WO2013105285A1 - 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 - Google Patents
導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 Download PDFInfo
- Publication number
- WO2013105285A1 WO2013105285A1 PCT/JP2012/061872 JP2012061872W WO2013105285A1 WO 2013105285 A1 WO2013105285 A1 WO 2013105285A1 JP 2012061872 W JP2012061872 W JP 2012061872W WO 2013105285 A1 WO2013105285 A1 WO 2013105285A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- target
- silver alloy
- mass
- pass
- rolling
- Prior art date
Links
- 238000005477 sputtering target Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910001316 Ag alloy Inorganic materials 0.000 title claims description 64
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 239000013078 crystal Substances 0.000 claims abstract description 61
- 238000005096 rolling process Methods 0.000 claims abstract description 46
- 238000005098 hot rolling Methods 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 36
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000003754 machining Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 18
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims 2
- 230000000171 quenching effect Effects 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 32
- 239000010408 film Substances 0.000 description 82
- 238000004544 sputter deposition Methods 0.000 description 39
- 230000000694 effects Effects 0.000 description 15
- 230000002159 abnormal effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010891 electric arc Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/818—Reflective anodes, e.g. ITO combined with thick metallic layers
Definitions
- the present invention relates to a silver alloy sputtering target for forming a conductive film such as a reflective electrode of an organic EL element or a wiring film of a touch panel, and a method for producing the same.
- organic EL element In the organic EL element, a voltage is applied between an anode and a cathode formed on both sides of the organic EL light emitting layer, and holes are injected from the anode and electrons are injected from the cathode into the organic EL film. Light is emitted when holes and electrons are combined in the organic EL light emitting layer.
- An organic EL element is a light-emitting element that uses this light-emitting principle, and has attracted much attention in recent years for use in display devices.
- the active matrix method is advantageous for high contrast ratio and high definition, and is a driving method capable of exhibiting the characteristics of the organic EL element.
- a top emission method with a high aperture ratio increases the brightness. It is advantageous.
- the reflective electrode film in this top emission structure desirably has high reflectivity and high corrosion resistance in order to efficiently reflect the light emitted from the organic EL layer. It is also desirable that the electrode has a low resistance.
- a material an Ag alloy and an Al alloy are known. However, in order to obtain an organic EL element with higher luminance, the Ag alloy is excellent because of its high visible light reflectance.
- a sputtering method is employed for forming the reflective electrode film on the organic EL element, and a silver alloy target is used (Patent Document 1).
- Patent Document 2 In order to solve such a problem, in Patent Document 2 and Patent Document 3, formation of a reflective electrode film of an organic EL element capable of suppressing splash even when a large amount of power is applied to the target with an increase in size of the target. Silver alloy targets and methods for producing the same have been proposed.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a silver alloy sputtering target for forming a conductive film that can further suppress arc discharge and splash and a method for manufacturing the same.
- the inventors of the present invention have further refined crystal grains to an average grain size of less than 120 ⁇ m in order to suppress an increase in the number of arc discharges associated with target consumption in a silver alloy target containing Sn, It was found that it is effective to suppress the variation to 20% or less of the average particle diameter.
- the first aspect of the silver alloy sputtering target for forming a conductive film of the present invention has a component composition containing 0.1 to 1.5% by mass of Sn and the balance of Ag and inevitable impurities.
- the average grain size of the alloy crystal grains is 30 ⁇ m or more and less than 120 ⁇ m, and the grain size variation of the crystal grains is 20% or less of the average grain size.
- Sn dissolves in Ag, suppresses the growth of target crystal grains, and is effective in refining crystal grains. Since Sn improves the hardness of the target, it suppresses warpage during machining. Sn improves the corrosion resistance and heat resistance of the film formed by sputtering. When the Sn content is less than 0.1% by mass, the above effect cannot be obtained. When the Sn content exceeds 1.5% by mass, the reflectance and electrical resistance of the film are lowered. The reason why the average particle size is 30 ⁇ m or more and less than 120 ⁇ m is shown below. An average particle size of less than 30 ⁇ m is not practical and causes an increase in manufacturing cost.
- the average particle size is 120 ⁇ m or more, the tendency of abnormal discharge to increase with the consumption of the target during sputtering becomes significant. If the variation in average particle diameter exceeds 20%, the tendency of abnormal discharge to increase with the consumption of the target during sputtering becomes significant.
- the second aspect of the silver alloy sputtering target for forming a conductive film of the present invention contains 0.1 to 1.5% by mass of Sn, and further includes one or both of Sb and Ga in a total of 0.1. -2.5% by mass, the balance is composed of Ag and inevitable impurities, the alloy crystal grains have an average grain size of 30 ⁇ m or more and less than 120 ⁇ m, and variations in the grain size of the crystal grains are average grains It is 20% or less of the diameter.
- Sb and Ga have an effect of solid solution in Ag and further suppressing crystal grain growth.
- Sb and Ga further improve the corrosion resistance and heat resistance of the film formed by sputtering.
- Ga improves the chloride resistance of the film. If the total content of Sb and Ga is less than 0.1% by mass, the above effect cannot be obtained. When the total content of Sb and Ga exceeds 2.5% by mass, not only the reflectance and electric resistance of the film are lowered, but also a tendency of cracking during hot rolling appears.
- the first aspect of the method for producing a silver alloy sputtering target for forming a conductive film of the present invention is a melt casting containing 0.1 to 1.5% by mass of Sn and the balance being composed of Ag and inevitable impurities.
- a silver alloy sputtering target is manufactured by subjecting the ingot to a hot rolling step, a cooling step, and a machining step in this order.
- the hot rolling step the rolling reduction per pass is 20 to 50%, the strain rate.
- Is finished hot rolling for one pass or more under the conditions of 3 to 15 / sec and the post-pass temperature is 400 to 650 ° C.
- rapid cooling is performed at a cooling rate of 200 to 1000 ° C./min.
- the second aspect of the method for producing a silver alloy sputtering target for forming a conductive film of the present invention includes 0.1 to 1.5% by mass of Sn, and further includes one or both of Sb and Ga in total.
- a silver alloy is obtained by subjecting a melt casting ingot containing 0.1 to 2.5% by mass and the balance of Ag and inevitable impurities to a molten cast ingot in this order, in this order, a hot rolling step, a cooling step, and a machining step.
- a sputtering target is manufactured, and in the hot rolling process, the rolling reduction per pass is 20 to 50%, the strain rate is 3 to 15 / sec, and the temperature after the pass is 400 to 650 ° C.
- rapid cooling is performed at a cooling rate of 200 to 1000 ° C./min.
- the reason why the rolling reduction per pass of the finish hot rolling is set to 20 to 50% is shown below. If the rolling reduction is less than 20%, the crystal grains are not sufficiently refined. If it is attempted to obtain a reduction ratio of more than 50%, the load of the rolling mill becomes excessive, which is not realistic.
- the reason why the strain rate is 3 to 15 / sec is shown below. When the strain rate is less than 3 / sec, the crystal grains are not sufficiently refined, and a tendency to generate a mixture of fine grains and coarse grains appears. A strain rate exceeding 15 / sec is not realistic because the load of the rolling mill is excessive. When the temperature after each pass is less than 400 ° C., dynamic recrystallization becomes insufficient, and the tendency of variation in crystal grain size becomes remarkable.
- a target capable of further suppressing arc discharge and splash is obtained.
- the reflectance is high and excellent.
- a conductive film having high durability can be obtained.
- This target has an area of 0.25 m 2 or more on the target surface (the surface on the side subjected to sputtering of the target).
- the upper limit of the length is preferably 3000 mm from the viewpoint of handling of the target.
- the upper limit of the width is preferably 1700 mm from the viewpoint of the upper limit of the size that can be generally rolled by a rolling mill used in the hot rolling process.
- the thickness of the target is preferably 6 mm or more, and from the viewpoint of discharge stability of magnetron sputtering, it is preferably 25 mm or less.
- the silver alloy sputtering target for forming a conductive film according to the first embodiment is made of a silver alloy containing 0.1 to 1.5% by mass of Sn and having the balance composed of Ag and inevitable impurities.
- the average crystal grain size of the alloy is 30 ⁇ m or more and less than 120 ⁇ m, and the variation in crystal grain size is 20% or less of the average grain size.
- Ag has the effect of giving high reflectivity and low resistance to the reflective electrode film of the organic EL element and the wiring film of the touch panel formed by sputtering.
- Sn improves the hardness of the target, it suppresses warpage during machining. In particular, warping during machining of a large target having a target surface with an area of 0.25 m 2 or more can be suppressed.
- Sn has an effect of improving the corrosion resistance and heat resistance of the reflective electrode film of the organic EL element formed by sputtering. This effect is brought about by the following actions. Sn refines crystal grains in the film and reduces the surface roughness of the film. Sn dissolves in Ag to increase the strength of the crystal grains and suppress the coarsening of the crystal grains due to heat. For this reason, In has an effect of suppressing an increase in the surface roughness of the film or suppressing a decrease in reflectance due to the corrosion of the film.
- this silver alloy sputtering target for conductive film formation contributes to the improvement in the brightness of organic EL elements and the reliability of wiring such as a touch panel.
- the reason why the content of Sn is limited to the above range is shown below.
- the content of Sn contained in the silver alloy sputtering target is set to 0.1 to 1.5 mass%.
- the Sn content is more preferably 0.2 to 1.0% by mass.
- the silver alloy sputtering target for forming a conductive film according to the second embodiment includes 0.1 to 1.5 mass% of Sn, and further includes either one or both of Sb and Ga in a total amount of 0.1 to 2. Containing 5% by mass, the balance is composed of a silver alloy having a component composition composed of Ag and inevitable impurities.
- the average crystal grain size of the alloy is 30 ⁇ m or more and less than 120 ⁇ m, and the variation in crystal grain size is 20% or less of the average grain size.
- Sb and Ga have an effect of solid solution in Ag and further suppressing crystal grain growth. Corrosion resistance and heat resistance of the film formed by sputtering are further improved. In particular, Ga improves the chloride resistance of the film.
- a film formed by sputtering is used as a lead wiring film of a touch panel, the touch panel is operated by touching with a finger, and thus the wiring film needs to be resistant to chlorine components contained in sweat from the human body. By adding Ga, a film having excellent chlorination resistance can be formed. If the total content of these Sb and Ga is less than 0.1% by mass, the above effect cannot be obtained. When the total content of Sb and Ga exceeds 2.5% by mass, not only the reflectance and electric resistance of the film are lowered, but also a tendency of cracking to occur during hot rolling appears.
- the average grain size of the silver alloy crystal grains in the silver alloy sputtering target is 30 ⁇ m or more and less than 120 ⁇ m.
- an average particle diameter of less than 30 ⁇ m is not practical and causes an increase in manufacturing cost.
- abnormal discharge is likely to occur during high power sputtering, and splash is generated.
- the average grain size is 120 ⁇ m or more, the unevenness of the sputtering surface increases due to the difference in sputtering rate due to the difference in crystal orientation of each crystal grain as the target is consumed by sputtering. For this reason, abnormal discharge is likely to occur during sputtering with high power, and splash is likely to occur.
- the average particle diameter of the silver alloy crystal grains is measured as follows.
- a rectangular parallelepiped sample having a side of about 10 mm is collected from 16 points evenly within the sputtering surface of the target.
- the target is divided into 16 vertical 4 ⁇ horizontal 4 locations and collected from the central part of each part.
- a large target having a sputter surface of 500 ⁇ 500 (mm) or more that is, a target surface having an area of 0.25 m 2 or more is taken into consideration
- a rectangular target generally used as a large target is used. The method of collecting the sample is described.
- the present invention is naturally effective in suppressing the occurrence of splash on the round target.
- the sample is equally divided into 16 places on the sputtering surface of the target and collected.
- the sputter surface side of each sample piece is polished.
- polishing is performed with water resistant paper of # 180 to # 4000, and then buffed with abrasive grains of 3 ⁇ m to 1 ⁇ m.
- etching is performed to such an extent that the grain boundary can be seen with an optical microscope.
- a mixed liquid of hydrogen peroxide water and ammonia water is used as an etchant, and the mixture is immersed for 1 to 2 seconds at room temperature to reveal grain boundaries.
- a photograph with a magnification of 60 times or 120 times is taken with an optical microscope for each sample.
- the magnification of the photograph is selected so that the crystal grains can be easily counted.
- a total of four 60 mm line segments are drawn vertically and horizontally at intervals of 20 mm (as indicated by symbol #), and the number of crystal grains cut along each straight line is counted.
- the number of crystal grains at the end of the line segment is counted as 0.5.
- the average value of the average particle diameter of the sample sampled from 16 places be the average particle diameter of the silver alloy crystal grains of the target.
- the variation in particle size is calculated as follows. Of the 16 average particle diameters obtained at 16 locations, the absolute value of deviation from the average value of the average particle sizes (
- ) is specified.
- the variation in particle size is calculated by the following formula. ⁇
- the manufacturing method of the silver alloy sputtering target for conductive film formation of this embodiment is demonstrated.
- Ag having a purity of 99.99% by mass or more and Sn having a purity of 99.9% by mass or more are used as raw materials.
- Ag is melted in a high vacuum or an inert gas atmosphere, and Sn having a predetermined content is added to the resulting molten metal. Thereafter, it is melted in a vacuum or an inert gas atmosphere to produce a silver alloy melting cast ingot containing Sn: 0.1 to 1.5% by mass, and the balance being Ag and inevitable impurities.
- the melting / casting described above is preferably performed in a vacuum or in an atmosphere of inert gas replacement, but an atmospheric melting furnace can also be used.
- an inert gas is blown on the surface of the molten metal, or it is melted and cast while covering the molten metal surface with a carbon-based solid sealing material such as charcoal. Thereby, the content of oxygen and nonmetallic inclusions in the ingot can be reduced.
- the melting furnace is preferably an induction heating furnace in order to make the components uniform. Further, it is efficient and desirable to obtain a rectangular parallelepiped ingot by casting with a rectangular mold, but it is also possible to obtain a substantially rectangular ingot by processing a cylindrical ingot cast on a round mold.
- the obtained rectangular parallelepiped ingot is heated and hot-rolled to a predetermined thickness, and then rapidly cooled.
- the condition of the final hot rolling in the final stage of hot rolling is important.
- the rolling reduction per pass is 20 to 50%
- the strain rate is 3 to 15 / sec
- the rolling temperature after each rolling pass is 400 to 650 ° C.
- This finish hot rolling is performed for one or more passes.
- the total rolling rate as the whole hot rolling is, for example, 70% or more.
- the finish hot rolling is a rolling pass that strongly influences the crystal grain size of the plate material after rolling, including the final rolling pass, and, if necessary, from the final rolling pass to the third pass. You may think. After this final rolling, rolling with a rolling reduction of 7% or less may be added in the rolling temperature range for adjusting the plate thickness. Further, the strain rate ⁇ (sec ⁇ 1 ) is given by the following equation.
- H 0 sheet thickness (mm) on the entry side with respect to the rolling roll
- n rolling roll rotation speed (rpm)
- R rolling roll radius (mm)
- r rolling reduction (%)
- r ' R / 100.
- the strain rate is less than 3 / sec, the crystal grains are not sufficiently refined and a mixture of fine grains and coarse grains tends to appear. If an attempt is made to obtain a strain rate exceeding 15 / sec, the load of the rolling mill becomes excessive, which is not realistic.
- the rolling temperature after each pass is 400 to 650 ° C., which is a low temperature for hot rolling. Thereby, coarsening of crystal grains is suppressed.
- the rolling temperature is less than 400 ° C., dynamic recrystallization becomes insufficient, and the tendency of variation in crystal grain size becomes remarkable.
- the rolling temperature exceeds 650 ° C. crystal grain growth proceeds and the average crystal grain size exceeds 120 ⁇ m.
- This final finish hot rolling is performed from one pass to multiple passes as necessary. More preferable conditions for the finish hot rolling are a rolling reduction rate of 25 to 50% per pass, a strain rate of 5 to 15 / sec, and a rolling temperature after the pass of 500 to 600 ° C. It is preferable to carry out three or more passes.
- the rolling start temperature does not have to be 400 to 650 ° C., and the rolling start temperature and the pass schedule are set so that the temperature at the end of each pass in the final hot rolling at the final stage is 400 to 650 ° C.
- rapid cooling is performed at a cooling rate of 200 to 1000 ° C./min from a temperature of 400 to 650 ° C. to a temperature of 200 ° C. or less.
- a cooling rate of 200 to 1000 ° C./min from a temperature of 400 to 650 ° C. to a temperature of 200 ° C. or less.
- the rolled plate thus obtained is corrected by a correction press, a roller leveler or the like, and then finished to a desired dimension by machining such as milling or electric discharge machining.
- the arithmetic average surface roughness (Ra) of the sputtering surface of the finally obtained sputtering target is preferably 0.2 to 2 ⁇ m.
- the silver alloy sputtering target for forming a conductive film of the present embodiment obtained in this way can suppress abnormal discharge and suppress the occurrence of splash even when high power is applied during sputtering.
- a conductive film having high reflectivity and excellent durability can be obtained.
- a conductive film having good corrosion resistance and heat resistance and having a lower electric resistance can be obtained. This is particularly effective when the target size is a large target having a width of 500 mm, a length of 500 mm, and a thickness of 6 mm or more.
- Example 1 Ag having a purity of 99.99% by mass or more and Sn having a purity of 99.9% by mass or more were prepared as an additive material and loaded into a high-frequency induction melting furnace constructed with a graphite crucible. The total mass at the time of dissolution was about 1100 kg. At the time of dissolution, Ag was first dissolved, and after the Ag had melted off, additional raw materials were added so that the target composition shown in Table 1 was obtained. The molten alloy was sufficiently stirred by the stirring effect by induction heating, and then cast into a cast iron mold.
- the shrinkage nest portion of the ingot obtained by this casting was cut out, and the surface that had been in contact with the mold was removed to obtain a rectangular parallelepiped ingot having a rough dimension of 640 ⁇ 640 ⁇ 180 (mm) as a healthy portion.
- the ingot was heated to 780 ° C. and repeatedly rolled in one direction to extend from 640 mm to 1700 mm. This was rotated 90 degrees, and then rolled in the other direction of 640 mm repeatedly to obtain a plate material having a size of approximately 1700 ⁇ 2200 ⁇ 19 (mm).
- a total of 12 passes were repeated.
- the conditions of the pass from the final pass to the third pass are as shown in Table 1.
- the total rolling rate of the entire hot rolling was 90%.
- the rolled plate was cooled under the conditions shown in Table 3. After cooling, the plate material was passed through a roller leveler to correct distortion caused by rapid cooling, and machined to a size of 1600 ⁇ 2000 ⁇ 15 (mm) to obtain a target.
- Examples 2 to 10, Comparative Examples 1 to 10 In the same manner as in Example 1, the heating temperature of the ingot before hot rolling was 510 to 880 ° C., the plate thickness after final rolling was 9.5 to 25.6 mm, the total number of passes was 11 to 14 times, and the total rolling rate was varied in the range of 86-95%.
- the target was produced with the conditions of the target composition shown in Table 3, the conditions of the pass from the last pass shown in Tables 1 and 3, and the cooling rate after hot rolling shown in Table 3. In Table 3, the cooling rate is indicated by cooling with a water shower, and “no water cooling” is simply allowed to cool. However, the thickness of the target after machining was in the range of 6 to 21 mm.
- Examples 11 to 13, Comparative Example 11 It melt-cast in the same manner as in Example 1 to produce an ingot having an approximate size of 640 ⁇ 640 ⁇ 60 (mm). The ingot was heated to 680 ° C. and then hot-rolled to obtain a plate material having a size of approximately 1200 ⁇ 1300 ⁇ 15 (mm). In this hot rolling, a total of 6 passes were repeated. Among them, the conditions of the pass from the final pass to the third pass (strain rate per pass, rolling reduction, plate material temperature after pass) are as shown in Table 2. The total rolling rate of the entire hot rolling was 75%. After completion of hot rolling, the rolled plate was cooled under the conditions shown in Table 3. After cooling, the plate material was passed through a roller leveler to correct distortion caused by rapid cooling, and machined to a size of 1000 ⁇ 1200 ⁇ 12 (mm) to obtain a target.
- Examples 14 to 21, Comparative Examples 12 to 14 Ag having a purity of 99.99% by mass or more and Sn, Sb, Ga having a purity of 99.9% by mass or more were prepared as additive raw materials.
- a high frequency induction melting furnace constructed with a graphite crucible Ag was first melted, and after the Ag had melted, the additive raw material was added so that the target composition shown in Table 3 was obtained.
- the molten alloy was sufficiently stirred by the stirring effect by induction heating, and then cast into a cast iron mold.
- the ingots obtained by casting had an approximate size of 640 ⁇ 640 ⁇ 60 (mm).
- variation were measured.
- the target was attached to a sputtering apparatus, and the number of abnormal discharges during sputtering was measured. Furthermore, the surface roughness, reflectance, chlorination resistance, and specific resistance of the conductive film obtained by sputtering were measured.
- Warpage after machining The amount of warpage per 1 m length of the silver alloy sputtering target after machining was measured, and Table 4 shows the results.
- (2) Average particle diameter and its variation The particle diameter of silver alloy crystal grains was measured by the method described in the embodiment for carrying out the invention.
- samples were collected uniformly from 16 points of the target manufactured as described above, and the average particle diameter of the surface of each sample viewed from the sputtering surface was measured. And the dispersion
- the target was consumed by repeating the sputter
- the silver alloy film was held for 100 hours in a constant temperature and high humidity bath at a temperature of 80 ° C. and a humidity of 85%. Then, the absolute reflectance in wavelength 550nm of the silver alloy film was measured with the spectrophotometer. (4-3) Chlorination resistance
- a silver alloy film was formed in the same manner as described above using a target to which Ga was added (Examples 18 to 21, Comparative Examples 13 and 14). did. Next, a 5 wt% NaCl aqueous solution was sprayed on the film surface of the silver alloy film.
- Spraying was performed in a direction parallel to the film surface from a position 20 cm in height from the film surface and a distance of 10 cm from the edge of the substrate, so that the NaCl aqueous solution sprayed on the film dropped as freely as possible and adhered to the film. Spraying was repeated 5 times every minute and then rinsed with pure water 3 times. Drying was performed by blowing dry air to blow off moisture. After spraying the salt water, the surface of the silver alloy film was visually observed to evaluate the surface state. As an evaluation standard of chlorination resistance, a sample in which white turbidity or spots could not be confirmed or only partially confirmed was evaluated as “good”. Those in which white turbidity or spots could be confirmed on the entire surface were evaluated as “bad”.
- the average grain diameter of the silver alloy crystal grains is in the range of 30 ⁇ m or more and less than 120 ⁇ m, and the variation in the grain diameter of the silver alloy crystal grains is within 20% of the average grain diameter of the silver alloy crystal grains.
- the warpage after machining was small, and the number of abnormal discharges during sputtering was small not only at the beginning of use but also after consumption.
- the target to which Sb and Ga were added had a tendency that the average crystal grain size tends to be small, and the number of abnormal discharges was as small as 1 or less.
- the target with too much added amount of Sb and Ga was cracked during finish hot rolling, and the warpage could not be measured.
- the conductive film obtained from the target material of the example was excellent in reflectance and specific resistance, and the surface roughness was as small as 2 ⁇ m or less.
- the conductive film obtained from the Ga-added target has excellent chlorination resistance and is effective for a conductive film such as a touch panel.
- the target of this embodiment When the target of this embodiment is sputtered, the occurrence of arc discharge and splash is suppressed. Moreover, the conductive film obtained by sputtering the target of this embodiment is excellent in reflectance and specific resistance, and has a small surface roughness. For this reason, the target of this embodiment can be suitably applied as a target for forming a conductive film such as a reflective electrode layer of an organic EL element or a wiring film of a touch panel.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Vapour Deposition (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
本願は、2012年1月13日に、日本に出願された特願2012-005053号に基づき優先権を主張し、その内容をここに援用する。
また、光の取り出し方式には、透明基板側から光を取り出すボトムエミッション方式と、基板とは反対側に光を取り出すトップエミッション方式とがあり、開口率の高いトップエミッション方式が、高輝度化に有利である。
このような課題を解決するため、特許文献2および特許文献3では、ターゲットの大型化に伴い、ターゲットに大電力が投入されてもスプラッシュを抑制することができる有機EL素子の反射電極膜の形成用銀合金ターゲットおよびその製造方法が提案されている。
また、有機EL素子用の反射電極膜の他に、タッチパネルの引き出し配線などの導電性膜にも、銀合金膜の使用が検討されている。このような配線膜として、例えば純Agを用いると、マイグレーションが生じて短絡不良が発生しやすくなる。このため、銀合金膜の採用が検討されている。
かかる知見に基づいて、本発明の導電性膜形成用銀合金スパッタリングターゲットの第1の態様は、Snを0.1~1.5質量%含み、残部がAgおよび不可避不純物からなる成分組成を有し、合金の結晶粒の平均粒径が30μm以上120μm未満であり、前記結晶粒の粒径のばらつきが平均粒径の20%以下である。
平均粒径を30μm以上120μm未満とする理由を以下に示す。30μm未満の平均粒径は、現実的でなく製造コストの増加を招く。また、平均粒径が120μm以上であると、スパッタ時にターゲットの消耗に伴って異常放電が増加する傾向が顕著になる。
平均粒径のばらつきが20%を超えると、スパッタ時にターゲットの消耗に伴って異常放電が増加する傾向が顕著になる。
また、ひずみ速度を3~15/secとする理由を以下に示す。ひずみ速度が3/sec未満では、結晶粒の微細化が不十分となり、微細粒と粗大粒の混粒が発生する傾向が現れる。15/secを超えるひずみ速度は、圧延機の負荷荷重が過大となり現実的ではない。
各パス後の温度が400℃未満では、動的再結晶が不十分となり、結晶粒径のばらつきが増大する傾向が顕著になる。各パス後の温度が650℃を超えると、結晶粒成長が進行し平均結晶粒径が150μm以上となる。
そして、この熱間圧延後に急冷することによって結晶粒の成長を抑制し、微細な結晶粒のターゲットを得ることができる。冷却速度が200℃/min未満では、結晶粒の成長を抑制する効果に乏しい。冷却速度が1000℃/minを超えても、それ以上の微細化には寄与しない。
Snの含有量を上記範囲に限定した理由を以下に示す。Sn含有量が0.1質量%未満では、上記に記載したSnを添加することによる効果が得られない。Sn含有量が1.5質量%を超えると、膜の電気抵抗が増大したり、スパッタにより形成された膜の反射率や耐食性がかえって低下する。このため、好ましくない。したがって、膜の組成は、ターゲット組成に依存するので、銀合金スパッタリングターゲットに含まれるSnの含有量は、0.1~1.5質量%に設定される。Sn含有量は、より好ましくは0.2~1.0質量%である。
これらSb及びGaの含有量の合計が0.1質量%未満では、上記効果が得られない。Sb及びGaの含有量の合計が2.5質量%を超えると、膜の反射率や電気抵抗が低下するだけでなく、熱間圧延の際に割れが発生する傾向が現れる。
ターゲットのスパッタ面内で均等に16カ所の地点から、一辺が10mm程度の直方体の試料を採取する。具体的には、ターゲットを縦4×横4の16カ所に区分し、各部の中央部から採取する。なお、本実施形態では、500×500(mm)以上のスパッタ面、すなわちターゲット表面が0.25m2以上の面積を有する大型ターゲットを念頭に置いているので、大型ターゲットとして一般に用いられる矩形ターゲットからの試料の採取法を記載する。しかし本発明は、当然に、丸形ターゲットのスプラッシュ発生の抑制にも効果を発揮する。このときには、大型の矩形ターゲットでの試料の採取法に準じて、ターゲットのスパッタ面内で均等に16カ所に区分し、採取することとする。
次に、各試料片のスパッタ面側を研磨する。この際、#180~#4000の耐水紙で研磨を行い、次いで3μm~1μmの砥粒でバフ研磨をする。
さらに、光学顕微鏡で粒界が見える程度にエッチングする。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、粒界を現出させる。次に、各試料について、光学顕微鏡で倍率60倍もしくは120倍の写真を撮影する。写真の倍率は結晶粒を計数し易い倍率を選択する。
各写真において、60mmの線分を、井げた状に(記号#のように)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る。なお、線分の端の結晶粒は、0.5個とカウントする。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)で求める。
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で算出する。
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粒の平均粒径とする。
{|〔(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(%)
第1実施形態の導電性膜形成用銀合金スパッタリングターゲットの製造方法では、原料として純度:99.99質量%以上のAg、純度:99.9質量%以上のSnを用いる。
まず、Agを高真空または不活性ガス雰囲気中で溶解し、得られた溶湯に所定の含有量のSnを添加する。その後、真空または不活性ガス雰囲気中で溶解して、Sn:0.1~1.5質量%含み、残部がAgおよび不可避不純物からなる銀合金の溶解鋳造インゴットを作製する。
ここで、Agの溶解とSnの添加を以下のように行うことが好ましい。雰囲気を一度真空にし、次いでアルゴンで置換し、この雰囲気でAgの溶解を行う。次いでAgの溶解後にアルゴン雰囲気の中でAgの溶湯にSnを添加する。これにより、AgとSnの組成比率が安定する。
溶解炉は、成分を均一化するため誘導加熱炉が好ましい。
また、角型の鋳型で鋳造し直方体のインゴットを得るのが効率的で望ましいが、丸型の鋳型に鋳造した円柱状のインゴットを加工して概略直方体のインゴットを得ることもできる。
この場合、熱間圧延の最終段階の仕上げ熱間圧延の条件が重要であり、この仕上げ熱間圧延条件を適切に設定することにより、結晶粒が微細で均一な銀合金板を製造することができる。
具体的には、仕上げ熱間圧延においては、1パス当りの圧下率が20~50%でひずみ速度が3~15/sec、各圧延パス後の圧延温度が400~650℃とする。この仕上げ熱間圧延を1パス以上行う。熱間圧延全体としての総圧延率は、例えば70%以上とする。
ここで、仕上げ熱間圧延とは、圧延後の板材の結晶粒径に強く影響を及ぼす圧延パスであり、最終圧延パスを含み、必要に応じて、最終圧延パスから3回目までのパスであると考えてよい。この最終圧延より後に、板厚の調整のために前記圧延温度範囲で、圧下率7%以下の圧延を加えてもかまわない。
また、ひずみ速度ε(sec-1)は次式で与えられる。
1パス当りの圧下率を20~50%とし、ひずみ速度を3~15/secとすることにより、比較的低温で大きなエネルギーによって強加工することになる。これにより粗大結晶粒の混在を防止し、動的再結晶により全体として微細で均一な結晶粒を生成することができる。1パス当りの圧下率が20%未満では、結晶粒の微細化が不十分となる。50%を超える圧下率を得ようとすると、圧延機の負荷荷重が過大となり現実的ではない。また、ひずみ速度が3/sec未満では、結晶粒の微細化が不十分となり、微細粒と粗大粒の混粒が発生する傾向が現れる。15/secを超えるひずみ速度を得ようとすると、圧延機の負荷荷重が過大となり現実的ではない。
この最終の仕上げ熱間圧延を1パスから必要に応じて複数パス行う。
仕上げ熱間圧延のより好ましい条件は、1パス当りの圧下率が25~50%、ひずみ速度が5~15/sec、パス後の圧延温度が500~600℃であり、この仕上げ熱間圧延を3パス以上実施するのが好ましい。
なお、圧延開始温度は400~650℃でなくともよく、最終段階の仕上げ熱間圧延での各パス終了時の温度が400~650℃となるように、圧延開始温度、パススケジュールを設定する。
純度99.99質量%以上のAgと、添加原料として純度99.9質量%以上のSnを用意し、黒鉛るつぼで築炉した高周波誘導溶解炉に装填した。溶解時の総質量は約1100kgとした。
溶解に際しては、まずAgを溶解し、Agが溶け落ちた後、表1に示すターゲット組成となるように添加原料を投入した。合金溶湯を誘導加熱による攪拌効果により十分に攪拌し、次いで鋳鉄製の鋳型に鋳造した。
この鋳造により得られたインゴットの引け巣部分を切除し、鋳型に接していた表面を面削除去し、健全部として概略寸法640×640×180(mm)の直方体状のインゴットを得た。
この熱間圧延では、全部で12回のパスを繰り返した。そのうち、最終パスから3回目までのパスの条件(1パス当りのひずみ速度、圧下率、パス後の板材温度)を表1の通りとした。熱間圧延全体の総圧延率は90%であった。
熱間圧延終了後、圧延後の板材を表3に示す条件で冷却した。
冷却後、板材をローラレベラーに通して、急冷によって生じたひずみを矯正し、1600×2000×15(mm)の寸法に機械加工してターゲットとした。
実施例1と同様にして、熱間圧延前のインゴットの加熱温度を510~880℃、最終圧延後の板厚を9.5~25.6mm、総パス回数を11~14回、総圧延率を86~95%の範囲で変化させた。そして、表3に示すターゲット組成、表1,2に示す最終パスから3回目までのパスの条件、および表3に示す熱間圧延後の冷却速度の条件でターゲットを作製した。表3中、冷却速度を表記したものは水シャワーにより冷却したものであり、“水冷無し”は、単に放冷したものである。但し、機械加工後のターゲットの厚さは6~21mmの範囲とした。
実施例1と同様にして溶解鋳造して、概略寸法640×640×60(mm)のインゴットを作製した。このインゴットを680℃に加熱し、次いで熱間圧延して、概略1200×1300×15(mm)の寸法の板材とした。
この熱間圧延では、全部で6回のパスを繰り返した。そのうち、最終パスから3回目までのパスの条件(1パス当りのひずみ速度、圧下率、パス後の板材温度)を表2の通りとした。熱間圧延全体の総圧延率は75%であった。
熱間圧延終了後、圧延後の板材を表3に示す条件で冷却した。
冷却後、板材をローラレベラーに通して、急冷によって生じたひずみを矯正し、1000×1200×12(mm)の寸法に機械加工してターゲットとした。
純度99.99質量%以上のAgと、添加原料として純度99.9質量%以上のSn,Sb、Gaを用意した。黒鉛るつぼで築炉した高周波誘導溶解炉にて、まずAgを溶解し、Agが溶け落ちた後、表3に示すターゲット組成となるように添加原料を投入した。合金溶湯を誘導加熱による攪拌効果により十分に攪拌し、次いで鋳鉄製の鋳型に鋳造した。
これら実施例14~21、比較例12~14では、鋳造後、上記実施例11~13、比較例11と同様にして、鋳造により得られたインゴットから概略寸法640×640×60(mm)のインゴットを作製した。そしてインゴットを680℃まで加熱し、次いで上記と同様に熱間圧延して、概略1200×1300×15(mm)の寸法の板材とした。
この熱間圧延では、全部で6回のパスを繰り返した。そのうち、最終パスから3回目までのパスの条件(1パス当りのひずみ速度、圧下率、パス後の板材温度)を表2に示す通りとした。熱間圧延全体の総圧延率は75%であった。そして、表3に示す条件で冷却した。次いで、板材をローラレベラーに通して、急冷によって生じたひずみを矯正し、1000×1200×12(mm)の寸法に機械加工してターゲットとした。
(1)機械加工後の反り
機械加工後の銀合金スパッタリングターゲットについて、長さ1m当りの反り量を測定し、表4に、この結果を示した。
(2)平均粒径、そのばらつき
発明を実施するための形態に記載した方法により、銀合金結晶粒の粒径測定を行った。詳細には、上記のように製造したターゲットの16カ所の地点から均等に試料を採取して、各試料のスパッタ面から見た表面の平均粒径を測定した。そして各試料の平均粒径の平均値である銀合金結晶粒の平均粒径と、銀合金結晶粒の平均粒径のばらつきを計算した。
上記のように製造したターゲットの任意の部分から、直径:152.4mm、厚さ:6mmの円板を切り出し、銅製バッキングプレートにはんだ付けした。このはんだ付けしたターゲットを、スパッタ時のスプラッシュ評価用ターゲットとして用い、スパッタ中の異常放電回数の測定を行った。
この場合、はんだ付けしたターゲットを通常のマグネトロンスパッタ装置に取り付け、1×10-4Paまで排気した。次いで、Arガス圧:0.5Pa、投入電力:DC1000W、ターゲット基板間距離:60mmの条件で、スパッタを行った。使用初期の30分間に生じた異常放電の回数を測定した。また4時間の空スパッタと防着板の交換とを繰り返して、断続的に20時間スパッタすることによりターゲットを消耗させた。その後に更にスパッタを行い、消耗(20時間のスパッタ)後の30分間に生じた異常放電の回数を測定した。これら異常放電の回数は、MKSインスツルメンツ社製DC電源(型番:RPDG-50A)のアークカウント機能により計測した。
(4-1)膜の表面粗さ
前記評価用ターゲットを用いて、前記と同様の条件でスパッタを行い、20×20(mm)のガラス基板上に100nmの膜厚を有する銀合金膜を成膜した。さらに、耐熱性の評価のため、この銀合金膜に対して250℃、10分間の熱処理を施した。この後、銀合金膜の平均面粗さ(Ra)を原子間力顕微鏡によって測定した。
(4-2)反射率
30×30(mm)のガラス基板上に前記と同様にして銀合金膜を成膜した。そして銀合金膜の波長550nmにおける絶対反射率を、分光光度計によって測定した。
さらに、耐食性の評価のため、銀合金膜を温度80℃、湿度85%の恒温高湿槽にて100時間保持した。その後、銀合金膜の波長550nmにおける絶対反射率を、分光光度計によって測定した。
(4-3)耐塩化性
Ga添加の効果を確認するため、Gaを添加したターゲット(実施例18~21、比較例13,14)を使用して前記と同様にして銀合金膜を成膜した。次いで、銀合金膜の膜面に5重量%のNaCl水溶液を噴霧した。噴霧は、膜面から高さ20cm、基板端からの距離10cmの位置から、膜面と平行方向に行い、膜上に噴霧されたNaCl水溶液が極力自由落下して膜に付着するようにした。1分おきに噴霧を5回繰り返し、次いで純水ですすぎ洗浄を3回繰り返した。乾燥空気を噴射して水分を吹き飛ばし乾燥した。
上記の塩水噴霧後に銀合金膜面を目視で観察し、表面の状態を評価した。耐塩化性の評価基準としては、白濁又は斑点が確認できない又は一部のみに確認できるものを“良好”と評価した。白濁又は斑点が全面に確認できるものを“不良”と評価した。以上により、2段階で表面の状態を評価した。Gaを添加していないターゲットについては評価していないので、表中では“-”と表記した。
(4-4)膜の比抵抗
前記と同様にして成膜した銀合金膜の比抵抗を測定した。
これらの各評価結果を表4~6に示す。
また、実施例のターゲット材により得た導電性膜は、反射率、比抵抗に優れており、表面粗さもRaが2μm以下と小さいものであった。
また、Gaを添加したターゲットから得られた導電性膜は、耐塩化性にも優れており、タッチパネル等の導電性膜に有効であることがわかる。
Claims (4)
- Snを0.1~1.5質量%含み、残部がAgおよび不可避不純物からなる成分組成を有し、
合金の結晶粒の平均粒径が30μm以上120μm未満であり、前記結晶粒の粒径のばらつきが平均粒径の20%以下であることを特徴とする導電性膜形成用銀合金スパッタリングターゲット。 - Snを0.1~1.5質量%含み、さらに、Sb、Gaのうちいずれか一方又は両方を合計で0.1~2.5質量%含有し、残部がAgおよび不可避不純物からなる成分組成を有し、
合金の結晶粒の平均粒径が30μm以上120μm未満であり、前記結晶粒の粒径のばらつきが平均粒径の20%以下であることを特徴とする導電性膜形成用銀合金スパッタリングターゲット。 - Snを0.1~1.5質量%含み、残部がAgおよび不可避不純物からなる成分組成を有した溶解鋳造インゴットに、熱間圧延工程、冷却工程、機械加工工程をこの順に施すことにより、銀合金スパッタリングターゲットを製造し、
前記熱間圧延工程では、1パス当りの圧下率が20~50%、ひずみ速度が3~15/sec、及びパス後の温度が400~650℃の条件で1パス以上の仕上げ熱間圧延を行い、
前記冷却工程では、200~1000℃/minの冷却速度にて急冷することを特徴とする導電性膜形成用銀合金スパッタリングターゲットの製造方法。 - Snを0.1~1.5質量%含み、さらに、Sb、Gaのうちいずれか一方又は両方を合計で0.1~2.5質量%含有し、残部がAgおよび不可避不純物からなる成分組成を有した溶解鋳造インゴットに、熱間圧延工程、冷却工程、機械加工工程をこの順に施すことにより、銀合金スパッタリングターゲットを製造し、
前記熱間圧延工程では、1パス当りの圧下率が20~50%、ひずみ速度が3~15/sec、及びパス後の温度が400~650℃の条件で1パス以上の仕上げ熱間圧延を行い、
前記冷却工程では、200~1000℃/minの冷却速度にて急冷することを特徴とする導電性膜形成用銀合金スパッタリングターゲットの製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147013670A KR101854009B1 (ko) | 2012-01-13 | 2012-05-09 | 도전성 막 형성용 은 합금 스퍼터링 타겟 및 그 제조 방법 |
CN201280058004.4A CN103958727B (zh) | 2012-01-13 | 2012-05-09 | 导电性膜形成用银合金溅射靶及其制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012005053A JP5159963B1 (ja) | 2012-01-13 | 2012-01-13 | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 |
JP2012-005053 | 2012-03-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013105285A1 true WO2013105285A1 (ja) | 2013-07-18 |
Family
ID=48013558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/061872 WO2013105285A1 (ja) | 2012-01-13 | 2012-05-09 | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5159963B1 (ja) |
KR (1) | KR101854009B1 (ja) |
CN (1) | CN103958727B (ja) |
TW (1) | TWI535876B (ja) |
WO (1) | WO2013105285A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8974707B2 (en) | 2012-04-04 | 2015-03-10 | Heraeus Deutschland GmbH & Co. KG | Planar or tubular sputtering target and method for the production thereof |
EP2832895A4 (en) * | 2012-03-27 | 2016-04-13 | Mitsubishi Materials Corp | SILVER-BASED CYLINDRICAL TARGET AND METHOD FOR MANUFACTURING THE SAME |
CN106574361A (zh) * | 2014-09-18 | 2017-04-19 | 三菱综合材料株式会社 | Ag合金溅射靶、Ag合金溅射靶的制造方法、Ag合金膜及Ag合金膜的制造方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5590258B2 (ja) * | 2013-01-23 | 2014-09-17 | 三菱マテリアル株式会社 | Ag合金膜形成用スパッタリングターゲットおよびAg合金膜、Ag合金反射膜、Ag合金導電膜、Ag合金半透過膜 |
JP2015079739A (ja) * | 2013-09-13 | 2015-04-23 | 三菱マテリアル株式会社 | 有機el用反射電極膜、積層反射電極膜、及び、反射電極膜形成用スパッタリングターゲット |
EP3168325B1 (de) * | 2015-11-10 | 2022-01-05 | Materion Advanced Materials Germany GmbH | Sputtertarget auf der basis einer silberlegierung |
JP2018176493A (ja) * | 2017-04-07 | 2018-11-15 | 三菱マテリアル株式会社 | 積層膜、及び、Ag合金スパッタリングターゲット |
US20210310113A1 (en) * | 2018-10-03 | 2021-10-07 | Mitsubishi Materials Corporation | Multilayer film, and ag alloy sputtering target |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004002929A (ja) * | 2001-08-03 | 2004-01-08 | Furuya Kinzoku:Kk | 銀合金、スパッタリングターゲット、反射型lcd用反射板、反射配線電極、薄膜、その製造方法、光学記録媒体、電磁波遮蔽体、電子部品用金属材料、配線材料、電子部品、電子機器、金属膜の加工方法、電子光学部品、積層体及び建材ガラス |
JP2005036291A (ja) * | 2003-07-16 | 2005-02-10 | Kobe Steel Ltd | Ag系スパッタリングターゲット及びその製造方法 |
JP2005314717A (ja) * | 2004-04-27 | 2005-11-10 | Hitachi Metals Ltd | Ag合金スパッタリングターゲット材およびAg合金膜 |
JP2006054032A (ja) * | 2004-07-15 | 2006-02-23 | Kobe Steel Ltd | 光情報記録用Ag合金反射膜、光情報記録媒体および光情報記録用Ag合金反射膜の形成用のAg合金スパッタリングターゲット |
WO2011078188A1 (ja) * | 2009-12-22 | 2011-06-30 | 三菱伸銅株式会社 | 純銅板の製造方法及び純銅板 |
JP2011162876A (ja) * | 2010-01-12 | 2011-08-25 | Mitsubishi Materials Corp | 有機el素子の反射電極膜形成用銀合金ターゲットおよびその製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4801279B2 (ja) * | 2001-05-09 | 2011-10-26 | 石福金属興業株式会社 | スパッタリングターゲット材 |
JP3765540B2 (ja) * | 2003-01-14 | 2006-04-12 | 田中貴金属工業株式会社 | 光記録媒体の反射膜用の銀合金 |
DE10327336A1 (de) * | 2003-06-16 | 2005-01-27 | W. C. Heraeus Gmbh & Co. Kg | Legierung und deren Verwendung |
JP4309227B2 (ja) * | 2003-10-16 | 2009-08-05 | 石福金属興業株式会社 | スパッタリングターゲット材 |
-
2012
- 2012-01-13 JP JP2012005053A patent/JP5159963B1/ja not_active Expired - Fee Related
- 2012-05-08 TW TW101116355A patent/TWI535876B/zh not_active IP Right Cessation
- 2012-05-09 CN CN201280058004.4A patent/CN103958727B/zh not_active Expired - Fee Related
- 2012-05-09 KR KR1020147013670A patent/KR101854009B1/ko active IP Right Grant
- 2012-05-09 WO PCT/JP2012/061872 patent/WO2013105285A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004002929A (ja) * | 2001-08-03 | 2004-01-08 | Furuya Kinzoku:Kk | 銀合金、スパッタリングターゲット、反射型lcd用反射板、反射配線電極、薄膜、その製造方法、光学記録媒体、電磁波遮蔽体、電子部品用金属材料、配線材料、電子部品、電子機器、金属膜の加工方法、電子光学部品、積層体及び建材ガラス |
JP2005036291A (ja) * | 2003-07-16 | 2005-02-10 | Kobe Steel Ltd | Ag系スパッタリングターゲット及びその製造方法 |
JP2005314717A (ja) * | 2004-04-27 | 2005-11-10 | Hitachi Metals Ltd | Ag合金スパッタリングターゲット材およびAg合金膜 |
JP2006054032A (ja) * | 2004-07-15 | 2006-02-23 | Kobe Steel Ltd | 光情報記録用Ag合金反射膜、光情報記録媒体および光情報記録用Ag合金反射膜の形成用のAg合金スパッタリングターゲット |
WO2011078188A1 (ja) * | 2009-12-22 | 2011-06-30 | 三菱伸銅株式会社 | 純銅板の製造方法及び純銅板 |
JP2011162876A (ja) * | 2010-01-12 | 2011-08-25 | Mitsubishi Materials Corp | 有機el素子の反射電極膜形成用銀合金ターゲットおよびその製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2832895A4 (en) * | 2012-03-27 | 2016-04-13 | Mitsubishi Materials Corp | SILVER-BASED CYLINDRICAL TARGET AND METHOD FOR MANUFACTURING THE SAME |
US8974707B2 (en) | 2012-04-04 | 2015-03-10 | Heraeus Deutschland GmbH & Co. KG | Planar or tubular sputtering target and method for the production thereof |
CN106574361A (zh) * | 2014-09-18 | 2017-04-19 | 三菱综合材料株式会社 | Ag合金溅射靶、Ag合金溅射靶的制造方法、Ag合金膜及Ag合金膜的制造方法 |
US10060025B2 (en) | 2014-09-18 | 2018-08-28 | Mitsubishi Materials Corporation | Ag alloy sputtering target, method of manufacturing Ag alloy sputtering target, Ag alloy film, and method of forming Ag alloy film |
Also Published As
Publication number | Publication date |
---|---|
CN103958727B (zh) | 2016-03-16 |
JP5159963B1 (ja) | 2013-03-13 |
KR20140113634A (ko) | 2014-09-24 |
CN103958727A (zh) | 2014-07-30 |
JP2013144823A (ja) | 2013-07-25 |
TW201329263A (zh) | 2013-07-16 |
KR101854009B1 (ko) | 2018-05-02 |
TWI535876B (zh) | 2016-06-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5612147B2 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP5159962B1 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP5159963B1 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP4793502B2 (ja) | 有機el素子の反射電極膜形成用銀合金ターゲットおよびその製造方法 | |
WO2012137461A1 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP5533545B2 (ja) | 有機el素子の反射電極膜形成用銀合金ターゲットおよびその製造方法 | |
JP2012162768A (ja) | Al基合金スパッタリングターゲット、及びCu基合金スパッタリングターゲット | |
JP5669014B2 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP5830907B2 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP5830908B2 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP5547574B2 (ja) | Al基合金スパッタリングターゲット | |
JP5669015B2 (ja) | 導電性膜形成用銀合金スパッタリングターゲットおよびその製造方法 | |
JP2016065290A (ja) | Ag合金スパッタリングターゲット |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201280058004.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12864767 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147013670 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12864767 Country of ref document: EP Kind code of ref document: A1 |