WO2022158231A1 - Ag alloy film, and ag alloy sputtering target - Google Patents

Ag alloy film, and ag alloy sputtering target Download PDF

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WO2022158231A1
WO2022158231A1 PCT/JP2021/047503 JP2021047503W WO2022158231A1 WO 2022158231 A1 WO2022158231 A1 WO 2022158231A1 JP 2021047503 W JP2021047503 W JP 2021047503W WO 2022158231 A1 WO2022158231 A1 WO 2022158231A1
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alloy
mass
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alloy film
content
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PCT/JP2021/047503
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French (fr)
Japanese (ja)
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悠人 歳森
智博 大谷
誠 漆原
荘平 野中
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三菱マテリアル株式会社
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Priority claimed from JP2021177712A external-priority patent/JP2022113107A/en
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    • 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
    • C22C5/06—Alloys based on silver
    • 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
    • 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
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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 invention relates to a Ga-containing Ag alloy film and an Ag alloy sputtering target used when forming this Ag alloy film.
  • This application claims priority based on Japanese Patent Application No. 2021-009035 filed in Japan on January 22, 2021 and Japanese Patent Application No. 2021-177712 filed in Japan on October 29, 2021. The contents are hereby incorporated by reference.
  • Ag films or Ag alloy films are excellent in optical properties and electrical properties, so they are used as reflective films and conductive films of various parts such as reflective electrode films such as displays and LEDs, and wiring films such as touch panels.
  • an Ag alloy film it is known that by adding a specific element to form an oxide on the surface of the film, for example, the reflectance and electrical conductivity can be improved when used as a reflective electrode film.
  • Patent Document 1 describes an Ag alloy film in which AgSbMg or AgSbZn is used as an Ag alloy and Sb is an oxide. Such Ag alloy films are said to be excellent in low resistance, heat resistance, and chloride resistance.
  • Patent Document 2 describes an Ag alloy film using AgIn as an Ag alloy and using In as an oxide.
  • Patent Document 3 describes an Ag alloy film in which AgSbAl or AgSbMn is used as an Ag alloy and Sb is an oxide. Such Ag alloy films are said to be excellent in low resistance, heat resistance, and chloride resistance.
  • Patent Document 4 describes an Ag alloy film using AgSb as an Ag alloy and Sb as an oxide. Such an Ag alloy film is said to have excellent moisture resistance, sulfurization resistance, heat resistance, high reflectance, and low resistance.
  • the various Ag alloy films described above are formed by sputtering targets made of Ag alloys.
  • the present invention has been made in view of the circumstances described above, and aims to provide an Ag alloy film having excellent heat resistance and sulfidation resistance, and an Ag alloy sputtering target for forming this Ag alloy film. aim.
  • the present inventors have made intensive studies and found that by forming a Ga segregation portion in which Ga is concentrated in the surface side region of the Ag alloy containing Ga, the heat resistance and It was found that sulfuration resistance can be improved.
  • an Ag alloy film according to an aspect of the present invention contains Ga in the range of 0.3% by mass to 3.5% by mass, and the balance is composed of Ag and unavoidable impurities, and the Ag alloy film has a Ga segregation portion in which Ga is concentrated in a surface side region of the Ag alloy film.
  • the Ag alloy film contains Ga in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities. Therefore, it has excellent heat resistance and is particularly suitable for use as a reflective conductive film, for example. Further, since the Ag alloy film has a Ga segregation portion in which Ga concentrates in the surface side region, the heat resistance and sulfuration resistance of the Ag alloy film can be improved.
  • the Ag alloy further includes one or more selected from Cu and Mg in a total amount of 0.5 mass ppm or more and 50.0 mass ppm or less. may be included in In this case, by adding Cu and Mg, it is possible to suppress the diffusion movement of Ag atoms due to heat, and to further improve the heat resistance of the Ag alloy film.
  • the Ag alloy further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 mass ppm or less, the Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 It is preferable that the mass ppm or more and 50 mass ppm or less.
  • Pd, Pt, Au, and Rh are solid-dissolved in Ag, so that heat resistance and sulfuration resistance can be further improved.
  • Pd, Pt, Au, and Rh act as catalysts in the reduction reaction of nitric acid. could be higher.
  • the Ag alloy may further contain Ca in the range of 0.005% by mass or more and 0.050% by mass or less.
  • Ca is segregated at the grain boundaries of Ag, grain boundary diffusion of Ag can be suppressed, and heat resistance can be further improved.
  • the Ag alloy further contains one or more selected from In, Sn, Ti, and Al in a total content of 0.1% by mass or more1. It may be contained in the range of 5% by mass or less. In this case, like Ga, In, Sn, Ti, and Al segregate in the surface-side region of the Ag alloy film, thereby further improving heat resistance and sulfurization resistance.
  • the length in the film thickness direction of the Ga segregation portion is preferably in the range of 2.0 nm or more and 12.0 nm or less.
  • the Ga segregation portion since the Ga segregation portion has a length in the film thickness direction within the above range, it is possible to sufficiently improve heat resistance and sulfurization resistance and prevent a decrease in reflectance.
  • Ga oxide may exist in the Ga segregation portion.
  • the presence of Ga oxide in the Ga segregation portion formed in the surface side region of the Ag alloy film can further improve the sulfuration resistance.
  • the Ga oxide is a transparent oxide, it can further improve the reflectance of the Ag alloy film.
  • the Ga segregation part may be distributed in a mesh shape along the grain boundaries as an oxide.
  • the Ga segregation portion formed in the surface side region of the Ag alloy film is distributed in a mesh shape along the grain boundaries as an oxide, so that the sulfidation resistance can be further improved, and the reflectance can be improved.
  • An Ag alloy sputtering target according to an aspect of the present invention contains Ga in the range of 0.3% by mass to 3.5% by mass, and the balance is Ag and inevitable impurities.
  • an Ag alloy film having a Ga segregation portion in which Ga is concentrated in the surface side region by sputtering and having excellent heat resistance and sulfidation resistance can be deposited.
  • the Ag alloy sputtering target according to one aspect of the present invention further contains one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less. good too.
  • the Ag alloy sputtering target according to one aspect of the present invention further contains one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less. good too.
  • the Ag alloy sputtering target according to one aspect of the present invention further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 ppm by mass or less.
  • the Pt content is 20 mass ppm or less
  • the Au content is 20 mass ppm or less
  • the Rh content is 10 mass ppm or less
  • the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 It may be mass ppm or less.
  • one or more selected from Pd, Pt, Au, and Rh are contained, and an Ag alloy film having excellent heat resistance and sulfurization resistance can be formed.
  • the Ag alloy sputtering target according to one aspect of the present invention may further contain Ca in the range of 0.005% by mass or more and 0.050% by mass or less.
  • an Ag alloy film containing Ca in addition to Ga and having excellent heat resistance can be formed.
  • one or more selected from In, Sn, Ti, and Al are added in a total amount of 0.1% by mass or more and 1.5% by mass or less. may be included in the range of In this case, in addition to Ga, it is possible to form an Ag alloy film containing one or more selected from In, Sn, Ti, and Al, and having excellent heat resistance and sulfurization resistance.
  • the oxygen content is preferably 0.005% by mass or less.
  • the oxygen content is limited to 0.005% by mass or less, it is possible to suppress the chemical adsorption of oxygen atoms to the growing Ag alloy film during the sputtering film formation. It is possible to suppress the deterioration of the properties.
  • the Ag alloy sputtering target is composed of a polycrystalline body containing a plurality of Ag alloy crystal grains, and is calculated from the grain size of the Ag alloy crystal grains measured at a plurality of measurement points.
  • the average grain size C is in the range of 10 ⁇ m or more and 200 ⁇ m or less, and the absolute deviation of the average grain size D from the average grain size C of the Ag alloy crystal grains at each measurement point
  • the grain size variation of the Ag alloy crystal grains is small and the average grain size C is within the above range, the occurrence of abnormal discharge during the sputtering film formation can be suppressed, and the Ag alloy can be stably formed.
  • a film can be deposited.
  • an Ag alloy film excellent in heat resistance and sulfidation resistance it is possible to provide an Ag alloy film excellent in heat resistance and sulfidation resistance, and an Ag alloy sputtering target for forming this Ag alloy film.
  • FIG. 10 is a graph showing the results of XPS analysis of the Ag alloy film (after heat treatment) of Inventive Example 102.
  • FIG. It is an example of the spectrum of the outermost surface of the Ag alloy film (after heat treatment) of Example 102 of the present invention. It is an example of the spectrum of the outermost surface of the Ag alloy film (before heat treatment) of Example 102 of the present invention. It is a surface observation result after heat processing of Ag alloy film in Example 120 of the present invention. 10 shows the surface observation results of the Ag alloy film after heat treatment in Comparative Example 101.
  • the Ag alloy film which is one embodiment of the present invention, is excellent in reflectance, heat resistance, and sulfidation resistance, and is particularly suitable for use as a reflective electrode film formed in contact with an organic layer in an organic EL device, for example. .
  • the Ag alloy film of the present embodiment contains Ga in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities.
  • a Ga segregation portion in which Ga is concentrated is formed in the side region.
  • This Ga segregation part is a part where the concentration of Ga is higher than other parts.
  • the portion where the Ga concentration is higher than other portions includes the surface side region of the Ag alloy film.
  • the Ga segregation part is not formed as a layer in which a clear interface or the like exists with the surrounding area, but a Ga concentration concentrated part where the concentration gradually changes from the Ga concentration peak position , identified by the peak intensity of the XPS analysis.
  • the Ag alloy film of the present embodiment contains Ga contained in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities, and the surface side region of the Ag alloy film A Ga segregation portion in which Ga is concentrated is formed in the .
  • a Ga segregation portion is formed in the surface side region of at least one of the two surfaces present at both ends in the film thickness direction of the Ag alloy film.
  • a Ga segregation portion is formed at least in the surface side region of the surface opposite to the substrate.
  • the Ga segregation portion may also be formed in the surface-side region of the substrate-side surface.
  • the surface side region of the Ag alloy film is a region extending from the surface of the Ag alloy film to 20% of the total thickness of the Ag alloy film in the thickness direction.
  • the Ag alloy constituting the Ag alloy film of the present embodiment further contains one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less. good.
  • the Ag alloy constituting the Ag alloy film of the present embodiment further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 ppm by mass or less.
  • the Pt content is 20 mass ppm or less
  • the Au content is 20 mass ppm or less
  • the Rh content is 10 mass ppm or less
  • the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 It may be mass ppm or less.
  • the Ag alloy forming the Ag alloy film of the present embodiment may further contain Ca in the range of 0.005% by mass or more and 0.050% by mass or less.
  • the Ag alloy constituting the Ag alloy film of the present embodiment one or two or more selected from In, Sn, Ti, and Al are further added in a total amount of 0.1% by mass or more and 1.5% by mass or less. may be included in the range of
  • the length in the film thickness direction of the Ga segregation portion is preferably in the range of 2.0 nm or more and 12.0 nm or less.
  • Ga oxide is preferably present in the Ga segregation portion.
  • the Ga segregation parts are preferably distributed as oxides in a network along the grain boundaries.
  • the Ga segregation part may be distributed entirely along the grain boundary as an oxide in the surface side region of the Ag alloy film, or may be distributed as an oxide. It may be partially distributed along grain boundaries.
  • the Ag alloy film contains oxygen, but the amount of oxygen is at the level of unavoidable impurities.
  • the Ag alloy sputtering target of the present embodiment is for forming the Ag alloy film of the above-described present embodiment, and has the same composition as the Ag alloy film to be formed. That is, it is composed of an Ag alloy having a composition containing Ga in the range of 0.3% by mass or more and 3.5% by mass or less, with the balance being Ag and unavoidable impurities.
  • one or more selected from Cu and Mg may be included in a total range of 0.5 ppm by mass or more and 50.0 ppm by mass or less.
  • it further contains one or more selected from Pd, Pt, Au, and Rh, the Pd content is 40 mass ppm or less, and the Pt content is 20 mass ppm.
  • the Au content may be 20 mass ppm or less
  • the Rh content may be 10 mass ppm or less
  • the total content of Pd, Pt, Au, and Rh may be 1 mass ppm or more and 50 mass ppm or less.
  • Ca may also be included in the range of 0.005% by mass or more and 0.050% by mass or less.
  • one or more selected from In, Sn, Ti, and Al may be contained in a total amount of 0.1% by mass or more and 1.5% by mass or less.
  • the oxygen content is preferably 50 mass ppm or less (0.005 mass% or less).
  • it is made of a polycrystalline body containing a plurality of Ag alloy crystal grains, and the average The crystal grain size C is in the range of 10 ⁇ m or more and 200 ⁇ m or less, and the absolute value of the deviation from the average crystal grain size C of the average value D of the grain size of the Ag alloy crystal grains at each measurement point.
  • the grain size variation E of the Ag alloy crystal grains defined by the following formula (1) is 20% or less, where D max is the average value at which the is maximum.
  • Formula: E (%) (D max -C) / C x 100
  • the Ga segregation portion of the Ag alloy film, the composition of the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target, the oxygen content of the Ag alloy sputtering target, and the crystal structure of the Ag alloy sputtering target are as described above. The reason for the stipulation is explained below.
  • Ga segregation part By forming a Ga segregation part in which Ga is segregated on the surface of the Ag alloy film, heat resistance and sulfurization resistance are improved, and it is possible to suppress the occurrence of protruding defects even in heat treatment and in a sulfurization atmosphere. .
  • a heat treatment at, for example, 200° C. or higher and 300° C. or lower can be performed to reliably form the Ga segregation part in the surface side region of the Ag alloy film.
  • the thickness direction length of the Ga segregation part is 1.0 nm or more, the heat resistance and the sulfuration resistance can be reliably improved. Further, when the length of the Ga segregation portion in the film thickness direction is 15.0 nm or less, it is possible to maintain a high reflectance. In order to more reliably improve the heat resistance and sulfuration resistance, it is more preferable to set the lower limit of the length of the Ga segregation portion in the film thickness direction to 5.0 nm or more. Further, in order to more reliably maintain a high reflectance, it is more preferable to set the upper limit of the length in the film thickness direction of the Ga segregation portion to 10.0 nm or less.
  • the sulfuration resistance of the Ag alloy film can be improved.
  • the Ga oxide formed in the surface-side region of the Ag alloy film acts as a stronger barrier against sulfur (hydrogen sulfide), improving the sulfuration resistance of the Ag alloy film.
  • the Ga oxide is a transparent oxide, it can improve the reflectance of the Ag alloy film.
  • the sulfuration resistance of the Ag alloy film can be further improved, and the reflectance of the Ag alloy film can be further improved. can be improved.
  • the Ga content in the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target is less than 0.3% by mass, the Ga segregation portion may not be sufficiently formed.
  • the Ga content exceeds 3.5% by mass the reflectance of the Ag alloy film may decrease. Therefore, in the present embodiment, the content of Ga in the Ag alloy forming the Ag alloy film and the Ag alloy sputtering target is set within the range of 0.3% by mass or more and 3.5% by mass or less.
  • the lower limit of the Ga content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more.
  • the upper limit of the Ga content is preferably 2.5% by mass or less, more preferably 2.0% by mass or less.
  • the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target contains, in addition to Ga, one or more selected from Cu and Mg in a total of 0.5 ppm by mass or more, the number of Ag atoms Diffusion due to heat can be suppressed, and heat resistance can be further improved.
  • the total content of one or more elements selected from Cu and Mg is more preferably 1.0 ppm by mass or more, more preferably 2.0 ppm by mass or more. is more preferable.
  • the upper limit of the total content of one or more selected from Cu and Mg is 20.0 ppm by mass or less, and 10.0 mass ppm. It is more preferable to make it below ppm.
  • the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target contains, in addition to Ga, one or more selected from Pd, Pt, Au, and Rh, and Pd, Pt and Au and Rh is 1 ppm by mass or more, these elements form a solid solution in Ag, thereby making it possible to further improve heat resistance and sulfurization resistance. Since elements such as Pd, Pt, Au, and Rh act as catalysts in the reduction reaction of nitric acid, when an Ag alloy film is etched with a nitric acid etchant, the etching rate of the film increases, and the etching process is stable.
  • the content of Pd is 40 ppm by mass or less
  • the content of Pt is 20 ppm by mass or less
  • the content of Au It is preferable that the amount is 20 mass ppm or less
  • the Rh content is 10 mass ppm or less
  • the total content of Pd, Pt, Au and Rh is 50 mass ppm or less.
  • the content of Pd is 40 ppm by mass or less
  • the content of Pt is 14 ppm by mass or less
  • the content of Au is 13 mass ppm or less
  • the Rh content is 10 mass ppm or less
  • the total content of Pd, Pt, Au and Rh is 50 mass ppm or less.
  • the total content of Pd, Pt, Au, and Rh is preferably 50 ppm by mass or less, and 40 mass It is more preferable to set it to ppm or less.
  • the total content of Pd, Pt, Au, and Rh is more preferably 2 ppm by mass or more, more preferably 3 ppm by mass or more.
  • the Pd content should be 20 mass ppm or less
  • the Pt content should be 10 mass ppm or less
  • the Au content should be 10 mass ppm or less
  • the Rh content should be 10 mass ppm or less.
  • the content of 8 ppm by mass or less, and the total content of Pd, Pt, Au and Rh is more preferably 20 ppm by mass or less, the Pd content is 10 mass ppm or less, and the Pt
  • the content is 5 ppm by mass or less
  • the content of Au is 5 ppm by mass or less
  • the content of Rh is 5 ppm by mass or less
  • the total content of Pd, Pt, Au and Rh is 10 ppm by mass or less. is more preferable.
  • the lower limits of the contents of Pd, Pt, Au, and Rh are not limited, but the content of Pd is 0.2 mass ppm or more, the Pt content is 0.01 mass ppm or more, and the Au content is 0.01 mass ppm or more. It is preferable to set the content of Rh to 2 ppm by mass or more and 0.01 ppm by mass or more.
  • the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target further contains 0.005% by mass or more of Ca in addition to Ga
  • the added Ca segregates at the grain boundary of Ag. It is possible to suppress the grain boundary diffusion of Ag and further improve the heat resistance.
  • the lower limit of the Ca content is more preferably 0.008% by mass or more, more preferably 0.010% by mass or more.
  • the upper limit of the Ca content is more preferably 0.040% by mass or less, and 0.030% by mass or less. is more preferred.
  • one or more selected from In, Sn, Ti, Al is added in a total of 0.1% by mass or more When it is contained, like Ga, In, Sn, Ti, and Al agglomerate in the surface-side region of the Ag alloy film, making it possible to further improve heat resistance and sulfurization resistance.
  • the total content of one or more selected from In, Sn, Ti, and Al may be set to 0.2% by mass or more.
  • the upper limit of the total content of one or more selected from In, Sn, Ti, and Al is 0.3% by mass or more.
  • the oxygen content of the Ag alloy sputtering target of the present embodiment when the oxygen content is 0.005% by mass or less, it is possible to suppress chemical adsorption of the oxygen element to the growing Ag alloy film during sputtering film formation. , deterioration of reflectance, heat resistance, and sulfidation resistance due to deterioration of crystallinity of the Ag alloy film can be suppressed.
  • the oxygen content of the Ag alloy sputtering target is more preferably 0.004% by mass or less, and more preferably 0.002% by mass. % or less.
  • the lower limit of the oxygen content of the Ag alloy sputtering target is preferably 0.001% by mass or more.
  • the average crystal grain size C of the Ag alloy crystal grains measured at a plurality of locations, and the average grain size of the Ag alloy crystal grains at each measured location. From the average value D max at which the absolute value of the deviation from the grain size C is maximum, when the grain size variation E of the Ag alloy crystal grains defined by the above formula (1) is set to 20% or less, It is possible to suppress the occurrence of unevenness on the sputtering surface even when sputtering progresses, and it is possible to suppress the occurrence of abnormal discharge during sputtering even after the sputtering progresses.
  • the lower limit of grain size variation E of Ag alloy crystal grains is not particularly limited, it is preferably 0.1% or more. Moreover, when the average crystal grain size C of the Ag alloy crystal grains is 200 ⁇ m or less, the occurrence of abnormal discharge can be suppressed. It should be noted that setting the average crystal grain size C of the Ag alloy crystal grains to less than 10 ⁇ m is not preferable because the manufacturing cost increases.
  • the grain size variation E of the Ag alloy crystal grains it is more preferable to set the grain size variation E of the Ag alloy crystal grains to 19% or less, more preferably 18% or less.
  • the average crystal grain size C of the Ag alloy crystal grains is more preferably 180 ⁇ m or less, more preferably 150 ⁇ m or less.
  • the lower limit of the average crystal grain size C of the Ag alloy crystal grains is more preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more.
  • an Ag raw material with a purity of 99.99% by mass or more and a Ga raw material with a purity of 99.9% by mass or more are prepared.
  • various raw materials (Cu, Mg, Pd, Pt, Au, Rh, Ca, In, Sn, Ti, Al) having a purity of 99.9% by mass or more are prepared as necessary.
  • the Ag raw material is leached with nitric acid or sulfuric acid, then electrorefined using an electrolytic solution having a predetermined silver concentration, and the refined Ag raw material is analyzed for impurities. It is preferable to reduce the amount of impurities in the Ag raw material by repeating these steps.
  • the above-mentioned Ag raw material, Ga raw material, and various raw materials according to need are weighed. Then, the Ag raw material is charged into the crucible of the atmosphere melting furnace. Next, the Ag raw material is melted under a high vacuum atmosphere or an inert gas atmosphere, and Ga and various raw materials are added to the obtained Ag molten metal to obtain an Ag alloy molten metal. An Ag alloy ingot is obtained by pouring this Ag alloy molten metal into a mold having a predetermined shape.
  • the easily oxidizable additive elements should be It is preferable to keep it in a state where it is not exposed to the atmosphere by vacuum packing or the like. Furthermore, it is preferable to keep the inside of the melting furnace in a state in which the operation of replacing the inert gas atmosphere has been performed several times during charging and melting. Moreover, in order to suppress the segregation of additive elements and variations in grain size in the Ag alloy ingot, it is preferable to pour the ingot into a water-cooled mold and rapidly cool it.
  • a unidirectional solidification method can be used.
  • the unidirectional solidification method for example, while the bottom of the mold is water-cooled, the molten metal is poured into the mold whose side parts are preheated by resistance heating, and then the set temperature of the resistance heating part at the bottom of the mold is gradually lowered.
  • a complete continuous casting method, a semi-continuous casting method, or the like may be used instead of the unidirectional solidification method described above.
  • the Ag alloy ingot is subjected to plastic working and formed into a predetermined shape.
  • the plastic working may be performed either hot or cold.
  • a plate material is formed by rolling an Ag alloy ingot.
  • the cumulative rolling reduction is 70% or more.
  • at least the last pass of rolling has a rolling reduction of 20% or more.
  • the heat treatment temperature is preferably 500° C. or higher and 700° C. or lower, and the holding time is preferably 1 hour or longer and 5 hours or shorter. Moreover, after the heat treatment, it is rapidly cooled by air cooling or water cooling.
  • the atmosphere for the heat treatment is not particularly limited, and may be, for example, an air atmosphere or an inert atmosphere.
  • the heat treatment temperature is less than 500° C., the effect of removing work hardening may not be sufficient.
  • the heat treatment temperature exceeds 700° C., the crystal grains may become coarse, or a liquid phase may appear.
  • the holding time is less than 1 hour, there is a possibility that the crystal grain size cannot be made sufficiently uniform.
  • the heat-treated material that has undergone the heat treatment described above is machined (cut) to finish it into a predetermined shape and dimensions.
  • the Ag alloy sputtering target of the present embodiment is manufactured through the steps described above.
  • the Ag alloy sputtering target of this embodiment is set in a target holder of a sputtering film forming apparatus. Then, a substrate on which a film is to be formed is attached, and an Ag alloy film is formed on the substrate.
  • An example of film formation conditions is shown below.
  • Deposition power density 2.0 to 5.0 (W/cm 2 )
  • Deposition gas Ar
  • Deposition gas pressure 0.2 to 0.4
  • Target-substrate distance 60 to 80 (mm)
  • a Ga segregation portion in which Ga is concentrated is formed in the surface side region of the Ag alloy film containing Ga.
  • the oxidation of Ga in the Ga segregation portion can be promoted.
  • a heat treatment condition for the Ag alloy film for example, it may be heated at 250 to 300° C. for about 1 to 2 hours in an atmosphere containing oxygen.
  • the atmosphere containing oxygen may be heating in an atmosphere containing 2% or more of oxygen, for example, air.
  • Ga is contained in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities. Since it is made of alloy, it has excellent heat resistance. Further, since the Ag alloy film has a Ga segregation portion in which Ga concentrates in the surface side region, the heat resistance and sulfuration resistance of the Ag alloy film can be improved.
  • Cu, and Mg in addition to Ga, when one or more selected from Cu and Mg are contained in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less , Cu, and Mg can suppress the diffusion movement of Ag atoms due to heat, and can further improve the heat resistance of the Ag alloy film.
  • the Ag alloy film of the present embodiment further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 ppm by mass or less, and the Pt The content of is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 mass ppm
  • Pd, Pt, Au, and Rh are solid-dissolved in Ag, so that heat resistance and sulfurization resistance can be further improved, and an etching solution containing nitric acid is used. The etching rate can be kept low even if the etching process is performed by
  • the Ag alloy film of the present embodiment in addition to Ga, when Ca is contained in the range of 0.005% by mass or more and 0.050% by mass or less, Ca segregates at the grain boundaries of Ag. By the presence of these elements, the grain boundary diffusion of Ag can be suppressed, and the heat resistance can be further improved.
  • In the Ag alloy film of the present embodiment in addition to Ga, one or more selected from In, Sn, Ti, and Al are added in a total amount of 0.1% by mass or more and 1.5% by mass or less. , In, Sn, Ti, and Al segregate in the surface-side region of the Ag alloy film in the same manner as Ga, thereby further improving heat resistance and sulfurization resistance.
  • the length in the film thickness direction of the Ga segregation part is within the range of 2.0 nm or more and 12.0 nm or less, the heat resistance and sulfuration resistance are sufficiently improved, and the reflection It is possible to prevent a decrease in the rate.
  • Ga oxide which is a transparent oxide
  • the reflectance of the Ag alloy film can be further improved, and the sulfidation resistance can be further improved. can be improved.
  • the Ga segregation part is distributed in a network along the grain boundary as an oxide, it is possible to further improve the sulfidation resistance and further improve the reflectance. can be made
  • the Ag alloy sputtering target of this embodiment by sputtering film formation, it has a Ga segregation part in which Ga is concentrated in the surface side region, and has excellent heat resistance and sulfidation resistance.
  • An alloy film can be deposited.
  • the Ag alloy sputtering target of the present embodiment in addition to Ga, when further containing one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less makes it possible to form an Ag alloy film with even better heat resistance.
  • the Ag alloy sputtering target of the present embodiment in addition to Ga, it further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 mass ppm or less, The Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh is 1 mass ppm or more and 50 mass ppm. When the concentration is set to ppm or less, an Ag alloy film having even better heat resistance and sulfurization resistance can be formed.
  • the Ag alloy sputtering target of the present embodiment in addition to Ga, when further containing Ca in the range of 0.005% by mass or more and 0.050% by mass or less, the Ag alloy film further excellent in heat resistance can be deposited.
  • the Ag alloy sputtering target of the present embodiment in addition to Ga, one or two or more selected from In, Sn, Ti, Al in a total amount of 0.1% by mass or more and 1.5% by mass or less When it is contained within the range, it is possible to form an Ag alloy film having even better heat resistance and sulfurization resistance.
  • the oxygen content is 0.005% by mass or less, it is possible to suppress the chemical adsorption of oxygen atoms to the growing Ag alloy film during sputtering film formation. It is possible to suppress deterioration of the reflectance, heat resistance, and sulfuration resistance of the Ag alloy film.
  • the average crystal grain size C calculated from the grain size of the Ag alloy crystal grains measured at a plurality of measurement points is within the range of 10 ⁇ m or more and 200 ⁇ m or less,
  • D max the average value of the average value D of the grain size of the Ag alloy crystal grains at each measurement point that has the maximum absolute value of the deviation from the average grain size C
  • E (%) (D max - C) / C ⁇ 100
  • the grain size variation E of the Ag alloy crystal grains is 20% or less, the occurrence of abnormal discharge during sputtering film formation can be suppressed, It becomes possible to form an Ag alloy film stably.
  • the present invention is not limited to this, and can be modified as appropriate without departing from the technical requirements of the invention.
  • a plate-shaped Ag alloy sputtering target has been described, but the present invention is not limited to this, and a cylindrical Ag alloy sputtering target may be used.
  • the obtained Ag alloy ingot was subjected to cold rolling (reduction rate of 80%, final reduction rate of 25%), and then heat treatment under conditions of a heat treatment temperature of 600°C and a holding time of 1 hour. Then, after the heat treatment, machining was performed to produce Ag alloy sputtering targets shown in Tables 1 to 3 in the form of discs having a diameter of 152.4 mm and a thickness of 6 mm.
  • an Ag alloy film was formed on a substrate under the following conditions.
  • film formation was performed for calculating the film formation rate.
  • an Ag alloy film having a film thickness of 100 nm was formed using the calculated film formation rate, and the Ag alloy films shown in Tables 4 to 6 were obtained.
  • Component composition A sample for analysis was cut out from each Ag alloy sputtering target, and the component composition was measured by ICP emission spectrometry. Further, the oxygen content was analyzed by heating a graphite crucible containing an analysis sample with high frequency, melting it in an inert gas, and detecting it by an infrared absorption method. The measurement results are shown in Tables 1-3.
  • the Ag alloy film As for the Ag alloy film, an Ag alloy film having a thickness of 500 nm was formed on a 4-inch silicon substrate by sputtering using the Ag alloy sputtering target described above. A sample for analysis was taken from this Ag alloy film, and the component composition was measured by ICP emission spectrometry. As a result, it was confirmed that the composition was the same as that of the Ag alloy sputtering target used for film formation.
  • the average value of the average grain sizes of the samples sampled from 16 locations was taken as the crystal grain size of the silver alloy crystal of the target.
  • the above average grain size d is the average value D of the grain size of the Ag alloy crystal grains at each measurement point, and the average value of the average grain size d at the 16 points is the average crystal grain size C.
  • the deviation between the average grain size C of the Ag alloy crystal grains measured at a plurality of locations and the average grain size C of the average value D of the grain size of the Ag alloy crystal grains at each measurement location The grain size variation E of the Ag alloy crystal grains was calculated from the average value D max that maximizes the absolute value of .
  • the absolute value of the deviation from the average value of the average particle diameter was identified.
  • the variation in particle size was calculated according to the following formula. ⁇
  • the inside of the sputtering apparatus was evacuated to 5 ⁇ 10 ⁇ 5 Pa, and then discharge was performed for 1 hour as preliminary sputtering under the conditions of Ar gas pressure: 0.4 Pa, input power: DC 500 W, and target-substrate distance: 70 mm. Next, continuous discharge was performed for 6 hours as the main sputtering, and the total number of abnormal discharges during the main sputtering was measured.
  • the arc count function of a DC power supply (RPDG-50A manufactured by MKS Instruments) was used to measure the abnormal discharge.
  • the peak intensity at the Ga peak position in the number of scans to excavate 50 nm is the Ga peak intensity (Ga amount) at a position at a depth of 50 nm from the surface.
  • the region of the number of scans in which the Ga peak intensity of 2.0 times or more the reference peak intensity described above is obtained is regarded as the Ga segregation portion where Ga is concentrated, and the thickness of the Ga segregation portion is set as described above. It was calculated by multiplying the number of scans by the etching rate.
  • the oxidation state of the Ga segregation part was confirmed from the position of each detected peak in the XPS depth analysis. Note that in reality, Ga is oxidized into Ga oxide Ga 2 O 3 by atmospheric transport, atmospheric heat treatment, etc. before the film is analyzed by XPS, so when using the peak intensity of Ga Similarly, the presence or absence of a Ga segregation part where Ga is concentrated may be judged from the change in the peak intensity of Ga 2 O 3 .
  • Each detection peak position is as follows. Ga: 1116.5 eV Ga2O3 : 1119.2 eV
  • FIG. 1 shows the XPS analysis results of the Ag alloy film (after heat treatment) of Example 102 of the present invention.
  • FIG. 2 shows the Ga2p3 spectrum (XPS) of the outermost surface of the Ag alloy film (after heat treatment) of Example 102 of the present invention. Ga is confirmed to be in an oxidized state. Regarding the intensity (Intensity) on the vertical axis in FIG. 1, the value of a ⁇ 10 b is expressed as aE+b.
  • FIG. 3 shows the Ga2p3 spectrum of the outermost surface of the Ag alloy film (before heat treatment) of Example 102 of the present invention. It has a peak between the metal and the oxide, confirming that Ga is in an incompletely oxidized state.
  • the reflectance was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). After film formation, heat treatment was performed at 250° C. for 2 hours in the air. Tables 4 to 6 show the reflectance of the Ag alloy film after this heat treatment. The table shows the reflectance at a wavelength of 450 nm.
  • a wiring pattern (wiring film) was formed by photolithography on a 100 nm-thick Ag alloy single film formed on a glass substrate. Specifically, a photoresist agent (OFPR-8600 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the formed Ag alloy film by a spin coater, and prebaked at 110°C. Then, it was exposed, and then the pattern was developed with a developing solution (NMD-W manufactured by Tokyo Ohka Kogyo Co., Ltd.) and post-baked at 150°C. Thus, a comb-shaped wiring pattern having a width of 100 ⁇ m and an interval of 100 ⁇ m was formed on the Ag alloy film.
  • a photoresist agent OFPR-8600 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • the Ga content is lower than the range of the present embodiment, and a Ga segregation part is formed in the surface side region of the Ag alloy film. it wasn't. Therefore, the heat resistance and sulfuration resistance were insufficient.
  • the Ga content is higher than the range of the present embodiment, and the reflectance after the formation of the Ag alloy film is low. rice field.
  • the Ag alloy film of Comparative Example 105 formed by the Ag alloy sputtering target of Comparative Example 5 the total content of Pd, Pt, Au and Rh is larger than the range of the present embodiment, and the amount of overetching is large. rice field.
  • Comparative Example 6 the Ca content was higher than the range of the present embodiment, cracks occurred during rolling, and an Ag alloy sputtering target could not be produced.
  • the total content of In, Sn, Ti, and Al was larger than the range of the present embodiment, and the reflectance after the formation of the Ag alloy film was low. .
  • the abnormal discharge during sputtering film formation could be suppressed, and the Ag alloy film could be stably formed.
  • the Ag alloy films of Inventive Examples 101 to 142 formed from the Ag alloy sputtering targets of Inventive Examples 1 to 42 had high reflectance and excellent heat resistance and sulfidation resistance. Also, the amount of over-etching was small.
  • the Ag alloy film of the present embodiment is excellent in heat resistance and sulfuration resistance, and is suitably applied as a reflective film and a conductive film for various parts such as reflective electrode films such as displays and LEDs, and wiring films such as touch panels.

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Abstract

This Ag alloy film is composed of an Ag alloy having a composition containing 0.3-3.5 mass% of Ga and the remainder comprising Ag and inevitable impurities, and has, in a surface-side region of the Ag alloy film, a Ga segregated portion in which Ga is concentrated. It is preferable that the length of the Ga segregated portion in the film thickness direction is within the range of 2.0-12.0 nm. In addition, it is preferable that a Ga oxide is present in the Ga segregated portion.

Description

Ａｇ合金膜、および、Ａｇ合金スパッタリングターゲットAg alloy film and Ag alloy sputtering target
　本発明は、Ｇａを含むＡｇ合金膜、および、このＡｇ合金膜を成膜する際に用いられるＡｇ合金スパッタリングターゲットに関するものである。
　本願は、２０２１年１月２２日に日本に出願された特願２０２１－００９０３５号、及び２０２１年１０月２９日に日本に出願された特願２０２１－１７７７１２号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a Ga-containing Ag alloy film and an Ag alloy sputtering target used when forming this Ag alloy film.
This application claims priority based on Japanese Patent Application No. 2021-009035 filed in Japan on January 22, 2021 and Japanese Patent Application No. 2021-177712 filed in Japan on October 29, 2021. The contents are hereby incorporated by reference.
　一般に、Ａｇ膜又はＡｇ合金膜は、光学特性および電気特性に優れていることから、ディスプレイやＬＥＤ等の反射電極膜、タッチパネル等の配線膜等の各種部品の反射膜及び導電膜として使用されている。
　Ａｇ合金膜として、特定の元素を添加して膜の表面に酸化物を形成するなどによって、例えば、反射電極膜として用いた際の反射率、導電率などを改善できることが知られている。
　例えば、特許文献１には、Ａｇ合金としてＡｇＳｂＭｇまたはＡｇＳｂＺｎを用い、Ｓｂを酸化物にしたＡｇ合金膜が記載されている。このようなＡｇ合金膜は、低抵抗性、耐熱性、および耐塩化性に優れているとされている。
　また、例えば、特許文献２には、Ａｇ合金としてＡｇＩｎを用い、Ｉｎを酸化物にしたＡｇ合金膜が記載されている。このようなＡｇ合金膜は、反射率を高めることができるとされている。
　また、例えば、特許文献３には、Ａｇ合金としてＡｇＳｂＡｌまたはＡｇＳｂＭｎを用いてＳｂを酸化物にしたＡｇ合金膜が記載されている。このようなＡｇ合金膜は、低抵抗性、耐熱性、および耐塩化性に優れているとされている。
　更に、例えば、特許文献４には、Ａｇ合金としてＡｇＳｂを用い、Ｓｂを酸化物にしたＡｇ合金膜が記載されている。このようなＡｇ合金膜は、耐湿性、耐硫化性、耐熱性に優れ、高反射率、かつ低抵抗であるとされている。
　ここで、上述の各種Ａｇ合金膜は、Ａｇ合金からなるスパッタリングターゲットによって成膜されている。 In general, Ag films or Ag alloy films are excellent in optical properties and electrical properties, so they are used as reflective films and conductive films of various parts such as reflective electrode films such as displays and LEDs, and wiring films such as touch panels. there is
As an Ag alloy film, it is known that by adding a specific element to form an oxide on the surface of the film, for example, the reflectance and electrical conductivity can be improved when used as a reflective electrode film.
For example, Patent Document 1 describes an Ag alloy film in which AgSbMg or AgSbZn is used as an Ag alloy and Sb is an oxide. Such Ag alloy films are said to be excellent in low resistance, heat resistance, and chloride resistance.
Further, for example, Patent Document 2 describes an Ag alloy film using AgIn as an Ag alloy and using In as an oxide. It is said that such an Ag alloy film can increase the reflectance.
Further, for example, Patent Document 3 describes an Ag alloy film in which AgSbAl or AgSbMn is used as an Ag alloy and Sb is an oxide. Such Ag alloy films are said to be excellent in low resistance, heat resistance, and chloride resistance.
Further, for example, Patent Document 4 describes an Ag alloy film using AgSb as an Ag alloy and Sb as an oxide. Such an Ag alloy film is said to have excellent moisture resistance, sulfurization resistance, heat resistance, high reflectance, and low resistance.
Here, the various Ag alloy films described above are formed by sputtering targets made of Ag alloys.
　ところで、上述のＡｇ合金膜においては、製造プロセス中の熱処理時の熱や雰囲気に含まれる微量の硫黄（硫化水素）により、Ａｇ合金膜の表面や端部に突起状の欠陥が生じ、電気的短絡などの原因となるおそれがあった。 By the way, in the Ag alloy film described above, due to heat during heat treatment during the manufacturing process and a small amount of sulfur (hydrogen sulfide) contained in the atmosphere, protruding defects occur on the surface and edges of the Ag alloy film, causing electrical damage. There was a risk of causing a short circuit or the like.
特開２０１４－０７４２２５号公報JP 2014-074225 A 特開２０１４－０１９９３２号公報JP 2014-019932 A 特開２０１４－００５５０３号公報JP 2014-005503 A 特開２０１３－２０９７２４号公報JP 2013-209724 A
　この発明は、前述した事情に鑑みてなされたものであって、耐熱性、耐硫化性に優れたＡｇ合金膜、およびこのＡｇ合金膜を成膜するためのＡｇ合金スパッタリングターゲットを提供することを目的とする。 The present invention has been made in view of the circumstances described above, and aims to provide an Ag alloy film having excellent heat resistance and sulfidation resistance, and an Ag alloy sputtering target for forming this Ag alloy film. aim.
　上記課題を解決するために、本発明者らが鋭意検討した結果、Ｇａを含むＡｇ合金の表面側領域に、Ｇａが濃集したＧａ偏析部を形成することによって、Ａｇ合金膜の耐熱性および耐硫化性を向上させることができるとの知見を得た。 In order to solve the above problems, the present inventors have made intensive studies and found that by forming a Ga segregation portion in which Ga is concentrated in the surface side region of the Ag alloy containing Ga, the heat resistance and It was found that sulfuration resistance can be improved.
　本発明は、上述の知見に基づいてなされたものであって、本発明の一態様に係るＡｇ合金膜は、Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金からなるＡｇ合金膜であって、前記Ａｇ合金膜の表面側領域に、Ｇａが濃集したＧａ偏析部を有することを特徴とする。 The present invention has been made based on the above findings, and an Ag alloy film according to an aspect of the present invention contains Ga in the range of 0.3% by mass to 3.5% by mass, and the balance is composed of Ag and unavoidable impurities, and the Ag alloy film has a Ga segregation portion in which Ga is concentrated in a surface side region of the Ag alloy film.
　本発明の一態様に係るＡｇ合金膜によれば、Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金で構成されているので、耐熱性に優れており、例えば反射導電膜用途として特に適している。
　そして、前記Ａｇ合金膜の表面側領域に、Ｇａが濃集したＧａ偏析部を有しているので、Ａｇ合金膜の耐熱性および耐硫化性を向上させることができる。 According to the Ag alloy film according to one aspect of the present invention, the Ag alloy film contains Ga in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities. Therefore, it has excellent heat resistance and is particularly suitable for use as a reflective conductive film, for example.
Further, since the Ag alloy film has a Ga segregation portion in which Ga concentrates in the surface side region, the heat resistance and sulfuration resistance of the Ag alloy film can be improved.
　ここで、本発明の一態様に係るＡｇ合金膜においては、前記Ａｇ合金は、さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含んでいてもよい。
　この場合、Ｃｕ，Ｍｇを添加することで、Ａｇ原子の熱による拡散移動を抑制でき、Ａｇ合金膜の耐熱性をさらに向上させることができる。 Here, in the Ag alloy film according to one aspect of the present invention, the Ag alloy further includes one or more selected from Cu and Mg in a total amount of 0.5 mass ppm or more and 50.0 mass ppm or less. may be included in
In this case, by adding Cu and Mg, it is possible to suppress the diffusion movement of Ag atoms due to heat, and to further improve the heat resistance of the Ag alloy film.
　また、本発明の一態様に係るＡｇ合金膜においては、前記Ａｇ合金は、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされていることが好ましい。
　この場合、Ｐｄ，Ｐｔ，Ａｕ，ＲｈがＡｇ中に固溶することで、耐熱性および耐硫化性をさらに向上させることが可能となる。
　また、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈは、硝酸の還元反応において触媒として作用するため、これらの元素を多く含むと、成膜したＡｇ合金膜を硝酸エッチング液でエッチングした際に膜のエッチングレートが高くなるおそれがある。このため、Ａｇ合金にＰｄ，Ｐｔ，Ａｕ，Ｒｈが含まれる場合、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈの含有量を上述のように制限することで、硝酸を含むエッチング液を用いてエッチング処理しても、エッチングレートを低く抑えることが可能となる。 Further, in the Ag alloy film according to one aspect of the present invention, the Ag alloy further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 mass ppm or less, the Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 It is preferable that the mass ppm or more and 50 mass ppm or less.
In this case, Pd, Pt, Au, and Rh are solid-dissolved in Ag, so that heat resistance and sulfuration resistance can be further improved.
In addition, Pd, Pt, Au, and Rh act as catalysts in the reduction reaction of nitric acid. could be higher. Therefore, when Pd, Pt, Au, and Rh are contained in the Ag alloy, by limiting the content of Pd, Pt, Au, and Rh as described above, etching is performed using an etchant containing nitric acid. Also, the etching rate can be kept low.
　また、本発明の一態様に係るＡｇ合金膜においては、前記Ａｇ合金は、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含んでいてもよい。
　この場合、ＣａがＡｇの結晶粒界に偏析して存在することにより、Ａｇの粒界拡散を抑制でき、さらに耐熱性を向上させることができる。 Moreover, in the Ag alloy film according to one aspect of the present invention, the Ag alloy may further contain Ca in the range of 0.005% by mass or more and 0.050% by mass or less.
In this case, since Ca is segregated at the grain boundaries of Ag, grain boundary diffusion of Ag can be suppressed, and heat resistance can be further improved.
　また、本発明の一態様に係るＡｇ合金膜においては、前記Ａｇ合金は、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含んでいてもよい。
　この場合、Ｇａと同様に、Ｉｎ，Ｓｎ，Ｔｉ，ＡｌがＡｇ合金膜の表面側領域に偏析することにより、耐熱性および耐硫化性をさらに向上させることができる。 In addition, in the Ag alloy film according to one aspect of the present invention, the Ag alloy further contains one or more selected from In, Sn, Ti, and Al in a total content of 0.1% by mass or more1. It may be contained in the range of 5% by mass or less.
In this case, like Ga, In, Sn, Ti, and Al segregate in the surface-side region of the Ag alloy film, thereby further improving heat resistance and sulfurization resistance.
　また、本発明の一態様に係るＡｇ合金膜においては、前記Ｇａ偏析部の膜厚方向長さが２．０ｎｍ以上１２．０ｎｍ以下の範囲内であることが好ましい。
　この場合、前記Ｇａ偏析部の膜厚方向長さが上述の範囲内とされているので、耐熱性および耐硫化性を十分に向上させるとともに、反射率の低下を防止することができる。 Moreover, in the Ag alloy film according to one aspect of the present invention, the length in the film thickness direction of the Ga segregation portion is preferably in the range of 2.0 nm or more and 12.0 nm or less.
In this case, since the Ga segregation portion has a length in the film thickness direction within the above range, it is possible to sufficiently improve heat resistance and sulfurization resistance and prevent a decrease in reflectance.
　また、本発明の一態様に係るＡｇ合金膜においては、前記Ｇａ偏析部には、Ｇａ酸化物が存在していてもよい。
　この場合、Ａｇ合金膜の表面側領域に形成された前記Ｇａ偏析部に、Ｇａ酸化物が存在することで、より耐硫化性を向上させることができる。また、Ｇａ酸化物は透明酸化物であるため、Ａｇ合金膜の反射率をさらに向上させることができる。 Further, in the Ag alloy film according to one aspect of the present invention, Ga oxide may exist in the Ga segregation portion.
In this case, the presence of Ga oxide in the Ga segregation portion formed in the surface side region of the Ag alloy film can further improve the sulfuration resistance. Moreover, since the Ga oxide is a transparent oxide, it can further improve the reflectance of the Ag alloy film.
　さらに、本発明の一態様に係るＡｇ合金膜においては、前記Ｇａ偏析部は、酸化物として結晶粒界に沿い網目状に分布していてもよい。
　この場合、Ａｇ合金膜の表面側領域に形成された前記Ｇａ偏析部が、酸化物として結晶粒界に沿い網目状に分布することで、より耐硫化性を向上させることができるとともに、反射率を向上させることができる。 Furthermore, in the Ag alloy film according to one aspect of the present invention, the Ga segregation part may be distributed in a mesh shape along the grain boundaries as an oxide.
In this case, the Ga segregation portion formed in the surface side region of the Ag alloy film is distributed in a mesh shape along the grain boundaries as an oxide, so that the sulfidation resistance can be further improved, and the reflectance can be improved.
　本発明の一態様に係るＡｇ合金スパッタリングターゲットは、Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金からなることを特徴とする。 An Ag alloy sputtering target according to an aspect of the present invention contains Ga in the range of 0.3% by mass to 3.5% by mass, and the balance is Ag and inevitable impurities. and
　本発明の一態様に係るＡｇ合金スパッタリングターゲットによれば、スパッタ成膜することにより、表面側領域にＧａが濃集したＧａ偏析部を有し、耐熱性および耐硫化性に優れたＡｇ合金膜を成膜することができる。 According to the Ag alloy sputtering target according to one aspect of the present invention, an Ag alloy film having a Ga segregation portion in which Ga is concentrated in the surface side region by sputtering and having excellent heat resistance and sulfidation resistance can be deposited.
　ここで、本発明の一態様に係るＡｇ合金スパッタリングターゲットにおいては、さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含んでいてもよい。
　この場合、Ｇａに加えてＣｕ，Ｍｇから選択される１種以上を含み、さらに耐熱性に優れたＡｇ合金膜を成膜することができる。 Here, the Ag alloy sputtering target according to one aspect of the present invention further contains one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less. good too.
In this case, in addition to Ga, it is possible to form an Ag alloy film that contains one or more selected from Cu and Mg and has excellent heat resistance.
　また、本発明の一態様に係るＡｇ合金スパッタリングターゲットにおいては、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされていてもよい。
　この場合、Ｇａに加えてＰｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有し、さらに耐熱性および耐硫化性に優れたＡｇ合金膜を成膜することができる。 In addition, the Ag alloy sputtering target according to one aspect of the present invention further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 ppm by mass or less. , the Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 It may be mass ppm or less.
In this case, in addition to Ga, one or more selected from Pd, Pt, Au, and Rh are contained, and an Ag alloy film having excellent heat resistance and sulfurization resistance can be formed.
　また、本発明の一態様に係るＡｇ合金スパッタリングターゲットにおいては、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含んでいてもよい。
　この場合、Ｇａに加えＣａを含有し、さらに耐熱性に優れたＡｇ合金膜を成膜することができる。 Further, the Ag alloy sputtering target according to one aspect of the present invention may further contain Ca in the range of 0.005% by mass or more and 0.050% by mass or less.
In this case, an Ag alloy film containing Ca in addition to Ga and having excellent heat resistance can be formed.
　また、本発明の一態様に係るＡｇ合金スパッタリングターゲットにおいては、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含んでいてもよい。
　この場合、Ｇａに加えＩｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を含有し、さらに耐熱性および耐硫化性に優れたＡｇ合金膜を成膜することができる。 Further, in the Ag alloy sputtering target according to one aspect of the present invention, one or more selected from In, Sn, Ti, and Al are added in a total amount of 0.1% by mass or more and 1.5% by mass or less. may be included in the range of
In this case, in addition to Ga, it is possible to form an Ag alloy film containing one or more selected from In, Sn, Ti, and Al, and having excellent heat resistance and sulfurization resistance.
　また、本発明の一態様に係るＡｇ合金スパッタリングターゲットにおいては、酸素含有量が０．００５質量％以下であることが好ましい。
　この場合、酸素含有量が０．００５質量％以下に制限されているので、スパッタ成膜時に酸素原子が成長中のＡｇ合金膜に化学吸着することを抑制でき、反射率、耐熱性、耐硫化性が低下することを抑制できる。 Moreover, in the Ag alloy sputtering target according to one aspect of the present invention, the oxygen content is preferably 0.005% by mass or less.
In this case, since the oxygen content is limited to 0.005% by mass or less, it is possible to suppress the chemical adsorption of oxygen atoms to the growing Ag alloy film during the sputtering film formation. It is possible to suppress the deterioration of the properties.
　また、本発明の一態様に係るＡｇ合金スパッタリングターゲットにおいては、複数のＡｇ合金結晶粒を含む多結晶体からなり、複数の測定箇所で測定された前記Ａｇ合金結晶粒の粒径から算出される平均結晶粒径Ｃが１０μｍ以上２００μｍ以下の範囲内とされているとともに、それぞれの測定箇所での前記Ａｇ合金結晶粒の粒径の平均値Ｄのうち前記平均結晶粒径Ｃとの偏差の絶対値が最大となる平均値をＤｍａｘとした場合に、Ｅ（％）＝（Ｄｍａｘ－Ｃ）／Ｃ×１００で定義される前記Ａｇ合金結晶粒の粒径ばらつきＥが２０％以下であることが好ましい。
　この場合、Ａｇ合金結晶粒の粒径ばらつきが小さく、かつ、平均結晶粒径Ｃが上述の範囲内とされているので、スパッタ成膜時の異常放電の発生を抑制でき、安定してＡｇ合金膜を成膜することができる。 Further, in the Ag alloy sputtering target according to one aspect of the present invention, it is composed of a polycrystalline body containing a plurality of Ag alloy crystal grains, and is calculated from the grain size of the Ag alloy crystal grains measured at a plurality of measurement points. The average grain size C is in the range of 10 μm or more and 200 μm or less, and the absolute deviation of the average grain size D from the average grain size C of the Ag alloy crystal grains at each measurement point When the average value with the maximum value is D max , the grain size variation E of the Ag alloy crystal grains defined by E (%) = (D max - C) / C × 100 is 20% or less. is preferred.
In this case, since the grain size variation of the Ag alloy crystal grains is small and the average grain size C is within the above range, the occurrence of abnormal discharge during the sputtering film formation can be suppressed, and the Ag alloy can be stably formed. A film can be deposited.
　本発明の一態様によれば、耐熱性、耐硫化性に優れたＡｇ合金膜、およびこのＡｇ合金膜を成膜するためのＡｇ合金スパッタリングターゲットを提供することが可能となる。 According to one aspect of the present invention, it is possible to provide an Ag alloy film excellent in heat resistance and sulfidation resistance, and an Ag alloy sputtering target for forming this Ag alloy film.
本発明例１０２のＡｇ合金膜（熱処理後）をＸＰＳ分析した結果を示すグラフである。10 is a graph showing the results of XPS analysis of the Ag alloy film (after heat treatment) of Inventive Example 102. FIG. 本発明例１０２のＡｇ合金膜（熱処理後）の最表面のスペクトル例である。It is an example of the spectrum of the outermost surface of the Ag alloy film (after heat treatment) of Example 102 of the present invention. 本発明例１０２のＡｇ合金膜（熱処理前）の最表面のスペクトル例である。It is an example of the spectrum of the outermost surface of the Ag alloy film (before heat treatment) of Example 102 of the present invention. 本発明例１２０におけるＡｇ合金膜の熱処理後の表面観察結果である。It is a surface observation result after heat processing of Ag alloy film in Example 120 of the present invention. 比較例１０１におけるＡｇ合金膜の熱処理後の表面観察結果である。10 shows the surface observation results of the Ag alloy film after heat treatment in Comparative Example 101. FIG.
　以下に、本発明の一実施形態であるＡｇ合金膜およびこれを成膜するためのスパッタリングターゲットについて説明する。
　本発明の一実施形態であるＡｇ合金膜は、反射率、耐熱性、耐硫化性に優れ、例えば、有機ＥＬ素子において有機層に接して形成される反射電極膜としての用途に特に適している。 An Ag alloy film and a sputtering target for forming the Ag alloy film, which is one embodiment of the present invention, will be described below.
The Ag alloy film, which is one embodiment of the present invention, is excellent in reflectance, heat resistance, and sulfidation resistance, and is particularly suitable for use as a reflective electrode film formed in contact with an organic layer in an organic EL device, for example. .
　本実施形態であるＡｇ合金膜は、Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金からなり、Ａｇ合金膜の表面側領域にＧａが濃集したＧａ偏析部が形成されている。
　このＧａ偏析部は、Ｇａの濃度が、他の部分よりも高くなっている部位である。ここで、このＧａの濃度が他の部分よりも高くなっている部位は、Ａｇ合金膜の表面側領域を含む。なお、Ｇａ偏析部は、その周辺の領域との間に明瞭な界面等が存在する層として形成されるものではなく、Ｇａ濃度のピーク位置からその濃度が徐々に変化するＧａ濃度の濃化部分であり、ＸＰＳ分析のピーク強度によって特定される。
　なお、本実施形態であるＡｇ合金膜は、０．３質量％以上３．５質量％以下の範囲で含有されたＧａと、残部としてＡｇおよび不可避不純物とを含み、Ａｇ合金膜の表面側領域にＧａが濃集したＧａ偏析部が形成されている。 The Ag alloy film of the present embodiment contains Ga in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities. A Ga segregation portion in which Ga is concentrated is formed in the side region.
This Ga segregation part is a part where the concentration of Ga is higher than other parts. Here, the portion where the Ga concentration is higher than other portions includes the surface side region of the Ag alloy film. In addition, the Ga segregation part is not formed as a layer in which a clear interface or the like exists with the surrounding area, but a Ga concentration concentrated part where the concentration gradually changes from the Ga concentration peak position , identified by the peak intensity of the XPS analysis.
Note that the Ag alloy film of the present embodiment contains Ga contained in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities, and the surface side region of the Ag alloy film A Ga segregation portion in which Ga is concentrated is formed in the .
　ここで、本実施形態におけるＡｇ合金膜においては、前記Ａｇ合金膜の膜厚方向の両端部に存在する２つの表面のうち少なくとも一方の表面の表面側領域に、Ｇａ偏析部が形成されている。例えば、基板上にＡｇ合金膜を成膜した場合には、少なくとも基板とは反対側の表面の表面側領域にＧａ偏析部が形成されている。なお、基板側の表面の表面側領域にもＧａ偏析部が形成されていてもよい。
　また、本実施形態において、Ａｇ合金膜の表面側領域とは、Ａｇ合金膜の表面から厚さ方向にＡｇ合金膜の全厚の２０％までの領域である。 Here, in the Ag alloy film of the present embodiment, a Ga segregation portion is formed in the surface side region of at least one of the two surfaces present at both ends in the film thickness direction of the Ag alloy film. . For example, when an Ag alloy film is formed on a substrate, a Ga segregation portion is formed at least in the surface side region of the surface opposite to the substrate. Note that the Ga segregation portion may also be formed in the surface-side region of the substrate-side surface.
Further, in the present embodiment, the surface side region of the Ag alloy film is a region extending from the surface of the Ag alloy film to 20% of the total thickness of the Ag alloy film in the thickness direction.
　本実施形態であるＡｇ合金膜を構成するＡｇ合金においては、さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含んでいてもよい。
　本実施形態であるＡｇ合金膜を構成するＡｇ合金においては、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされていてもよい。 The Ag alloy constituting the Ag alloy film of the present embodiment further contains one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less. good.
The Ag alloy constituting the Ag alloy film of the present embodiment further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 ppm by mass or less. , the Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 It may be mass ppm or less.
　本実施形態であるＡｇ合金膜を構成するＡｇ合金においては、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含んでいてもよい。
　本実施形態であるＡｇ合金膜を構成するＡｇ合金においては、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含んでいてもよい。 The Ag alloy forming the Ag alloy film of the present embodiment may further contain Ca in the range of 0.005% by mass or more and 0.050% by mass or less.
In the Ag alloy constituting the Ag alloy film of the present embodiment, one or two or more selected from In, Sn, Ti, and Al are further added in a total amount of 0.1% by mass or more and 1.5% by mass or less. may be included in the range of
　本実施形態であるＡｇ合金膜においては、Ｇａ偏析部の膜厚方向長さが２．０ｎｍ以上１２．０ｎｍ以下の範囲内であることが好ましい。
　本実施形態であるＡｇ合金膜においては、Ｇａ偏析部に、Ｇａ酸化物が存在していることが好ましい。
　本実施形態であるＡｇ合金膜においては、Ｇａ偏析部は、酸化物として結晶粒界に沿い網目状に分布していることが好ましい。また、本実施形態であるＡｇ合金膜においては、Ｇａ偏析部は、Ａｇ合金膜の表面側領域において、酸化物として結晶粒界に沿って全体的に分布してもよいし、酸化物として結晶粒界に沿って部分的に分布してもよい。
　なお、Ｇａ偏析部にＧａ酸化物が存在している場合、Ａｇ合金膜は、酸素を含むが、酸素の量は不可避不純物レベルである。 In the Ag alloy film of the present embodiment, the length in the film thickness direction of the Ga segregation portion is preferably in the range of 2.0 nm or more and 12.0 nm or less.
In the Ag alloy film of the present embodiment, Ga oxide is preferably present in the Ga segregation portion.
In the Ag alloy film of the present embodiment, the Ga segregation parts are preferably distributed as oxides in a network along the grain boundaries. In addition, in the Ag alloy film of the present embodiment, the Ga segregation part may be distributed entirely along the grain boundary as an oxide in the surface side region of the Ag alloy film, or may be distributed as an oxide. It may be partially distributed along grain boundaries.
When Ga oxide exists in the Ga segregation part, the Ag alloy film contains oxygen, but the amount of oxygen is at the level of unavoidable impurities.
　本実施形態であるＡｇ合金スパッタリングターゲットは、上述の本実施形態であるＡｇ合金膜を成膜するためのものであり、成膜するＡｇ合金膜と同様の組成とされている。
　すなわち、Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金で構成されている。 The Ag alloy sputtering target of the present embodiment is for forming the Ag alloy film of the above-described present embodiment, and has the same composition as the Ag alloy film to be formed.
That is, it is composed of an Ag alloy having a composition containing Ga in the range of 0.3% by mass or more and 3.5% by mass or less, with the balance being Ag and unavoidable impurities.
　なお、Ｇａに加えて、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含んでいてもよい。
　また、Ｇａに加えて、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされていてもよい。 In addition to Ga, one or more selected from Cu and Mg may be included in a total range of 0.5 ppm by mass or more and 50.0 ppm by mass or less.
In addition to Ga, it further contains one or more selected from Pd, Pt, Au, and Rh, the Pd content is 40 mass ppm or less, and the Pt content is 20 mass ppm. Hereinafter, the Au content may be 20 mass ppm or less, the Rh content may be 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh may be 1 mass ppm or more and 50 mass ppm or less. .
　また、Ｇａに加えて、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含んでいてもよい。
　また、Ｇａに加えて、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含んでいてもよい。 In addition to Ga, Ca may also be included in the range of 0.005% by mass or more and 0.050% by mass or less.
Further, in addition to Ga, one or more selected from In, Sn, Ti, and Al may be contained in a total amount of 0.1% by mass or more and 1.5% by mass or less.
　さらに、本実施形態であるＡｇ合金スパッタリングターゲットにおいては、酸素含有量が５０質量ｐｐｍ以下（０．００５質量％以下）であることが好ましい。
　また、本実施形態であるＡｇ合金スパッタリングターゲットにおいては、複数のＡｇ合金結晶粒を含む多結晶体からなり、複数の測定箇所で測定された前記Ａｇ合金結晶粒の粒径から算出される前記平均結晶粒径Ｃが１０μｍ以上２００μｍ以下の範囲内とされているとともに、それぞれの測定箇所での前記Ａｇ合金結晶粒の粒径の平均値Ｄのうち前記平均結晶粒径Ｃとの偏差の絶対値が最大となる平均値をＤｍａｘとした場合に、下記の（１）式で定義される前記Ａｇ合金結晶粒の粒径ばらつきＥが２０％以下であることが好ましい。
　（１）式：Ｅ（％）＝（Ｄｍａｘ－Ｃ）／Ｃ×１００ Furthermore, in the Ag alloy sputtering target of the present embodiment, the oxygen content is preferably 50 mass ppm or less (0.005 mass% or less).
Further, in the Ag alloy sputtering target of the present embodiment, it is made of a polycrystalline body containing a plurality of Ag alloy crystal grains, and the average The crystal grain size C is in the range of 10 μm or more and 200 μm or less, and the absolute value of the deviation from the average crystal grain size C of the average value D of the grain size of the Ag alloy crystal grains at each measurement point. It is preferable that the grain size variation E of the Ag alloy crystal grains defined by the following formula (1) is 20% or less, where D max is the average value at which the is maximum.
(1) Formula: E (%) = (D max -C) / C x 100
　本実施形態において、Ａｇ合金膜のＧａ偏析部、Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金の組成、Ａｇ合金スパッタリングターゲットの酸素含有量、Ａｇ合金スパッタリングターゲットの結晶組織を、上述のように規定した理由について、以下に説明する。 In the present embodiment, the Ga segregation portion of the Ag alloy film, the composition of the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target, the oxygen content of the Ag alloy sputtering target, and the crystal structure of the Ag alloy sputtering target are as described above. The reason for the stipulation is explained below.
（Ｇａ偏析部）
　Ａｇ合金膜の表面に、Ｇａが偏析したＧａ偏析部が形成されることにより、耐熱性および耐硫化性が向上し、熱処理や硫化雰囲気においても突起状欠陥の発生を抑制することが可能となる。なお、Ａｇ合金膜をスパッタ成膜した後に、例えば２００℃以上３００℃以下の熱処理を行うことにより、Ａｇ合金膜の表面側領域にＧａ偏析部を確実に形成することが可能となる。 (Ga segregation part)
By forming a Ga segregation part in which Ga is segregated on the surface of the Ag alloy film, heat resistance and sulfurization resistance are improved, and it is possible to suppress the occurrence of protruding defects even in heat treatment and in a sulfurization atmosphere. . After forming the Ag alloy film by sputtering, a heat treatment at, for example, 200° C. or higher and 300° C. or lower can be performed to reliably form the Ga segregation part in the surface side region of the Ag alloy film.
　ここで、Ｇａ偏析部の膜厚方向長さが１．０ｎｍ以上である場合には、耐熱性および耐硫化性を確実に向上することができる。また、Ｇａ偏析部の膜厚方向長さが１５．０ｎｍ以下である場合には、反射率を高く維持することが可能となる。
　なお、耐熱性および耐硫化性をさらに確実に向上するためには、Ｇａ偏析部の膜厚方向長さの下限を５．０ｎｍ以上とすることがより好ましい。また、反射率をさらに確実に高く維持するためには、Ｇａ偏析部の膜厚方向長さの上限を１０．０ｎｍ以下とすることがより好ましい。 Here, when the thickness direction length of the Ga segregation part is 1.0 nm or more, the heat resistance and the sulfuration resistance can be reliably improved. Further, when the length of the Ga segregation portion in the film thickness direction is 15.0 nm or less, it is possible to maintain a high reflectance.
In order to more reliably improve the heat resistance and sulfuration resistance, it is more preferable to set the lower limit of the length of the Ga segregation portion in the film thickness direction to 5.0 nm or more. Further, in order to more reliably maintain a high reflectance, it is more preferable to set the upper limit of the length in the film thickness direction of the Ga segregation portion to 10.0 nm or less.
　Ｇａ偏析部に、Ｇａ酸化物が存在する場合には、Ａｇ合金膜の耐硫化性を向上させることができる。Ａｇ合金膜の表面側領域にＧａ酸化物が形成されることで、硫黄（硫化水素）に対してより強固なバリアとして働き、Ａｇ合金膜の耐硫化性が向上する。さらに、Ｇａ酸化物は透明酸化物であるため、Ａｇ合金膜の反射率を向上させることができる。
　また、Ｇａ偏析部が、酸化物として結晶粒界に沿い網目状に分布している場合には、Ａｇ合金膜の耐硫化性をさらに向上させることができるとともに、Ａｇ合金膜の反射率をさらに向上させることができる。 When Ga oxide exists in the Ga segregation part, the sulfuration resistance of the Ag alloy film can be improved. The Ga oxide formed in the surface-side region of the Ag alloy film acts as a stronger barrier against sulfur (hydrogen sulfide), improving the sulfuration resistance of the Ag alloy film. Furthermore, since the Ga oxide is a transparent oxide, it can improve the reflectance of the Ag alloy film.
In addition, when the Ga segregation part is distributed in a mesh shape along the grain boundary as an oxide, the sulfuration resistance of the Ag alloy film can be further improved, and the reflectance of the Ag alloy film can be further improved. can be improved.
（Ａｇ合金膜およびＡｇ合金スパッタリングターゲットの組成）
　Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金において、Ｇａの含有量が０．３質量％未満の場合には、上述のＧａ偏析部を十分に形成できないおそれがある。一方、Ｇａの含有量が３．５質量％を超える場合には、Ａｇ合金膜の反射率が低下するおそれがある。
　このため、本実施形態では、Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金におけるＧａの含有量を０．３質量％以上３．５％質量％以下の範囲内に設定している。
　なお、Ｇａの含有量の下限は０．５質量％以上であることが好ましく、１．０質量％以上であることがさらに好ましい。一方、Ｇａの含有量の上限は２．５質量％以下であることが好ましく、２．０質量％以下であることがさらに好ましい。 (Composition of Ag alloy film and Ag alloy sputtering target)
If the Ga content in the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target is less than 0.3% by mass, the Ga segregation portion may not be sufficiently formed. On the other hand, when the Ga content exceeds 3.5% by mass, the reflectance of the Ag alloy film may decrease.
Therefore, in the present embodiment, the content of Ga in the Ag alloy forming the Ag alloy film and the Ag alloy sputtering target is set within the range of 0.3% by mass or more and 3.5% by mass or less.
The lower limit of the Ga content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. On the other hand, the upper limit of the Ga content is preferably 2.5% by mass or less, more preferably 2.0% by mass or less.
　また、Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金において、Ｇａに加えて、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上含有する場合には、Ａｇ原子の熱による拡散を抑制でき、耐熱性をより向上させることが可能となる。一方、Ｃｕ，Ｍｇから選択される１種以上の合計含有量を５０．０質量ｐｐｍ以下に制限することにより、耐硫化性の低下を抑制することが可能となる。
　なお、さらなる耐熱性の向上を図るには、Ｃｕ，Ｍｇから選択される１種以上の合計含有量の下限を１．０質量ｐｐｍ以上とすることがさらに好ましく、２．０質量ｐｐｍ以上とすることがより好ましい。一方、耐硫化性の低下を確実に抑制するためには、Ｃｕ，Ｍｇから選択される１種以上の合計含有量の上限を２０．０質量ｐｐｍ以下とすることがさらに好ましく、１０．０質量ｐｐｍ以下とすることがより好ましい。 Further, when the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target contains, in addition to Ga, one or more selected from Cu and Mg in a total of 0.5 ppm by mass or more, the number of Ag atoms Diffusion due to heat can be suppressed, and heat resistance can be further improved. On the other hand, by limiting the total content of one or more elements selected from Cu and Mg to 50.0 ppm by mass or less, it is possible to suppress deterioration in resistance to sulfurization.
In order to further improve heat resistance, the lower limit of the total content of one or more selected from Cu and Mg is more preferably 1.0 ppm by mass or more, more preferably 2.0 ppm by mass or more. is more preferable. On the other hand, in order to reliably suppress deterioration of sulfuration resistance, it is more preferable that the upper limit of the total content of one or more selected from Cu and Mg is 20.0 ppm by mass or less, and 10.0 mass ppm. It is more preferable to make it below ppm.
　また、Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金において、Ｇａに加えて、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上とされている場合には、これらの元素がＡｇに固溶することにより、耐熱性および耐硫化性をより向上させることが可能となる。
　なお、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈといった元素は、硝酸の還元反応において触媒として作用するため、Ａｇ合金膜を硝酸エッチング液でエッチングした際に、膜のエッチングレートが高くなり、安定してエッチング処理をできなくなるおそれがある。このため、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有する場合には、Ｐｄの含有量を４０質量ｐｐｍ以下、Ｐｔの含有量を２０質量ｐｐｍ以下、Ａｕの含有量を２０質量ｐｐｍ以下、Ｒｈの含有量を１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量を５０質量ｐｐｍ以下とすることが好ましい。また、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有する場合には、Ｐｄの含有量を４０質量ｐｐｍ以下、Ｐｔの含有量を１４質量ｐｐｍ以下、Ａｕの含有量を１３質量ｐｐｍ以下、Ｒｈの含有量を１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量を５０質量ｐｐｍ以下とすることがさらに好ましい。なお、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有する場合には、ＰｄとＰｔとＡｕとＲｈの合計含有量は５０質量ｐｐｍ以下とすることが好ましく、４０質量ｐｐｍ以下とすることがさらに好ましい。 Further, the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target contains, in addition to Ga, one or more selected from Pd, Pt, Au, and Rh, and Pd, Pt and Au and Rh is 1 ppm by mass or more, these elements form a solid solution in Ag, thereby making it possible to further improve heat resistance and sulfurization resistance.
Since elements such as Pd, Pt, Au, and Rh act as catalysts in the reduction reaction of nitric acid, when an Ag alloy film is etched with a nitric acid etchant, the etching rate of the film increases, and the etching process is stable. may not be able to Therefore, when one or more selected from Pd, Pt, Au, and Rh are contained, the content of Pd is 40 ppm by mass or less, the content of Pt is 20 ppm by mass or less, and the content of Au It is preferable that the amount is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 50 mass ppm or less. In addition, when one or more selected from Pd, Pt, Au, and Rh are contained, the content of Pd is 40 ppm by mass or less, the content of Pt is 14 ppm by mass or less, and the content of Au is 13 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 50 mass ppm or less. In addition, when one or more selected from Pd, Pt, Au, and Rh are contained, the total content of Pd, Pt, Au, and Rh is preferably 50 ppm by mass or less, and 40 mass It is more preferable to set it to ppm or less.
　ここで、耐熱性および耐硫化性をさらに向上させるためには、ＰｄとＰｔとＡｕとＲｈの合計含有量を２質量ｐｐｍ以上とすることがさらに好ましく、３質量ｐｐｍ以上とすることがより好ましい。
　また、硝酸エッチング液によるエッチング時のエッチングレートをさらに低く抑えるためには、Ｐｄの含有量を２０質量ｐｐｍ以下、Ｐｔの含有量を１０質量ｐｐｍ以下、Ａｕの含有量を１０質量ｐｐｍ以下、Ｒｈの含有量含有量を８質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量含有量を２０質量ｐｐｍ以下とすることがさらに好ましく、Ｐｄの含有量を１０質量ｐｐｍ以下、Ｐｔの含有量を５質量ｐｐｍ以下、Ａｕの含有量を５質量ｐｐｍ以下、Ｒｈの含有量含有量を５質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量含有量を１０質量ｐｐｍ以下とすることがより好ましい。
　Ｐｄ，Ｐｔ，Ａｕ，Ｒｈの含有量の下限値は、限定されないが、Ｐｄの含有量を０．２質量ｐｐｍ以上、Ｐｔの含有量を０．０１質量ｐｐｍ以上、Ａｕの含有量を０．２質量ｐｐｍ以上、Ｒｈの含有量を０．０１質量ｐｐｍ以上とすることが好ましい。 Here, in order to further improve heat resistance and sulfurization resistance, the total content of Pd, Pt, Au, and Rh is more preferably 2 ppm by mass or more, more preferably 3 ppm by mass or more. .
In order to further reduce the etching rate during etching with a nitric acid etchant, the Pd content should be 20 mass ppm or less, the Pt content should be 10 mass ppm or less, the Au content should be 10 mass ppm or less, and the Rh content should be 10 mass ppm or less. The content of 8 ppm by mass or less, and the total content of Pd, Pt, Au and Rh is more preferably 20 ppm by mass or less, the Pd content is 10 mass ppm or less, and the Pt The content is 5 ppm by mass or less, the content of Au is 5 ppm by mass or less, the content of Rh is 5 ppm by mass or less, and the total content of Pd, Pt, Au and Rh is 10 ppm by mass or less. is more preferable.
The lower limits of the contents of Pd, Pt, Au, and Rh are not limited, but the content of Pd is 0.2 mass ppm or more, the Pt content is 0.01 mass ppm or more, and the Au content is 0.01 mass ppm or more. It is preferable to set the content of Rh to 2 ppm by mass or more and 0.01 ppm by mass or more.
　また、Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金において、Ｇａに加えて、さらに、Ｃａを０．００５質量％以上含んでいる場合には、添加したＣａがＡｇの粒界に偏析してＡｇの粒界拡散を抑制し、さらなる耐熱性の向上を図ることが可能となる。一方、Ｃａの含有量を０．０５０質量％以下に制限することにより、Ａｇ合金スパッタリングターゲットを製造する際に割れが発生することを抑制できる。
　なお、さらなる耐熱性の向上を図るには、Ｃａの含有量の下限を０．００８質量％以上とすることがさらに好ましく、０．０１０質量％以上とすることがより好ましい。一方、Ａｇ合金スパッタリングターゲットを製造する際の割れを確実に抑制するためには、Ｃａの含有量の上限を０．０４０質量％以下とすることがさらに好ましく、０．０３０質量％以下とすることがより好ましい。 Further, when the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target further contains 0.005% by mass or more of Ca in addition to Ga, the added Ca segregates at the grain boundary of Ag. It is possible to suppress the grain boundary diffusion of Ag and further improve the heat resistance. On the other hand, by limiting the Ca content to 0.050% by mass or less, it is possible to suppress the occurrence of cracks when manufacturing the Ag alloy sputtering target.
In order to further improve the heat resistance, the lower limit of the Ca content is more preferably 0.008% by mass or more, more preferably 0.010% by mass or more. On the other hand, in order to reliably suppress cracking when manufacturing an Ag alloy sputtering target, the upper limit of the Ca content is more preferably 0.040% by mass or less, and 0.030% by mass or less. is more preferred.
　また、Ａｇ合金膜およびＡｇ合金スパッタリングターゲットを構成するＡｇ合金において、Ｇａに加えて、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上含有する場合には、Ｇａと同様に、Ｉｎ，Ｓｎ，Ｔｉ，ＡｌがＡｇ合金膜の表面側領域に凝集し、耐熱性および耐硫化性をさらに向上させることが可能となる。一方、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上の合計含有量を１．５質量％以下に制限することにより、反射率を高く維持することが可能となる。
　なお、さらなる耐熱性および耐硫化性の向上を図るには、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上の合計含有量の下限を０．２質量％以上とすることがさらに好ましく、０．３質量％以上とすることがより好ましい。一方、反射率の低減をさらに抑制するためには、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上の合計含有量の上限を１．０質量％以下とすることがさらに好ましく、０．８質量％以下とすることがより好ましい。 Further, in the Ag alloy constituting the Ag alloy film and the Ag alloy sputtering target, in addition to Ga, one or more selected from In, Sn, Ti, Al is added in a total of 0.1% by mass or more When it is contained, like Ga, In, Sn, Ti, and Al agglomerate in the surface-side region of the Ag alloy film, making it possible to further improve heat resistance and sulfurization resistance. On the other hand, by limiting the total content of one or more selected from In, Sn, Ti, and Al to 1.5% by mass or less, it is possible to maintain a high reflectance.
In order to further improve heat resistance and sulfurization resistance, the lower limit of the total content of one or more selected from In, Sn, Ti, and Al may be set to 0.2% by mass or more. More preferably, it is 0.3% by mass or more. On the other hand, in order to further suppress the decrease in reflectance, it is more preferable to set the upper limit of the total content of one or more selected from In, Sn, Ti, and Al to 1.0% by mass or less. , 0.8% by mass or less.
（Ａｇ合金スパッタリングターゲットの酸素含有量）
　本実施形態であるＡｇ合金スパッタリングターゲットにおいて、酸素含有量が０．００５質量％以下である場合には、スパッタ成膜時に、酸素元素が成長中のＡｇ合金膜に化学吸着されることを抑制でき、Ａｇ合金膜の結晶性の低下による反射率、耐熱性、耐硫化性の劣化を抑制することができる。
　なお、反射率、耐熱性、耐硫化性の劣化をさらに確実に抑制するためには、Ａｇ合金スパッタリングターゲットの酸素含有量は、０．００４質量％以下であることがさらに好ましく、０．００２質量％以下であることがより好ましい。Ａｇ合金スパッタリングターゲットの酸素含有量の下限値は、０．００１質量％以上であることが好ましい。 (Oxygen content of Ag alloy sputtering target)
In the Ag alloy sputtering target of the present embodiment, when the oxygen content is 0.005% by mass or less, it is possible to suppress chemical adsorption of the oxygen element to the growing Ag alloy film during sputtering film formation. , deterioration of reflectance, heat resistance, and sulfidation resistance due to deterioration of crystallinity of the Ag alloy film can be suppressed.
In order to more reliably suppress deterioration of reflectance, heat resistance, and sulfurization resistance, the oxygen content of the Ag alloy sputtering target is more preferably 0.004% by mass or less, and more preferably 0.002% by mass. % or less. The lower limit of the oxygen content of the Ag alloy sputtering target is preferably 0.001% by mass or more.
（Ａｇ合金スパッタリングターゲットの結晶粒径）
　本実施形態であるＡｇ合金スパッタリングターゲットにおいて、複数の箇所で測定されたＡｇ合金結晶粒の平均結晶粒径Ｃと、測定した各箇所でのＡｇ合金結晶粒の粒径の平均値のうち平均結晶粒径Ｃとの偏差の絶対値が最大となる平均値Ｄｍａｘとから、上記（１）式で定義されるＡｇ合金結晶粒の粒径ばらつきＥが２０％以下とされている場合には、スパッタが進行してもスパッタ面に凹凸が生じることを抑制でき、スパッタが進行した後でもスパッタ時の異常放電の発生を抑制することが可能となる。Ａｇ合金結晶粒の粒径ばらつきＥの下限値は、特に限定されないが、０．１％以上であることが好ましい。
　また、Ａｇ合金結晶粒の平均結晶粒径Ｃが２００μｍ以下である場合には、異常放電の発生を抑制することができる。なお、Ａｇ合金結晶粒の平均結晶粒径Ｃを１０μｍ未満にすることは製造コストが増大するため好ましくない。 (Crystal grain size of Ag alloy sputtering target)
In the Ag alloy sputtering target of the present embodiment, the average crystal grain size C of the Ag alloy crystal grains measured at a plurality of locations, and the average grain size of the Ag alloy crystal grains at each measured location. From the average value D max at which the absolute value of the deviation from the grain size C is maximum, when the grain size variation E of the Ag alloy crystal grains defined by the above formula (1) is set to 20% or less, It is possible to suppress the occurrence of unevenness on the sputtering surface even when sputtering progresses, and it is possible to suppress the occurrence of abnormal discharge during sputtering even after the sputtering progresses. Although the lower limit of grain size variation E of Ag alloy crystal grains is not particularly limited, it is preferably 0.1% or more.
Moreover, when the average crystal grain size C of the Ag alloy crystal grains is 200 μm or less, the occurrence of abnormal discharge can be suppressed. It should be noted that setting the average crystal grain size C of the Ag alloy crystal grains to less than 10 μm is not preferable because the manufacturing cost increases.
　ここで、異常放電の発生をさらに抑制するためには、Ａｇ合金結晶粒の粒径ばらつきＥを１９％以下とすることがさらに好ましく、１８％以下とすることがより好ましい。また、Ａｇ合金結晶粒の平均結晶粒径Ｃを１８０μｍ以下とすることがさらに好ましく、１５０μｍ以下とすることがより好ましい。
　また、Ａｇ合金スパッタリングターゲットの製造コストをさらに抑制するためには、Ａｇ合金結晶粒の平均結晶粒径Ｃの下限は、２０μｍ以上とすることがさらに好ましく、３０μｍ以上とすることがより好ましい。 Here, in order to further suppress the occurrence of abnormal discharge, it is more preferable to set the grain size variation E of the Ag alloy crystal grains to 19% or less, more preferably 18% or less. Further, the average crystal grain size C of the Ag alloy crystal grains is more preferably 180 μm or less, more preferably 150 μm or less.
In order to further reduce the production cost of the Ag alloy sputtering target, the lower limit of the average crystal grain size C of the Ag alloy crystal grains is more preferably 20 μm or more, more preferably 30 μm or more.
　次に、本実施形態であるＡｇ合金スパッタリングターゲットの製造方法の一例を説明する。
　まず、純度が９９．９９質量％以上のＡｇ原料と、純度が９９．９質量％以上のＧａ原料を準備する。また、必要に応じて、純度が９９．９質量％以上の各種原料（Ｃｕ，Ｍｇ，Ｐｄ，Ｐｔ，Ａｕ，Ｒｈ，Ｃａ，Ｉｎ，Ｓｎ，Ｔｉ，Ａｌ）を準備する。
　なお、Ａｇ合金の純度を向上させるために、Ａｇ原料を硝酸または硫酸で浸出し、次いで所定の銀濃度の電解液を用いて電解精錬を行い、精錬したＡｇ原料の不純物分析を実施する。これらを繰り返し行うことで、Ａｇ原料の不純物量を低減することが好ましい。 Next, an example of the method for producing the Ag alloy sputtering target according to this embodiment will be described.
First, an Ag raw material with a purity of 99.99% by mass or more and a Ga raw material with a purity of 99.9% by mass or more are prepared. Moreover, various raw materials (Cu, Mg, Pd, Pt, Au, Rh, Ca, In, Sn, Ti, Al) having a purity of 99.9% by mass or more are prepared as necessary.
In order to improve the purity of the Ag alloy, the Ag raw material is leached with nitric acid or sulfuric acid, then electrorefined using an electrolytic solution having a predetermined silver concentration, and the refined Ag raw material is analyzed for impurities. It is preferable to reduce the amount of impurities in the Ag raw material by repeating these steps.
　次に、上述のＡｇ原料とＧａ原料と必要に応じて各種原料を秤量する。そして、Ａｇ原料を、雰囲気溶解炉の坩堝内に装入する。
　次いで、高真空下雰囲気又は不活性ガス雰囲気下でＡｇ原料を溶解し、得られたＡｇ溶湯に、Ｇａおよび各種原料を添加し、Ａｇ合金溶湯を得る。このＡｇ合金溶湯を所定の形状の鋳型に流し込むことでＡｇ合金インゴットを得る。 Next, the above-mentioned Ag raw material, Ga raw material, and various raw materials according to need are weighed. Then, the Ag raw material is charged into the crucible of the atmosphere melting furnace.
Next, the Ag raw material is melted under a high vacuum atmosphere or an inert gas atmosphere, and Ga and various raw materials are added to the obtained Ag molten metal to obtain an Ag alloy molten metal. An Ag alloy ingot is obtained by pouring this Ag alloy molten metal into a mold having a predetermined shape.
　ここで、Ａｇ合金インゴット中の添加元素を均一化するために、高周波で溶湯を攪拌できる高周波誘導溶解炉を用いることが好ましい。
　また、Ａｇ合金インゴット中の酸素含有量を低減するためには、易酸化性の添加元素（Ｇａ，Ｃｕ，Ｍｇ，Ｉｎ，Ｓｎ，Ａｌ，Ｔｉ，Ｃａ）については、溶解炉に投入する直前まで、真空パック等で大気に晒されない状態としておくことが好ましい。さらに、投入時および溶解時には、溶解炉内を、不活性ガス雰囲気の置換操作を数回実施した状態としておくことが好ましい。
　また、Ａｇ合金インゴットにおける添加元素の偏析や結晶粒径のばらつきを抑制するためには、水冷した鋳型に流し込んで急冷することが好ましい。 Here, in order to homogenize the additive elements in the Ag alloy ingot, it is preferable to use a high-frequency induction melting furnace capable of stirring the molten metal at high frequencies.
In addition, in order to reduce the oxygen content in the Ag alloy ingot, the easily oxidizable additive elements (Ga, Cu, Mg, In, Sn, Al, Ti, Ca) should be It is preferable to keep it in a state where it is not exposed to the atmosphere by vacuum packing or the like. Furthermore, it is preferable to keep the inside of the melting furnace in a state in which the operation of replacing the inert gas atmosphere has been performed several times during charging and melting.
Moreover, in order to suppress the segregation of additive elements and variations in grain size in the Ag alloy ingot, it is preferable to pour the ingot into a water-cooled mold and rapidly cool it.
　なお、鋳造方法としては、例えば、一方向凝固法を用いて実施することができる。一方向凝固法は、例えば、鋳型の底部を水冷させた状態で、抵抗加熱により予め側面部を加熱した鋳型に、溶湯を鋳込み、その後、鋳型下部の抵抗加熱部の設定温度を徐々に低下させることで実施できる。なお、鋳造方法としては、上記説明した一方向凝固法に替えて、完全連続鋳造法や半連続鋳造法等を用いて行ってもよい。 As a casting method, for example, a unidirectional solidification method can be used. In the unidirectional solidification method, for example, while the bottom of the mold is water-cooled, the molten metal is poured into the mold whose side parts are preheated by resistance heating, and then the set temperature of the resistance heating part at the bottom of the mold is gradually lowered. can be implemented by As the casting method, a complete continuous casting method, a semi-continuous casting method, or the like may be used instead of the unidirectional solidification method described above.
　次いで、Ａｇ合金インゴットに対して塑性加工を行い、所定の形状に成形する。なお、塑性加工は、熱間および冷間のいずれで実施してもよい。
　本実施形態では、Ａｇ合金インゴットに対して圧延を行い、板材を成形する構成とされている。なお、累計圧延率は７０％以上であることが好ましい。また、結晶粒径の微細化の観点から、少なくとも圧延の最後の１パスは、圧下率が２０％以上であることが好ましい。 Then, the Ag alloy ingot is subjected to plastic working and formed into a predetermined shape. The plastic working may be performed either hot or cold.
In the present embodiment, a plate material is formed by rolling an Ag alloy ingot. In addition, it is preferable that the cumulative rolling reduction is 70% or more. Moreover, from the viewpoint of refining the crystal grain size, it is preferable that at least the last pass of rolling has a rolling reduction of 20% or more.
　次いで、加工硬化の除去および結晶組織の均一化のために、板材に対して熱処理を実施する。熱処理温度は５００℃以上７００℃以下、保持時間は１時間以上５時間以下とすることが好ましい。また、熱処理後には、空冷又は水冷によって急冷する。なお、熱処理の雰囲気に特に制限はなく、例えば、大気雰囲気、不活性雰囲気であってもよい。
　ここで、熱処理温度が５００℃未満の場合には、加工硬化を除去する効果が十分ではないおそれがある。一方、熱処理温度が７００℃を超える場合には、結晶粒が粗大化したり、液相が出現したりするおそれがある。また、保持時間が１時間未満の場合には、結晶粒径を十分に均一化できないおそれがある。 Next, heat treatment is performed on the sheet material in order to remove work hardening and homogenize the crystal structure. The heat treatment temperature is preferably 500° C. or higher and 700° C. or lower, and the holding time is preferably 1 hour or longer and 5 hours or shorter. Moreover, after the heat treatment, it is rapidly cooled by air cooling or water cooling. The atmosphere for the heat treatment is not particularly limited, and may be, for example, an air atmosphere or an inert atmosphere.
Here, if the heat treatment temperature is less than 500° C., the effect of removing work hardening may not be sufficient. On the other hand, if the heat treatment temperature exceeds 700° C., the crystal grains may become coarse, or a liquid phase may appear. Moreover, when the holding time is less than 1 hour, there is a possibility that the crystal grain size cannot be made sufficiently uniform.
　次に、上述の熱処理を施した熱処理材に対して機械加工（切削加工）を行い、所定の形状および寸法に仕上げる。 Next, the heat-treated material that has undergone the heat treatment described above is machined (cut) to finish it into a predetermined shape and dimensions.
　以上のような工程により、本実施形態であるＡｇ合金スパッタリングターゲットが製造される。 The Ag alloy sputtering target of the present embodiment is manufactured through the steps described above.
　次に、本実施形態であるＡｇ合金スパッタリングターゲットを用いて、本実施形態であるＡｇ合金膜を成膜する方法について説明する。
　まず、本実施形態であるＡｇ合金スパッタリングターゲットをスパッタ成膜装置のターゲットホルダにセットする。そして、成膜する基板を取り付けて、基板上にＡｇ合金膜を成膜する。
　成膜条件の一例を以下に示す。
　成膜電力密度：２．０～５．０（Ｗ／ｃｍ２）
　成膜ガス：Ａｒ
　成膜ガス圧：０．２～０．４（Ｐａ）
　ターゲット－基板間距離：６０～８０（ｍｍ） Next, a method for forming an Ag alloy film according to this embodiment using the Ag alloy sputtering target according to this embodiment will be described.
First, the Ag alloy sputtering target of this embodiment is set in a target holder of a sputtering film forming apparatus. Then, a substrate on which a film is to be formed is attached, and an Ag alloy film is formed on the substrate.
An example of film formation conditions is shown below.
Deposition power density: 2.0 to 5.0 (W/cm 2 )
Deposition gas: Ar
Deposition gas pressure: 0.2 to 0.4 (Pa)
Target-substrate distance: 60 to 80 (mm)
　上述したＡｇ合金スパッタリングターゲットを用い、上述した条件でスパッタリングを行うことにより、Ｇａを含むＡｇ合金膜の表面側領域に、Ｇａが濃集したＧａ偏析部が形成される。
　次に、この成膜されたＡｇ合金膜を熱処理することにより、Ｇａ偏析部におけるＧａの酸化を促進させることができる。Ａｇ合金膜を熱処理条件としては、例えば、酸素を含む雰囲気下で２５０～３００℃で１～２時間程度加熱すればよい。酸素を含む雰囲気下としては、酸素を２％以上含む雰囲気、例えば、空気中での加熱であればよい。 By performing sputtering under the conditions described above using the Ag alloy sputtering target described above, a Ga segregation portion in which Ga is concentrated is formed in the surface side region of the Ag alloy film containing Ga.
Next, by heat-treating the formed Ag alloy film, the oxidation of Ga in the Ga segregation portion can be promoted. As a heat treatment condition for the Ag alloy film, for example, it may be heated at 250 to 300° C. for about 1 to 2 hours in an atmosphere containing oxygen. The atmosphere containing oxygen may be heating in an atmosphere containing 2% or more of oxygen, for example, air.
　以上のような構成とされた本実施形態であるＡｇ合金膜においては、Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金で構成されているので、耐熱性に優れている。
　そして、Ａｇ合金膜の表面側領域にＧａが濃集したＧａ偏析部を有しているので、Ａｇ合金膜の耐熱性および耐硫化性を向上させることができる。 In the Ag alloy film of the present embodiment configured as described above, Ga is contained in the range of 0.3% by mass or more and 3.5% by mass or less, and the balance is Ag and unavoidable impurities. Since it is made of alloy, it has excellent heat resistance.
Further, since the Ag alloy film has a Ga segregation portion in which Ga concentrates in the surface side region, the heat resistance and sulfuration resistance of the Ag alloy film can be improved.
　本実施形態のＡｇ合金膜において、Ｇａに加えて、さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含んでいる場合には、Ｃｕ，ＭｇによってＡｇ原子の熱による拡散移動を抑制でき、Ａｇ合金膜の耐熱性をさらに向上させることができる。 In the Ag alloy film of the present embodiment, in addition to Ga, when one or more selected from Cu and Mg are contained in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less , Cu, and Mg can suppress the diffusion movement of Ag atoms due to heat, and can further improve the heat resistance of the Ag alloy film.
　本実施形態のＡｇ合金膜において、Ｇａに加えて、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされている場合には、Ｐｄ，Ｐｔ，Ａｕ，ＲｈがＡｇ中に固溶することで、耐熱性および耐硫化性をさらに向上させることが可能となるとともに、硝酸を含むエッチング液を用いてエッチング処理しても、エッチングレートを低く抑えることが可能となる。 In addition to Ga, the Ag alloy film of the present embodiment further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 ppm by mass or less, and the Pt The content of is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 mass ppm In the following cases, Pd, Pt, Au, and Rh are solid-dissolved in Ag, so that heat resistance and sulfurization resistance can be further improved, and an etching solution containing nitric acid is used. The etching rate can be kept low even if the etching process is performed by
　本実施形態のＡｇ合金膜において、Ｇａに加えて、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含んでいる場合には、ＣａがＡｇの結晶粒界に偏析して存在することにより、Ａｇの粒界拡散を抑制でき、さらに耐熱性を向上させることが可能となる。 In the Ag alloy film of the present embodiment, in addition to Ga, when Ca is contained in the range of 0.005% by mass or more and 0.050% by mass or less, Ca segregates at the grain boundaries of Ag. By the presence of these elements, the grain boundary diffusion of Ag can be suppressed, and the heat resistance can be further improved.
　本実施形態のＡｇ合金膜において、Ｇａに加えて、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含んでいる場合には、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌが、Ｇａと同様にＡｇ合金膜の表面側領域に偏析することにより、耐熱性および耐硫化性をさらに向上させることができる。 In the Ag alloy film of the present embodiment, in addition to Ga, one or more selected from In, Sn, Ti, and Al are added in a total amount of 0.1% by mass or more and 1.5% by mass or less. , In, Sn, Ti, and Al segregate in the surface-side region of the Ag alloy film in the same manner as Ga, thereby further improving heat resistance and sulfurization resistance.
　本実施形態のＡｇ合金膜において、Ｇａ偏析部の膜厚方向長さが２．０ｎｍ以上１２．０ｎｍ以下の範囲内である場合には、耐熱性および耐硫化性を十分に向上させるとともに、反射率の低下を防止することができる。
　本実施形態のＡｇ合金膜において、Ｇａ偏析部に透明酸化物であるＧａ酸化物が存在している場合には、Ａｇ合金膜の反射率をさらに向上させることができるとともに、より耐硫化性を向上させることができる。
　本実施形態のＡｇ合金膜において、Ｇａ偏析部が、酸化物として結晶粒界に沿い網目状に分布している場合には、さらに耐硫化性を向上させることができるとともに、さらに反射率を向上させることができる。 In the Ag alloy film of the present embodiment, when the length in the film thickness direction of the Ga segregation part is within the range of 2.0 nm or more and 12.0 nm or less, the heat resistance and sulfuration resistance are sufficiently improved, and the reflection It is possible to prevent a decrease in the rate.
In the Ag alloy film of the present embodiment, when Ga oxide, which is a transparent oxide, is present in the Ga segregation part, the reflectance of the Ag alloy film can be further improved, and the sulfidation resistance can be further improved. can be improved.
In the Ag alloy film of the present embodiment, when the Ga segregation part is distributed in a network along the grain boundary as an oxide, it is possible to further improve the sulfidation resistance and further improve the reflectance. can be made
　本実施形態のＡｇ合金スパッタリングターゲットによれば、スパッタ成膜することにより、表面側領域にＧａが濃集したＧａ偏析部を有し、耐熱性および耐硫化性に優れた本実施形態であるＡｇ合金膜を成膜することができる。 According to the Ag alloy sputtering target of this embodiment, by sputtering film formation, it has a Ga segregation part in which Ga is concentrated in the surface side region, and has excellent heat resistance and sulfidation resistance. An alloy film can be deposited.
　本実施形態のＡｇ合金スパッタリングターゲットにおいて、Ｇａに加えて、さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含んでいる場合には、さらに耐熱性に優れたＡｇ合金膜を成膜することが可能となる。 In the Ag alloy sputtering target of the present embodiment, in addition to Ga, when further containing one or more selected from Cu and Mg in a total range of 0.5 mass ppm or more and 50.0 mass ppm or less makes it possible to form an Ag alloy film with even better heat resistance.
　本実施形態のＡｇ合金スパッタリングターゲットにおいて、Ｇａに加えて、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされている場合には、さらに耐熱性および耐硫化性に優れたＡｇ合金膜を成膜することができる。 In the Ag alloy sputtering target of the present embodiment, in addition to Ga, it further contains one or more selected from Pd, Pt, Au, and Rh, and the Pd content is 40 mass ppm or less, The Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh is 1 mass ppm or more and 50 mass ppm. When the concentration is set to ppm or less, an Ag alloy film having even better heat resistance and sulfurization resistance can be formed.
　本実施形態のＡｇ合金スパッタリングターゲットにおいて、Ｇａに加えて、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含んでいる場合には、さらに耐熱性に優れたＡｇ合金膜を成膜することができる。 In the Ag alloy sputtering target of the present embodiment, in addition to Ga, when further containing Ca in the range of 0.005% by mass or more and 0.050% by mass or less, the Ag alloy film further excellent in heat resistance can be deposited.
　本実施形態のＡｇ合金スパッタリングターゲットにおいて、Ｇａに加えて、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含んでいる場合には、さらに耐熱性および耐硫化性に優れたＡｇ合金膜を成膜することができる。 In the Ag alloy sputtering target of the present embodiment, in addition to Ga, one or two or more selected from In, Sn, Ti, Al in a total amount of 0.1% by mass or more and 1.5% by mass or less When it is contained within the range, it is possible to form an Ag alloy film having even better heat resistance and sulfurization resistance.
　本実施形態のＡｇ合金スパッタリングターゲットにおいて、酸素含有量が０．００５質量％以下である場合には、スパッタ成膜時に酸素原子が成長中のＡｇ合金膜に化学吸着することを抑制でき、成膜したＡｇ合金膜の反射率、耐熱性、耐硫化性が低下することを抑制できる。 In the Ag alloy sputtering target of the present embodiment, when the oxygen content is 0.005% by mass or less, it is possible to suppress the chemical adsorption of oxygen atoms to the growing Ag alloy film during sputtering film formation. It is possible to suppress deterioration of the reflectance, heat resistance, and sulfuration resistance of the Ag alloy film.
　本実施形態のＡｇ合金スパッタリングターゲットにおいて、複数の測定箇所で測定された前記Ａｇ合金結晶粒の粒径から算出される前記平均結晶粒径Ｃが１０μｍ以上２００μｍ以下の範囲内とされているとともに、それぞれの測定箇所での前記Ａｇ合金結晶粒の粒径の平均値Ｄのうち前記平均結晶粒径Ｃとの偏差の絶対値が最大となる平均値をＤｍａｘとした場合に、Ｅ（％）＝（Ｄｍａｘ－Ｃ）／Ｃ×１００で定義される前記Ａｇ合金結晶粒の粒径ばらつきＥが２０％以下とされている場合には、スパッタ成膜時の異常放電の発生を抑制でき、安定してＡｇ合金膜を成膜することが可能となる。 In the Ag alloy sputtering target of the present embodiment, the average crystal grain size C calculated from the grain size of the Ag alloy crystal grains measured at a plurality of measurement points is within the range of 10 μm or more and 200 μm or less, When the average value of the average value D of the grain size of the Ag alloy crystal grains at each measurement point that has the maximum absolute value of the deviation from the average grain size C is defined as D max , E (%) = (D max - C) / C × 100 When the grain size variation E of the Ag alloy crystal grains is 20% or less, the occurrence of abnormal discharge during sputtering film formation can be suppressed, It becomes possible to form an Ag alloy film stably.
　以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的要件を逸脱しない範囲で適宜変更可能である。
　例えば、本実施形態では、板形状のＡｇ合金スパッタリングターゲットとして説明したが、これに限定されることはなく、円筒形状のＡｇ合金スパッタリングターゲットであってもよい。 Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the technical requirements of the invention.
For example, in the present embodiment, a plate-shaped Ag alloy sputtering target has been described, but the present invention is not limited to this, and a cylindrical Ag alloy sputtering target may be used.
　以下に、本発明の有効性を確認するために行った確認実験の結果について説明する。 The results of confirmation experiments conducted to confirm the effectiveness of the present invention are described below.
（試料の作製）
　純度９９．９９質量％以上のＡｇ原料を準備し、このＡｇ原料を真空雰囲気下の溶解炉で融解し、溶解炉内の雰囲気をＡｒガスに置換する置換操作を３回実施した。次いで純度９９．９質量％以上のＧａおよび各種原料（Ｃｕ，Ｍｇ，Ｐｄ，Ｐｔ，Ａｕ，Ｒｈ，Ｃａ，Ｉｎ，Ｓｎ，Ｔｉ，Ａｌ）を添加し、所定の組成のＡｇ合金溶湯を溶製した。そして、このＡｇ合金溶湯を、鋳造し、次いで水冷してＡｇ合金インゴットを製造した。なお、Ａｇ原料は、必要に応じて、発明の実施の形態の欄に記載されたように、電解精錬によってＰｄ，Ｐｔ，Ａｕ，Ｒｈの含有量を低減した。 (Preparation of sample)
An Ag raw material having a purity of 99.99% by mass or more was prepared, the Ag raw material was melted in a melting furnace under a vacuum atmosphere, and the replacement operation of replacing the atmosphere in the melting furnace with Ar gas was performed three times. Next, Ga with a purity of 99.9% by mass or more and various raw materials (Cu, Mg, Pd, Pt, Au, Rh, Ca, In, Sn, Ti, Al) are added to produce a molten Ag alloy of a predetermined composition. did. Then, this Ag alloy molten metal was cast and then water-cooled to produce an Ag alloy ingot. In addition, as described in the column of the embodiment of the invention, the contents of Pd, Pt, Au, and Rh in the Ag raw material were reduced by electrolytic refining, if necessary.
　得られたＡｇ合金インゴットに対して、冷間圧延（圧下率８０％、最終圧下率２５％）を行い、その後、熱処理温度６００℃、保持時間１時間の条件で熱処理を実施した。そして、熱処理後に機械加工を実施し、直径１５２．４ｍｍ、厚さ６ｍｍの円板形状で表１～３に示すＡｇ合金スパッタリングターゲットを製造した。 The obtained Ag alloy ingot was subjected to cold rolling (reduction rate of 80%, final reduction rate of 25%), and then heat treatment under conditions of a heat treatment temperature of 600°C and a holding time of 1 hour. Then, after the heat treatment, machining was performed to produce Ag alloy sputtering targets shown in Tables 1 to 3 in the form of discs having a diameter of 152.4 mm and a thickness of 6 mm.
　上記の方法で作製したＡｇ合金スパッタリングターゲットを用いて、次の条件で基板にＡｇ合金膜の成膜を行った。
　成膜開始真空度：７．０×１０－４Ｐａ以下
　スパッタガス：高純度アルゴン１００ｖｏｌ％
　チャンバー内スパッタガス圧力：０．４Ｐａ
　直流電力：１００Ｗ
　なお、上述した成膜条件で３０分間放電を行った（空スパッタ）。次いで、成膜レートを算出するための成膜を行った。そして、算出した成膜レートから膜厚１００ｎｍのＡｇ合金膜を成膜し、表４～６に示すＡｇ合金膜を得た。 Using the Ag alloy sputtering target produced by the above method, an Ag alloy film was formed on a substrate under the following conditions.
Deposition start vacuum degree: 7.0 × 10 -4 Pa or less Sputtering gas: 100 vol% high-purity argon
Sputtering gas pressure in the chamber: 0.4 Pa
DC power: 100W
In addition, discharge was performed for 30 minutes under the film forming conditions described above (empty sputtering). Next, film formation was performed for calculating the film formation rate. Then, an Ag alloy film having a film thickness of 100 nm was formed using the calculated film formation rate, and the Ag alloy films shown in Tables 4 to 6 were obtained.
（成分組成）
　それぞれのＡｇ合金スパッタリングターゲットから分析用サンプルを切り出し、ＩＣＰ発光分光分析法によって成分組成を測定した。また、酸素含有量は、分析用サンプルを入れた黒鉛るつぼを高周波加熱し、不活性ガス中で融解させ、赤外線吸収法にて検出して分析を行った。測定結果を表１～３に示す。 (Component composition)
A sample for analysis was cut out from each Ag alloy sputtering target, and the component composition was measured by ICP emission spectrometry. Further, the oxygen content was analyzed by heating a graphite crucible containing an analysis sample with high frequency, melting it in an inert gas, and detecting it by an infrared absorption method. The measurement results are shown in Tables 1-3.
　また、Ａｇ合金膜については、４インチシリコン基板上に、上述のＡｇ合金スパッタリングターゲットを用いてスパッタ成膜して厚さ５００ｎｍのＡｇ合金膜を作製した。このＡｇ合金膜から分析用サンプルを採取して、ＩＣＰ発光分光分析法によって成分組成を測定した。その結果、成膜に用いたＡｇ合金スパッタリングターゲットと同等の組成であることを確認した。 As for the Ag alloy film, an Ag alloy film having a thickness of 500 nm was formed on a 4-inch silicon substrate by sputtering using the Ag alloy sputtering target described above. A sample for analysis was taken from this Ag alloy film, and the component composition was measured by ICP emission spectrometry. As a result, it was confirmed that the composition was the same as that of the Ag alloy sputtering target used for film formation.
（Ａｇ合金スパッタリングターゲットの結晶粒径）
　スパッタ面内で均等に１６か所の地点から一辺が１０ｍｍ程度の立方体の試料片を採取した。次に各試料片のスパッタ面を研磨した。この際、＃１８０～＃４０００の耐水紙で研磨を行い、次いで３μｍ～１μｍの砥粒でバフ研磨した。さらに、光学顕微鏡で粒界が見える程度にエッチングした。ここで、エッチング液には、過酸化水素水とアンモニア水との混合液を用い、室温で１～２秒間浸漬し、粒界を現出させた。次に、各試料について、光学顕微鏡で写真を撮影した。写真の倍率としては、結晶粒を計数し易い倍率を選択した。各写真において、６０ｍｍの線分を、井げた状に２０ｍｍ間隔で縦横に合計４本引き、それぞれの直線で切断された結晶粒の数を数えた。なお、線分の端の結晶粒は、０．５個とカウントした。平均切片長さ：Ｌ（μｍ）を、Ｌ＝６００００／（Ｍ・Ｎ）（ここで、Ｍは実倍率、Ｎは切断された結晶粒数の平均値である）で求めた。次に、求めた平均切片長さ：Ｌ（μｍ）から、試料の平均粒径：ｄ（μｍ）を、ｄ＝（３／２）・Ｌで算出した。このように１６カ所からサンプリングした試料の平均粒径の平均値をターゲットの銀合金結晶の結晶粒径とした。
　なお、上記の平均粒径ｄは、それぞれの測定箇所でのＡｇ合金結晶粒の粒径の平均値Ｄであり、１６カ所の平均粒径ｄの平均値は、平均結晶粒径Ｃである。 (Crystal grain size of Ag alloy sputtering target)
A cubic sample piece having a side of about 10 mm was sampled from 16 points evenly on the sputtering surface. The sputtered surface of each sample piece was then polished. At this time, polishing was performed with waterproof paper of #180 to #4000, followed by buffing with abrasive grains of 3 μm to 1 μm. Further, etching was performed to such an extent that grain boundaries were visible with an optical microscope. Here, a mixed solution of hydrogen peroxide water and ammonia water was used as an etchant, and the substrate was immersed at room temperature for 1 to 2 seconds to reveal grain boundaries. Each sample was then photographed with an optical microscope. As the magnification of the photograph, a magnification that facilitates counting of crystal grains was selected. In each photograph, a total of four 60-mm line segments were drawn vertically and horizontally at intervals of 20 mm, and the number of crystal grains cut by each straight line was counted. The number of crystal grains at the end of the line segment was counted as 0.5. Average intercept length: L (μm) was determined by L=60000/(M·N) (where M is the actual magnification and N is the average number of cut crystal grains). Next, from the obtained average intercept length: L (μm), the average particle diameter of the sample: d (μm) was calculated by d=(3/2)·L. The average value of the average grain sizes of the samples sampled from 16 locations was taken as the crystal grain size of the silver alloy crystal of the target.
The above average grain size d is the average value D of the grain size of the Ag alloy crystal grains at each measurement point, and the average value of the average grain size d at the 16 points is the average crystal grain size C.
　そして、複数の箇所で測定されたＡｇ合金結晶粒の平均結晶粒径Ｃと、それぞれの測定箇所での前記Ａｇ合金結晶粒の粒径の平均値Ｄのうち前記平均結晶粒径Ｃとの偏差の絶対値が最大となる平均値Ｄｍａｘとから、前記Ａｇ合金結晶粒の粒径ばらつきＥを算出した。具体的には、１６カ所で求めた１６個の平均粒径のうち、平均粒径の平均値との偏差の絶対値（｜〔（ある１個の箇所の平均粒径）－（１６カ所の平均粒径の平均値）〕｜）が最大となるものを特定した。次いで、その特定した平均粒径（特定平均粒径）を用いて、下記の式により粒径のばらつきを算出した。
｛｜〔（特定平均粒径）－（１６カ所の平均粒径の平均値）〕｜／（１６カ所の平均粒径の平均値）｝×１００（％） Then, the deviation between the average grain size C of the Ag alloy crystal grains measured at a plurality of locations and the average grain size C of the average value D of the grain size of the Ag alloy crystal grains at each measurement location The grain size variation E of the Ag alloy crystal grains was calculated from the average value D max that maximizes the absolute value of . Specifically, among the 16 average particle diameters obtained at 16 locations, the absolute value of the deviation from the average value of the average particle diameter (|[(average particle diameter at one location) - (16 locations The one that maximizes the average value of average particle diameters)]|) was identified. Then, using the specified average particle size (specified average particle size), the variation in particle size was calculated according to the following formula.
{|[(specific average particle size)-(average value of average particle size at 16 locations)]|/(average value of average particle size at 16 locations)}×100 (%)
（異常放電発生回数）
　スパッタ装置内を５×１０－５Ｐａまで排気し、次いでＡｒガス圧：０．４Ｐａ、投入電力：直流５００Ｗ、ターゲット基板間距離：７０ｍｍの条件で予備スパッタとして１時間放電を実施した。次いで、本スパッタとして６時間連続放電を実施し、本スパッタ中の異常放電の合計回数を計測した。異常放電の計測には、ＤＣ電源（ＭＫＳインスツルメント社製ＲＰＤＧ－５０Ａ）のアークカウント機能を用いた。 (Number of abnormal discharge occurrences)
The inside of the sputtering apparatus was evacuated to 5×10 −5 Pa, and then discharge was performed for 1 hour as preliminary sputtering under the conditions of Ar gas pressure: 0.4 Pa, input power: DC 500 W, and target-substrate distance: 70 mm. Next, continuous discharge was performed for 6 hours as the main sputtering, and the total number of abnormal discharges during the main sputtering was measured. The arc count function of a DC power supply (RPDG-50A manufactured by MKS Instruments) was used to measure the abnormal discharge.
（Ｇａ偏析部の確認）
　成膜したＡｇ合金膜の表面（この場合、基板とは反対側の面）から基板側の方向（膜厚方向）にかけて、Ｘ線光分子分光法（ＸＰＳ）により深さ方向分析を行った。この分析には、Ｘ線光電子分光分析装置（ＵＬＶＡＣ－ＰＨＩ社製ＰＨＩ　Ｑｕａｎｔｅｒａ）を用いた。そして、Ｇａ偏析部の有無を確認し、Ｇａ偏析部の厚さを算出した。具体的には、まず、１００ｎｍのＡｇを掘りきる時間（スキャン回数）からエッチングレート（ｎｍ／スキャン）を算出した。次に１００ｎｍの半分である５０ｎｍを掘りきるスキャン回数でのＧａのピーク位置のピーク強度（カウント数／ｓｅｃ）を確認し、基準ピーク強度とした。なお、５０ｎｍを掘りきるスキャン回数でのＧａのピーク位置のピーク強度とは、表面から深さ５０ｎｍの位置でのＧａのピーク強度（Ｇａ量）である。
　そして、上述の基準ピーク強度の２．０倍以上のＧａのピーク強度が得られているスキャン回数の領域をＧａが濃集しているＧａ偏析部とみなし、Ｇａ偏析部の厚さを前述のスキャン回数×エッチングレートにて算出した。 (Confirmation of Ga segregation part)
Depth direction analysis was performed by X-ray photomolecule spectroscopy (XPS) from the surface of the formed Ag alloy film (in this case, the surface opposite to the substrate) toward the substrate side (film thickness direction). An X-ray photoelectron spectrometer (PHI Quantera manufactured by ULVAC-PHI) was used for this analysis. Then, the presence or absence of the Ga segregation portion was confirmed, and the thickness of the Ga segregation portion was calculated. Specifically, first, the etching rate (nm/scan) was calculated from the time (number of scans) required for digging 100 nm of Ag. Next, the peak intensity (number of counts/sec) at the Ga peak position in the number of scans to excavate 50 nm, which is half of 100 nm, was confirmed and used as the reference peak intensity. The peak intensity at the Ga peak position in the number of scans to excavate 50 nm is the Ga peak intensity (Ga amount) at a position at a depth of 50 nm from the surface.
Then, the region of the number of scans in which the Ga peak intensity of 2.0 times or more the reference peak intensity described above is obtained is regarded as the Ga segregation portion where Ga is concentrated, and the thickness of the Ga segregation portion is set as described above. It was calculated by multiplying the number of scans by the etching rate.
　また、ＸＰＳの深さ分析の各検出ピークの位置により、Ｇａ偏析部の酸化状態を確認した。なお、現実的には、成膜してＸＰＳにて分析するまでには大気搬送や大気熱処理等によってＧａは酸化してＧａ酸化物のＧａ２Ｏ３になるので、Ｇａのピーク強度を用いる場合と同様に、Ｇａ２Ｏ３のピーク強度の変化でＧａが濃集しているＧａ偏析部の有無を判断してもよい。それぞれの検出ピーク位置は以下のとおりである。
　Ｇａ：１１１６．５ｅＶ
　Ｇａ２Ｏ３：１１１９．２ｅＶ Moreover, the oxidation state of the Ga segregation part was confirmed from the position of each detected peak in the XPS depth analysis. Note that in reality, Ga is oxidized into Ga oxide Ga 2 O 3 by atmospheric transport, atmospheric heat treatment, etc. before the film is analyzed by XPS, so when using the peak intensity of Ga Similarly, the presence or absence of a Ga segregation part where Ga is concentrated may be judged from the change in the peak intensity of Ga 2 O 3 . Each detection peak position is as follows.
Ga: 1116.5 eV
Ga2O3 : 1119.2 eV
　図１に本発明例１０２のＡｇ合金膜（熱処理後）のＸＰＳ分析結果を示す。図２に本発明例１０２のＡｇ合金膜（熱処理後）の最表面のＧａ２ｐ３スペクトル（ＸＰＳ）を示す。Ｇａが酸化状態であることが確認される。なお、図１の縦軸の強度（Intensity）に関して、ａ×１０ｂの値は、ａＥ+ｂと表している。
　また、図３に、本発明例１０２のＡｇ合金膜（熱処理前）の最表面のＧａ２ｐ３スペクトルを示す。金属と酸化物の中間にピークを有し、Ｇａが不完全な酸化状態であることが確認される。
　また、Ｇａ酸化物の網目状分布の確認として、走査型オージェ電子分光分析装置（ＵＬＶＡＣ－ＰＨＩ社製ＰＨＩ７００）を用いて、オージェ電子分光分析法（ＡＥＳ）により表面分析を行った。具体的には、１００ｎｍのＡｇ膜表面に対して倍率２０万倍にてＳＥＭ像及びＧａ元素のオージェマップを取得した。なお、最表層の汚染物を除去する目的でＡｒスパッタリングを５００ｅＶで３０秒間行い、その後に表面分析を行った。Ｇａ元素のオージェマップからＧａ酸化物の網目状分布の有無を確認した。 FIG. 1 shows the XPS analysis results of the Ag alloy film (after heat treatment) of Example 102 of the present invention. FIG. 2 shows the Ga2p3 spectrum (XPS) of the outermost surface of the Ag alloy film (after heat treatment) of Example 102 of the present invention. Ga is confirmed to be in an oxidized state. Regarding the intensity (Intensity) on the vertical axis in FIG. 1, the value of a×10 b is expressed as aE+b.
Further, FIG. 3 shows the Ga2p3 spectrum of the outermost surface of the Ag alloy film (before heat treatment) of Example 102 of the present invention. It has a peak between the metal and the oxide, confirming that Ga is in an incompletely oxidized state.
Further, to confirm the mesh-like distribution of Ga oxide, surface analysis was performed by Auger electron spectroscopy (AES) using a scanning Auger electron spectrometer (ULVAC-PHI PHI700). Specifically, an SEM image and an Auger map of Ga element were obtained at a magnification of 200,000 times with respect to the Ag film surface of 100 nm. In order to remove contaminants on the outermost layer, Ar sputtering was performed at 500 eV for 30 seconds, after which surface analysis was performed. The presence or absence of network-like distribution of Ga oxide was confirmed from the Auger map of Ga element.
（反射率）
　反射率は分光光度計（株式会社日立ハイテクノロジーズ製Ｕ－４１００）を用いて測定した。成膜後に、大気中にて２５０℃で２時間熱処理した。この熱処理後のＡｇ合金膜の反射率を表４～６に示す。なお、表には波長４５０ｎｍにおける反射率を記載した。 (Reflectance)
The reflectance was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). After film formation, heat treatment was performed at 250° C. for 2 hours in the air. Tables 4 to 6 show the reflectance of the Ag alloy film after this heat treatment. The table shows the reflectance at a wavelength of 450 nm.
（耐熱性評価）
　成膜後に大気中にて２５０℃で２時間熱処理した。この熱処理後のＡｇ合金膜について、走査型電子顕微鏡（ＳＥＭ）により倍率２００００倍（観察面積：６０００ｎｍ×４５００ｎｍ）にて３箇所観察を行い、直径２００ｎｍ以上のヒロック（突起）発生の有無（個数）を確認した。評価結果を表４～６に示す。また、観察結果の一例を図４Ａ，図４Ｂに示す。図４Ａが本発明例１２０のＡｇ合金膜であり、図４Ｂが比較例１０１のＡｇ合金膜である。比較例１０１では、ヒロック（突起）が多く発生していることが確認される。 (Heat resistance evaluation)
After film formation, heat treatment was performed at 250° C. for 2 hours in the air. The Ag alloy film after this heat treatment was observed at three locations with a scanning electron microscope (SEM) at a magnification of 20000 (observation area: 6000 nm × 4500 nm), and the presence or absence (number) of hillocks (projections) with a diameter of 200 nm or more. It was confirmed. The evaluation results are shown in Tables 4-6. An example of observation results is shown in FIGS. 4A and 4B. 4A is the Ag alloy film of Inventive Example 120, and FIG. 4B is the Ag alloy film of Comparative Example 101. FIG. In Comparative Example 101, it is confirmed that many hillocks (protrusions) are generated.
（耐硫化性評価）
　耐硫化性評価として、成膜後に大気中にて２５０℃で２時間熱処理した。この熱処理後のＡｇ合金膜をガス腐食試験機にて２５℃－７５％ＲＨ雰囲気下にて３質量ｐｐｍのＨ２Ｓを導入して１時間保管した。次いで、分光光度計にて反射率を測定し、硫化処理前後における反射率の変化量を評価した。評価結果を表４～６に示す。 (Sulfurization resistance evaluation)
As a sulfidation resistance evaluation, heat treatment was performed at 250° C. for 2 hours in the atmosphere after the film formation. After this heat treatment, the Ag alloy film was stored for 1 hour in an atmosphere of 25° C.-75% RH by introducing 3 mass ppm of H 2 S using a gas corrosion tester. Then, the reflectance was measured with a spectrophotometer to evaluate the amount of change in reflectance before and after the sulfurization treatment. The evaluation results are shown in Tables 4-6.
（エッチング特性評価）
　ガラス基板上に成膜された厚さ１００ｎｍのＡｇ合金単膜に、フォトリソグラフィーによって配線パターン（配線膜）を形成した。具体的には、成膜したＡｇ合金膜上にフォトレジスト剤（東京応化工業株式会社製ＯＦＰＲ－８６００）をスピンコーターにより塗布し、１１０℃でプリベークした。次いで露光し、その後現像液（東京応化工業株式会社製ＮＭＤ－Ｗ）によりパターンを現像し、１５０℃でポストベークを行った。これにより、Ａｇ合金膜上に幅１００μｍ、間隔１００μｍの櫛形配線パターンを形成した。そして、上述のＡｇ合金膜に対してウェットエッチングを行った。エッチング液としては、関東化学社製ＳＥＡ－５を用い、液温４０℃、浸漬時間３０秒にてエッチングを行った。以上のようにして得られた配線膜について、配線断面を観察するために基板を劈開し、その断面を、ＳＥＭ（走査型電子顕微鏡）を用いて観察した。そして、ＳＥＭにより観察されたＡｇ合金膜端部とフォトレジスト端部の平行な位置の差分をＡｇ合金膜のオーバーエッチング量として測定した。評価結果を表４～６に示す。 (Evaluation of etching characteristics)
A wiring pattern (wiring film) was formed by photolithography on a 100 nm-thick Ag alloy single film formed on a glass substrate. Specifically, a photoresist agent (OFPR-8600 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the formed Ag alloy film by a spin coater, and prebaked at 110°C. Then, it was exposed, and then the pattern was developed with a developing solution (NMD-W manufactured by Tokyo Ohka Kogyo Co., Ltd.) and post-baked at 150°C. Thus, a comb-shaped wiring pattern having a width of 100 μm and an interval of 100 μm was formed on the Ag alloy film. Then, wet etching was performed on the Ag alloy film. As an etchant, SEA-5 manufactured by Kanto Kagaku Co., Ltd. was used, and etching was performed at a liquid temperature of 40° C. and an immersion time of 30 seconds. For the wiring film obtained as described above, the substrate was cleaved to observe the cross section of the wiring, and the cross section was observed using an SEM (scanning electron microscope). Then, the difference between the parallel positions of the edge of the Ag alloy film and the edge of the photoresist observed by SEM was measured as the amount of overetching of the Ag alloy film. The evaluation results are shown in Tables 4-6.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　比較例１のＡｇ合金スパッタリングターゲットで成膜された比較例１０１のＡｇ合金膜においては、Ｇａの含有量が本実施形態の範囲よりも少なく、Ａｇ合金膜の表面側領域にＧａ偏析部が形成されなかった。このため、耐熱性および耐硫化性が不十分であった。
　比較例２のＡｇ合金スパッタリングターゲットで成膜された比較例１０２のＡｇ合金膜においては、Ｇａの含有量が本実施形態の範囲よりも多く、Ａｇ合金膜の成膜後の反射率が低くなった。 In the Ag alloy film of Comparative Example 101 formed with the Ag alloy sputtering target of Comparative Example 1, the Ga content is lower than the range of the present embodiment, and a Ga segregation part is formed in the surface side region of the Ag alloy film. it wasn't. Therefore, the heat resistance and sulfuration resistance were insufficient.
In the Ag alloy film of Comparative Example 102 formed by the Ag alloy sputtering target of Comparative Example 2, the Ga content is higher than the range of the present embodiment, and the reflectance after the formation of the Ag alloy film is low. rice field.
　比較例３のＡｇ合金スパッタリングターゲットで成膜された比較例１０３のＡｇ合金膜および比較例４のＡｇ合金スパッタリングターゲットで成膜された比較例１０４のＡｇ合金膜においては、Ｃｕ，Ｍｇの合計含有量が本実施形態の範囲よりも多く、耐硫化性が不十分であった。
　比較例５のＡｇ合金スパッタリングターゲットで成膜された比較例１０５のＡｇ合金膜においては、ＰｄとＰｔとＡｕとＲｈの合計含有量が本実施形態の範囲よりも多く、オーバーエッチング量が大きくなった。 In the Ag alloy film of Comparative Example 103 formed with the Ag alloy sputtering target of Comparative Example 3 and the Ag alloy film of Comparative Example 104 formed with the Ag alloy sputtering target of Comparative Example 4, the total content of Cu and Mg The amount was larger than the range of this embodiment, and the sulfuration resistance was insufficient.
In the Ag alloy film of Comparative Example 105 formed by the Ag alloy sputtering target of Comparative Example 5, the total content of Pd, Pt, Au and Rh is larger than the range of the present embodiment, and the amount of overetching is large. rice field.
　比較例６においては、Ｃａの含有量が本実施形態の範囲よりも多く、圧延加工時に割れが発生し、Ａｇ合金スパッタリングターゲットを製造することができなかった。
　比較例７のＡｇ合金スパッタリングターゲットで成膜された比較例１０７のＡｇ合金膜、比較例８のＡｇ合金スパッタリングターゲットで成膜された比較例１０８のＡｇ合金膜および比較例９のＡｇ合金スパッタリングターゲットで成膜された比較例１０９のＡｇ合金膜においては、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌの合計含有量が本実施形態の範囲よりも多く、Ａｇ合金膜の成膜後の反射率が低くなった。 In Comparative Example 6, the Ca content was higher than the range of the present embodiment, cracks occurred during rolling, and an Ag alloy sputtering target could not be produced.
The Ag alloy film of Comparative Example 107 formed with the Ag alloy sputtering target of Comparative Example 7, the Ag alloy film of Comparative Example 108 formed with the Ag alloy sputtering target of Comparative Example 8, and the Ag alloy sputtering target of Comparative Example 9 In the Ag alloy film of Comparative Example 109 formed by , the total content of In, Sn, Ti, and Al was larger than the range of the present embodiment, and the reflectance after the formation of the Ag alloy film was low. .
　これに対して、本発明例１～４２のＡｇ合金スパッタリングターゲットにおいては、スパッタ成膜時の異常放電を抑制でき、安定してＡｇ合金膜を成膜することができた。
　また、本発明例１～４２のＡｇ合金スパッタリングターゲットで成膜された本発明例１０１～１４２のＡｇ合金膜においては、反射率が高く、かつ、耐熱性および耐硫化性に優れていた。また、オーバーエッチング量が少なかった。 On the other hand, in the Ag alloy sputtering targets of Examples 1 to 42 of the present invention, the abnormal discharge during sputtering film formation could be suppressed, and the Ag alloy film could be stably formed.
In addition, the Ag alloy films of Inventive Examples 101 to 142 formed from the Ag alloy sputtering targets of Inventive Examples 1 to 42 had high reflectance and excellent heat resistance and sulfidation resistance. Also, the amount of over-etching was small.
　以上のことから、本発明例によれば、耐熱性、耐硫化性に優れたＡｇ合金膜、およびこのＡｇ合金膜を成膜するためのＡｇ合金スパッタリングターゲットを提供可能であることが確認された。 From the above, it was confirmed that according to the example of the present invention, it is possible to provide an Ag alloy film excellent in heat resistance and sulfidation resistance, and an Ag alloy sputtering target for forming this Ag alloy film. .
　本実施形態のＡｇ合金膜は、耐熱性、耐硫化性に優れ、ディスプレイやＬＥＤ等の反射電極膜、タッチパネル等の配線膜等の各種部品の反射膜及び導電膜として好適に適用される。 The Ag alloy film of the present embodiment is excellent in heat resistance and sulfuration resistance, and is suitably applied as a reflective film and a conductive film for various parts such as reflective electrode films such as displays and LEDs, and wiring films such as touch panels.

Claims (15)

  1. 　Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金からなるＡｇ合金膜であって、
    　前記Ａｇ合金膜の表面側領域に、Ｇａが濃集したＧａ偏析部を有することを特徴とするＡｇ合金膜。     An Ag alloy film made of an Ag alloy having a composition containing Ga in the range of 0.3% by mass or more and 3.5% by mass or less, the balance being Ag and inevitable impurities,
    An Ag alloy film comprising a Ga segregation portion in which Ga is concentrated in a surface side region of the Ag alloy film.
  2. 　前記Ａｇ合金は、さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含むことを特徴とする請求項１に記載のＡｇ合金膜。 The Ag alloy film according to claim 1, wherein the Ag alloy further contains one or more selected from Cu and Mg in a total range of 0.5 ppm by mass or more and 50.0 ppm by mass or less. .
  3. 　前記Ａｇ合金は、さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされていることを特徴とする請求項１又は請求項２に記載のＡｇ合金膜。 The Ag alloy further contains one or more selected from Pd, Pt, Au, and Rh, and has a Pd content of 40 mass ppm or less, a Pt content of 20 mass ppm or less, The Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh is 1 mass ppm or more and 50 mass ppm or less. The Ag alloy film according to claim 1 or 2.
  4. 　前記Ａｇ合金は、さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含むことを特徴とする請求項１から請求項３のいずれか一項に記載のＡｇ合金膜。 The Ag alloy film according to any one of claims 1 to 3, wherein the Ag alloy further contains Ca in a range of 0.005% by mass to 0.050% by mass.
  5. 　前記Ａｇ合金は、さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含むことを特徴とする請求項１から請求項４のいずれか一項に記載のＡｇ合金膜。 The Ag alloy further contains one or more selected from In, Sn, Ti, and Al in a total amount of 0.1% by mass or more and 1.5% by mass or less. The Ag alloy film according to any one of claims 1 to 4.
  6. 　前記Ｇａ偏析部の膜厚方向長さが２．０ｎｍ以上１２．０ｎｍ以下の範囲であることを特徴とする請求項１から請求項５のいずれか一項に記載のＡｇ合金膜。 The Ag alloy film according to any one of claims 1 to 5, wherein the length in the film thickness direction of the Ga segregation part is in the range of 2.0 nm or more and 12.0 nm or less.
  7. 　前記Ｇａ偏析部には、Ｇａ酸化物が存在することを特徴とする請求項１から請求項６のいずれか一項に記載のＡｇ合金膜。 The Ag alloy film according to any one of claims 1 to 6, characterized in that Ga oxide is present in the Ga segregation part.
  8. 　前記Ｇａ偏析部は、酸化物として結晶粒界に沿い網目状に分布していることを特徴とする請求項１から請求項７のいずれか一項に記載のＡｇ合金膜。 The Ag alloy film according to any one of claims 1 to 7, characterized in that the Ga segregation parts are distributed as oxides in a network along grain boundaries.
  9. 　Ｇａを０．３質量％以上３．５質量％以下の範囲で含有し、残部がＡｇおよび不可避不純物からなる組成のＡｇ合金からなることを特徴とするＡｇ合金スパッタリングターゲット。 An Ag alloy sputtering target characterized by comprising an Ag alloy having a composition containing Ga in the range of 0.3% by mass or more and 3.5% by mass or less, with the balance being Ag and unavoidable impurities.
  10. 　さらに、Ｃｕ，Ｍｇから選択される１種以上を合計で０．５質量ｐｐｍ以上５０．０質量ｐｐｍ以下の範囲で含むことを特徴とする請求項９に記載のＡｇ合金スパッタリングターゲット。 The Ag alloy sputtering target according to claim 9, further comprising one or more selected from Cu and Mg in a total amount of 0.5 ppm by mass or more and 50.0 ppm by mass or less.
  11. 　さらに、Ｐｄ，Ｐｔ，Ａｕ，Ｒｈから選択される１種又は２種以上を含有しており、Ｐｄの含有量が４０質量ｐｐｍ以下、Ｐｔの含有量が２０質量ｐｐｍ以下、Ａｕの含有量が２０質量ｐｐｍ以下、Ｒｈの含有量が１０質量ｐｐｍ以下、かつ、ＰｄとＰｔとＡｕとＲｈの合計含有量が１質量ｐｐｍ以上５０質量ｐｐｍ以下とされていることを特徴とする請求項９又は請求項１０に記載のＡｇ合金スパッタリングターゲット。 Furthermore, it contains one or more selected from Pd, Pt, Au, and Rh, the Pd content is 40 mass ppm or less, the Pt content is 20 mass ppm or less, and the Au content is 20 mass ppm or less, the content of Rh is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 1 mass ppm or more and 50 mass ppm or less. The Ag alloy sputtering target according to claim 10.
  12. 　さらに、Ｃａを０．００５質量％以上０．０５０質量％以下の範囲で含むことを特徴とする請求項９から請求項１１のいずれか一項に記載のＡｇ合金スパッタリングターゲット。 The Ag alloy sputtering target according to any one of claims 9 to 11, further comprising Ca in the range of 0.005% by mass to 0.050% by mass.
  13. 　さらに、Ｉｎ，Ｓｎ，Ｔｉ，Ａｌから選択される１種又は２種以上を合計で０．１質量％以上１．５質量％以下の範囲で含むことを特徴とする請求項９から請求項１２のいずれか一項に記載のＡｇ合金スパッタリングターゲット。 Further, one or more selected from In, Sn, Ti, and Al are contained in a total amount of 0.1% by mass or more and 1.5% by mass or less. Ag alloy sputtering target according to any one of.
  14. 　酸素含有量が０．００５質量％以下であることを特徴とする請求項９から請求項１３のいずれか一項に記載のＡｇ合金スパッタリングターゲット。 The Ag alloy sputtering target according to any one of claims 9 to 13, characterized in that the oxygen content is 0.005% by mass or less.
  15. 　複数のＡｇ合金結晶粒を含む多結晶体からなり、
    　複数の測定箇所で測定された前記Ａｇ合金結晶粒の粒径から算出される平均結晶粒径Ｃが１０μｍ以上２００μｍ以下の範囲内とされているとともに、
    　それぞれの測定箇所での前記Ａｇ合金結晶粒の粒径の平均値Ｄのうち前記平均結晶粒径Ｃとの偏差の絶対値が最大となる平均値をＤｍａｘとした場合に、下記の式で定義される前記Ａｇ合金結晶粒の粒径ばらつきＥが２０％以下であることを特徴とする請求項９から請求項１４のいずれか一項に記載のＡｇ合金スパッタリングターゲット。
    　Ｅ（％）＝（Ｄｍａｘ－Ｃ）／Ｃ×１００     Consisting of a polycrystalline body containing a plurality of Ag alloy crystal grains,
    The average crystal grain size C calculated from the grain size of the Ag alloy crystal grains measured at a plurality of measurement points is in the range of 10 μm or more and 200 μm or less,
    When D max is the average value of the maximum absolute value of the deviation from the average grain size C of the average value D of the grain size of the Ag alloy crystal grains at each measurement point, the following formula is used. The Ag alloy sputtering target according to any one of claims 9 to 14, characterized in that the defined grain size variation E of the Ag alloy crystal grains is 20% or less.
    E (%) = (D max -C)/C x 100
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JP2012219307A (en) * 2011-04-06 2012-11-12 Mitsubishi Materials Corp Silver alloy sputtering target for forming conductive film and method for manufacturing the same
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