably 40% or more, and more preferably 45% or more in order to further stabilize the sputtering rate of the entire sputtering surface, and the upper limit of the twin ratio is preferably 60% or less, and more preferably 55% or less in order to further suppress abnormal discharge during sputtering.
(average grain size)
As described above, in the Cu — Ni alloy sputtering target, the sputtering rate of the entire sputtering surface can be stabilized by making the grain size finer. Further, if the grain size is coarsened, abnormal discharge may occur during sputtering film formation.
Therefore, in the present embodiment, in order to further stabilize the sputtering rate of the entire sputtering surface and suppress the occurrence of abnormal discharge during sputter film formation, it is preferable to set the average crystal grain diameter to 100 μm or less. On the other hand, in order to further suppress an increase in production cost, it is preferable to set the average crystal grain diameter to 5 μm or more.
The lower limit of the average crystal grain size is preferably 10 μm or more, and more preferably 20 μm or more. The upper limit of the average crystal grain size is preferably 80 μm or less, and more preferably 50 μm or less.
(composition of ingredients)
As described above, since Ni and Cu form a complete solid solution, the characteristics of the Cu — Ni alloy film, such as resistance and corrosion resistance, can be controlled by adjusting the Ni content. Therefore, the Ni content in the Cu — Ni alloy sputtering target is set according to the required characteristics of the formed Cu — Ni alloy film.
When a Cu — Ni alloy film having sufficiently excellent corrosion resistance is formed, the Ni content in the Cu — Ni alloy sputtering target is preferably 16 mass% or more. On the other hand, when the electrical resistance of the Cu — Ni alloy film is suppressed to be low to ensure the electrical conductivity, it is preferable that the Ni content in the Cu — Ni alloy sputtering target is 55 mass% or less, and the resistivity of the Cu — Ni alloy sputtering target thus produced is 5 × 10-4Omega cm or less.
When a Cu — Ni alloy film having further excellent corrosion resistance is to be formed, 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. On the other hand, when the electrical resistance of the Cu — Ni alloy film is further suppressed to be low, the upper limit of the Ni content in the Cu — Ni alloy sputtering target is preferably 50 mass% or less, and more preferably 45 mass% or less.
Next, a method for manufacturing the Cu — Ni alloy sputtering target according to the present embodiment will be described.
In the present embodiment, a Cu — Ni alloy sputtering target is manufactured by a fusion casting method or a powder sintering method. Therefore, the following describes the production method by the fusion casting method and the powder sintering method, respectively.
Next, a method for producing a Cu — Ni alloy sputtering target by the fusion casting method will be described with reference to a flowchart of fig. 3.
(fusion casting step S01)
The Cu raw material and the Ni raw material were weighed so as to be a prescribed formulation ratio. As the Cu raw material, a Cu raw material having a purity of 99.99 mass% or more is preferably used. As the Ni material, it is preferable to use a Ni material having a purity of 99.9 mass% or more. Specifically, oxygen-free copper is preferably used as the Cu raw material, and electrolytic Ni is preferably used as the Ni raw material.
The Cu raw material and the Ni raw material weighed as described above were charged into a melting furnace to be melted. In vacuum or in an inert gas atmosphere (Ar, N)2Etc.) of the Cu raw material and the Ni raw material. When the vacuum treatment is performed in a vacuum, the degree of vacuum is preferably 10Pa or less. In the case of performing the reaction in an inert gas atmosphere, it is preferable to introduce an inert gas after performing vacuum replacement until 10Pa or less.
When melting is performed in an atmospheric atmosphere, it is preferable to make the surface of the melt a reducing atmosphere by using a carbon crucible or covering the surface of the melt with carbon powder or the like.
Then, the obtained melt was poured into a casting mold, thereby obtaining a Cu — Ni alloy ingot. The casting method is not particularly limited. In order to reduce the production cost, it is preferable to use a continuous casting method, a semi-continuous casting method, or the like.
(Hot Rolling Process S02)
Subsequently, the obtained Cu — Ni alloy ingot was hot-rolled to obtain a hot-rolled material.
The twin ratio is changed by the hot rolling temperature and the total reduction ratio in the hot rolling step S02.
In the case where the hot rolling temperature is less than 600 ℃, there is a fear that the twin ratio becomes excessively high. On the other hand, in the case where the hot rolling temperature exceeds 1050 ℃, there is a fear that the twin ratio cannot be increased.
Therefore, in the present embodiment, the hot rolling temperature is set in the range of 600 ℃ to 1050 ℃.
The lower limit of the hot rolling temperature is preferably 650 ℃ or higher, and more preferably 700 ℃ or higher. On the other hand, the upper limit of the hot rolling temperature is preferably 1000 ℃ or lower, and more preferably 950 ℃ or lower.
If the total reduction ratio in the hot rolling step S02 is less than 70%, the twin ratio may not be increased.
Therefore, in the present embodiment, the total reduction ratio in the hot rolling step S02 is set to 70% or more.
The total reduction ratio in the hot rolling step S02 is preferably 75% or more, and more preferably 80% or more.
In the hot rolling step S02, the variation in twin ratio can be suppressed by suppressing the reduction ratio per 1 pass.
Therefore, in the present embodiment, the reduction ratio per 1 pass in the hot rolling step S02 is set to 15% or less.
The reduction ratio per 1 pass in the hot rolling step S02 is preferably 14% or less, and more preferably 12% or less.
(Plastic working Process S03)
Next, if necessary, the hot rolled material is subjected to plastic working such as cold working or straightening to obtain a plastic worked material. In the plastic working step S03, the working ratio is preferably limited to 15% or less per 1 pass.
(Heat treatment step S04)
Subsequently, the hot rolled material or the plastic working material is subjected to heat treatment. The plastic working step S03 and the heat treatment step S04 may be repeated as necessary.
In the final heat treatment step S04, it is preferable that the heat treatment temperature be in the range of 800 ℃ to 1000 ℃ and the holding time at the heat treatment temperature be in the range of 0.5 hours to 2 hours. By performing the final heat treatment under such conditions, the crystal grain size can be made finer.
The lower limit of the heat treatment temperature in the final heat treatment step S04 is preferably 820 ℃ or higher, and more preferably 850 ℃ or higher. The upper limit of the heat treatment temperature in the final heat treatment step S04 is preferably 980 ℃ or lower, and more preferably 950 ℃ or lower.
The lower limit of the holding time in 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 in the final heat treatment step S04 is preferably 1.8 hours or less, and more preferably 1.5 hours or less.
(machining operation S05)
After the final heat treatment, a Cu — Ni alloy sputtering target having a predetermined shape and size is obtained by machining.
Next, a method for producing a Cu — Ni alloy sputtering target by the powder sintering method will be described with reference to the flowchart of fig. 4.
(Cu-Ni alloy powder Forming Process S11)
The Cu raw material and the Ni raw material were weighed so as to be a prescribed formulation ratio. As the Cu raw material, a Cu raw material having a purity of 99.99 mass% or more is preferably used. As the Ni material, it is preferable to use a Ni material having a purity of 99.9 mass% or more. Specifically, oxygen-free copper is preferably used as the Cu raw material, and electrolytic Ni is preferably used as the Ni raw material.
The Cu raw material and the Ni raw material weighed as described above were filled into a crucible, and heated to be melted. As a material of the crucible, a ceramic refractory such as alumina, mullite, magnesia, or zirconia, or carbon can be used. For example, it is put in an alumina crucible and mounted on an atomizing device. After melting a Cu material and a Ni material in a vacuum atmosphere, an Ar gas was sprayed while dropping a melt from a nozzle to produce atomized powder. After cooling, the obtained atomized powder is classified by a sieve to obtain a Cu — Ni alloy powder having a predetermined particle diameter. In the present embodiment, the particle size of the Cu — Ni alloy powder is set in the range of 5 μm to 300 μm.
The aperture of the nozzle is preferably set in the range of 0.5mm to 5.0mm, and the injection pressure of the Ar gas is preferably set in the range of 1MPa to 10 MPa.
(sintering step S12)
Next, the obtained Cu — Ni alloy powder is pressurized and heated to obtain a sintered body having a predetermined shape. As the sintering method in the sintering step S12, for example, a hot isostatic pressing method (HIP), a hot pressing method (HP), or the like can be applied. In the present embodiment, a hot isostatic pressing method (HIP) is applied.
The twin ratio is changed by the pressure and the sintering temperature in the sintering step S12.
When the pressing pressure in the sintering step S12 is less than 50MPa, the twin ratio may not be increased. On the other hand, when the pressurization pressure in the sintering step S12 exceeds 150MPa, the twin ratio may excessively increase.
Therefore, in the present embodiment, the pressure in the sintering step S12 is set to be in the range of 50MPa to 150 MPa.
The lower limit of the pressure in the sintering step S12 is preferably 65MPa or more, and more preferably 80MPa or more. On the other hand, the upper limit of the pressure in the sintering step S12 is preferably 135MPa or less, and more preferably 120MPa or less.
When the sintering temperature in the sintering step S12 is less than 800 ℃, the twin ratio may not be increased. On the other hand, when the sintering temperature in the sintering step S12 exceeds 1200 ℃, the twin ratio may excessively increase.
Therefore, in the present embodiment, the sintering temperature in the sintering step S12 is set to be in the range of 800 ℃ to 1200 ℃.
The lower limit of the sintering temperature in the sintering step S12 is preferably 850 ℃ or higher, and more preferably 900 ℃ or higher. On the other hand, the upper limit of the sintering temperature in the sintering step S12 is preferably 1150 ℃ or less, and more preferably 1100 ℃ or less.
The holding time at the sintering temperature in the sintering step S12 is preferably set within a range of 1 hour to 6 hours.
(machining operation S13)
The sintered body obtained in the sintering step S12 is machined to obtain a Cu — Ni alloy sputtering target having a predetermined shape and size.
According to the Cu — Ni alloy sputtering target of the present embodiment having the above-described configuration, since the twin crystal ratio is set to 35% or more, variation in sputtering rate on the sputtering surface is reduced, and a Cu — Ni alloy film having a uniform film thickness and composition can be formed. On the other hand, since the twin ratio is set to 65% or less, it is possible to suppress the occurrence of abnormal discharge during sputtering and to stably form a Cu — Ni alloy film.
In the Cu — Ni alloy sputtering target according to the present embodiment, when the Ni content is 16 mass% or more, a Cu — Ni alloy film having excellent corrosion resistance can be formed. When the Ni content is 55 mass% or less, a Cu — Ni alloy film with low resistance can be formed. Therefore, a Cu — Ni alloy film particularly suitable for applications requiring corrosion resistance and electrical conductivity can be formed.
In the Cu — Ni alloy sputtering target according to the present embodiment, when the average crystal grain size is 100 μm or less, the sputtering rate of the entire sputtering surface can be further stabilized, and the occurrence of abnormal discharge during sputter deposition can be further suppressed. On the other hand, when the average crystal grain size is 5 μm or more, an increase in production cost can be suppressed.
In the present embodiment, when the Cu — Ni alloy sputtering target is produced by the fusion casting method, the twin ratio can be set to 35% to 65% because the hot rolling temperature in the hot rolling step S02 is set to 600 ℃ to 1050 ℃ and the total reduction ratio is set to 70% or more.
In the final heat treatment step S04, the heat treatment temperature is set to be in the range of 800 ℃ to 1000 ℃ inclusive, and the holding time at the heat treatment temperature is set to be in the range of 0.5 hours to 2 hours inclusive, so the average crystal grain size can be set to 100 μm or less.
In the hot rolling step S02 and the plastic working step S03, the reduction ratio per 1 pass is limited to 15% or less, and therefore variation in the twin ratio can be suppressed.
In the present embodiment, when the Cu — Ni alloy sputtering target is produced by the powder sintering method, the twin ratio can be set to 35% to 65% because the pressure applied in the sintering step S12 is set to 50MPa to 150MPa and the sintering temperature in the sintering step S12 is set to 800 ℃ to 1200 ℃.
Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and can be modified as appropriate without departing from the scope of the technical idea of the present invention.
For example, in the present embodiment, the fusion casting method shown in fig. 3 and the powder sintering method shown in fig. 4 are given as examples of the method for producing the Cu — Ni alloy sputtering target, but the method is not particularly limited as long as the twin ratio is within a range of 35% to 65%.
Examples
The results of the evaluation test for evaluating the Cu — Ni alloy sputtering target of the present invention will be described below.
First, Cu — Ni alloy sputtering targets of invention examples 1 to 10 and comparative examples 1 and 2 were produced by a fusion 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. It was weighed so as to be the compounding composition shown in table 1.
The weighed Cu raw material and Ni raw material were charged into a vacuum melting furnace and melted under a vacuum degree of 10 Pa. The obtained melt was poured into a mold to produce a Cu — Ni alloy ingot.
Next, the Cu — Ni alloy ingot was hot-rolled under the conditions shown in table 1, and subjected to final heat treatment. The heat treatment time was set to 1.5 hours.
The obtained plate material was subjected to mechanical working, thereby obtaining a Cu-Ni alloy sputtering target having a width of 150mm, a length of 500mm and a thickness of 15 mm.
Further, 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.
Oxygen-free copper having a purity of 99.99 mass% was prepared as a Cu raw material, electrolytic Ni having a purity of 99.9% or more was prepared as a Ni raw material, and the Ni raw material was placed in an alumina crucible and attached to an atomizing device, and atomized under conditions of an injection temperature of 1550 ℃, an injection pressure of 5MPa, and a nozzle diameter of 1.5mm, to obtain Cu — Ni alloy powders having the compositions and particle diameters shown in table 2.
The obtained Cu — Ni alloy powder was subjected to pressurization and heating under the conditions shown in table 2 by the HIP method to obtain a sintered body.
The obtained sintered body was subjected to mechanical processing, thereby obtaining a Cu-Ni alloy sputtering target having a width of 150 mm. times.a length of 500 mm. times.a thickness of 15 mm.
With respect to the Cu — Ni alloy sputtering target obtained in the above manner, the composition of the composition, the twin ratio, the average crystal grain diameter, the abnormal discharge, and the uniformity of the film (film thickness, composition) were evaluated in the following manner. The evaluation results are shown in tables 3 and 4.
(composition of ingredients)
A measurement sample was taken from the obtained Cu-Ni alloy sputtering target, and the Ni content was measured using an XRF device (ZSX PrimusII manufactured by Rigaku Corporation). Cu and other components are described as the remainder.
(twin ratio)
The sputtering surface of the obtained Cu — Ni alloy sputtering target was set as an observation surface, structure observation was performed using an EBSD apparatus (TSLSolutions OIM Data Collection 5), the misorientation between adjacent crystal grains was measured using analysis software, and the grain boundaries having misorientation in the range of 5 ° to 180 ° were extracted to calculate the total grain boundary length L.
Then, when the (111) plane and the (110) plane of the face-centered cubic crystal were rotated as the rotation axes, the double site grain boundary of Σ 3(111), which is a grain boundary in which the difference in orientation of 3 lattice points was observed, was extracted as a twin crystal boundary, and the twin crystal boundary length L was calculatedT。
The double-site grain boundary of Σ 3(111) means a symmetric boundary having a 60-degree orientation difference in the (111) plane.
Then, the total grain boundary length L and the twin grain boundary length L calculated in the above mannerTCalculate the sum of LTTwin ratio defined by/L × 100.
As for the twin ratio, as shown in fig. 5, the twin ratio was measured at 5 points of the intersection (1) where the diagonal lines intersect and the corner portions (2), (3), (4), and (5) on each diagonal line in the sputtering surface of the Cu — Ni alloy sputtering target, and the average value of the twin ratio measured at 5 points and the difference between the maximum value and the minimum value were marked as deviations in tables 3 and 4. The corners (2), (3), (4), and (5) are set within a range within 10% of the total length of the diagonal lines from the corner to the inside.
(average grain size)
A measurement sample was collected from the obtained Cu — Ni alloy sputtering target, and the sputtering surface was polished and observed for microstructure using an optical microscope, according to JIS H0501: 1986 (cutting method), the average grain diameter was calculated by measuring the grain diameter.
(abnormal discharge)
A Cu-Ni alloy sputtering target was welded to an oxygen-free copper backing plate and mounted in a magnetron DC sputtering apparatus.
Next, film formation by the sputtering method was continuously performed for 60 minutes under the following sputtering conditions. During this sputtering film formation, the number of occurrences of abnormal discharge was counted using an arc counter attached to the power supply of the DC sputtering apparatus.
Ultimate vacuum degree: 5X 10-5Pa
Ar gas pressure: 0.3Pa
And (3) sputtering output: DC 1000W
(uniformity of film)
The uniformity of the Cu-Ni alloy films formed using the Cu-Ni alloy sputtering targets of the present invention examples and comparative examples was evaluated by the film thickness and composition.
The film thickness was evaluated as follows.
A Cu-Ni alloy sputtering target was welded to an oxygen-free copper backing plate and mounted in a magnetron DC sputtering apparatus. A100 mm square glass substrate was prepared, and sputtering deposition was performed on the surface of the glass substrate under the following conditions with a target film thickness of 100 nm.
Distance between the target and the substrate: 60mm
Ultimate vacuum degree: 5X 10-5Pa
Ar gas pressure: 0.3Pa
And (3) sputtering output: DC 1000W
As shown in fig. 6, the Cu — Ni alloy film was formed, and each film thickness was measured at 5 points of the intersection (1) where the diagonals crossed and the corners (2), (3), (4), and (5) on each diagonal line using a step meter. The difference between the maximum value and the minimum value of the measured film thickness is shown as "film thickness difference" in tables 3 and 4. The corners (2), (3), (4), and (5) are set within a range within 10% of the total length of the diagonal lines from the corner to the inside.
The composition was evaluated as follows.
A Cu-Ni alloy sputtering target was welded to an oxygen-free copper backing plate and mounted in a magnetron DC sputtering apparatus. A100 mm square glass substrate was prepared, and 3 times of sputtering deposition was performed on the surface of the glass substrate under the following conditions with a target film thickness of 300 nm.
Ultimate vacuum degree: 5X 10-5Pa
Ar gas pressure: 0.3Pa
And (3) sputtering output: DC 1000W
The Cu concentration and the Ni concentration of the formed Cu — Ni alloy film were measured by an XRF apparatus (ZSX primus ii manufactured by Rigaku Corporation), and the Ni concentration was normalized by the following formula. The Cu concentration and the Ni concentration were calculated from the detection intensities of Cu and Ni using calibration curves.
Ni normalized concentration (Ni concentration/(Ni concentration + Cu concentration) × 100
This calculation was performed 3 times per film formation, and the difference between the maximum value and the minimum value of the normalized Ni concentration is shown as "composition difference" in tables 3 and 4.
[ Table 1]
Figure BDA0002703777290000121
[ Table 2]
Figure BDA0002703777290000122
[ Table 3]
Figure BDA0002703777290000131
[ Table 4]
Figure BDA0002703777290000132
In the fusion casting method, in comparative example 1 in which the total reduction ratio in the hot rolling process was set to 60%, the twin ratio was reduced to 30%. Therefore, the film thickness difference and the composition difference are large, and a uniform film cannot be formed.
In the fusion casting method, in comparative example 2 in which the hot rolling temperature in the hot rolling step was set to 400 ℃, the twin ratio was as high as 70%. The average grain size was 120 μm. Therefore, the difference in film thickness is large and a uniform film cannot be formed. In addition, the number of abnormal discharges is relatively large.
In the powder sintering method, in comparative example 11 in which the pressurization pressure in the sintering step was set to 10MPa, the twin ratio was reduced to 31%. Therefore, the film thickness difference and the composition difference are large, and a uniform film cannot be formed.
In the powder sintering method, in comparative example 12 in which the pressing pressure in the sintering step was set to 200MPa, the twin ratio was as high as 69%. Therefore, the difference in film thickness is large and a uniform film cannot be formed. In addition, the number of abnormal discharges is relatively large.
On the other hand, according to inventive examples 1 to 10 produced by the fusion casting method and inventive examples 11 to 17 produced by the powder sintering method, the twin ratio is set in the range of 35% or more and 65% or less, the difference in film thickness and the difference in composition are relatively small, and a uniform film can be formed.
In inventive examples 1 to 10 produced by the fusion casting method, the variation in twin ratio was suppressed in inventive examples 1 to 4 and inventive examples 6 to 10 in which the 1-pass reduction ratio was 15%, compared to inventive example 5 in which the 1-pass reduction ratio was 20%.
Further, in invention examples 1 to 6 and 8 to 10, in which the final heat treatment temperature was 1000 ℃ or lower, the average crystal grain size could be made smaller than in invention example 7, in which the final heat treatment temperature was 1100 ℃.
As described above, it was confirmed that the present invention provides a Cu — Ni alloy sputtering target capable of stably forming a Cu — Ni alloy film having a uniform film thickness and composition.
Industrial applicability
According to the present invention, a Cu — Ni alloy sputtering target capable of stably forming a Cu — Ni alloy film having a uniform film thickness and composition can be provided.

Claims (3)

1. A Cu-Ni alloy sputtering target comprising Ni and the balance consisting of Cu and unavoidable impurities, characterized in that,
the length of a grain boundary formed between crystal grains having a misorientation between adjacent crystal grains in the range of 5 DEG to 180 DEG is defined as a total grain boundary length L, and the length of a grain boundary in which misorientation is confirmed to 3 lattice points when the (111) plane and the (110) plane of a face-centered cubic lattice are rotated as a rotation axis is defined as a twin crystal boundary length LTWhen is driven by LTThe twin ratio defined by/L x 100 is in the range of 35% or more and 65% or less.
2. The Cu-Ni alloy sputtering target according to claim 1,
the composition is as follows: the content of Ni is in the range of 16 mass% or more and 55 mass% or less, and the remainder is composed of Cu and unavoidable impurities.
3. The Cu-Ni alloy sputtering target according to claim 1 or 2,
the average crystal grain diameter is in the range of 5 μm or more and 100 μm or less.
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