TW201305353A - Silver alloy sputtering target for forming electroconductive film, and method for manufacture same - Google Patents

Abstract

Provided is a silver alloy sputtering target for forming an electroconductive film, the sputtering target being capable of inhibiting splashing even when high power is introduced into the target in line with increased target size, having excellent corrosion resistance and heat resistance, and being capable of forming a low-electrical-resistance film. Also provided is a method for manufacturing such a sputtering target. This silver alloy sputtering target for forming an electroconductive film comprises a silver alloy having a component composition containing a total of 0.1 to 1.5 mass% of Ga and/or Sn, with the balance being Ag and unavoidable impurities; or comprises a silver alloy having a component composition further containing 0.1 to 1.5 mass% of In. The average size of the crystal grains of the silver alloy is 120 to 400 μm, or 120 to 250 μm when In is included. The variation in the grain size of the crystal grains is 20% or less of the average grain size.

Description

Silver alloy sputtering target for forming conductive film and manufacturing method thereof

The present invention relates to a silver alloy sputtering target for forming a conductive film such as a reflective electrode film of an organic electroluminescence (EL) device or a wiring film of a touch panel, and a method for producing the same. Further, in detail, it relates to a large silver alloy sputtering target.

An organic EL (electroluminescence) element is formed by applying a voltage between an anode and a cathode formed on both sides of an organic EL light-emitting layer, injecting a positive hole into an organic EL film from an anode, and injecting electrons from a cathode in an organic EL light-emitting layer. A light-emitting element that emits light when a positive hole is combined with an electron has been attracting attention in recent years as a display device. The driving method of the organic EL element includes a passive array method and an active array method. The active array method is capable of switching at a high speed by providing one or more thin film transistors on one pixel, so that it is advantageous in high contrast and high definition, and can be driven by the characteristics of the organic EL element. the way.

Further, the light extraction method includes a bottom emission method in which light is taken out from the transparent plate side, and a top emission method in which light is taken out on the side opposite to the substrate, and a top emission method having a high aperture ratio is advantageous for high luminance.

In Fig. 2, an example of a layer structure of a top emission structure in which a reflective electrode is used as an anode is shown. Here, the reflective electrode film (described as "reflective anodic film" in FIG. 2) is preferably a high reflectance and high corrosion resistance in order to efficiently reflect light emitted from the organic EL film. In addition, as an electrode with low resistance It is better. As such a material, a silver alloy and an aluminum alloy are known, and in order to obtain a higher-luminance organic EL element, since the visible light reflectance is high, the silver alloy is excellent. Here, when a reflective electrode film is formed on an organic EL element, a silver alloy sputtering target is used by a sputtering method (Patent Document 1).

In addition to the reflective electrode film for an organic EL device, a silver alloy film is also used for the conductive film such as the pull-out wiring of the touch panel. When such a wiring film is used, for example, pure silver is used, and short-circuit failure is likely to occur, so that the use of the silver alloy film is reviewed.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2002/077317

However, the aforementioned prior art has the following problems.

In other words, with the increase in the size of the glass substrate during the production of the organic EL element, the silver alloy target used for the reflective electrode film has also begun to use a large target. Here, when high-power is applied to a large-scale target for sputtering, a phenomenon called "splash" occurs when the target is abnormally discharged, and the wiring or the electrode is short-circuited because the molten fine particles adhere to the substrate. This causes a problem that the productivity of the organic EL element is lowered. The reflective electrode film of the organic EL element of the top emission type is to be the lower layer of the organic EL light-emitting layer. Therefore, it is required to have higher flatness, and it is necessary to suppress splash more.

In addition, as a reflective film of an organic EL element, a high reflectance is expected, and a conductive film such as a reflective electrode film of an organic EL element and a wiring film of a touch panel is required to have good corrosion resistance and heat resistance of the film. Sex or low resistance.

The present invention has been made in view of the above-described problems, and it is an object of the invention to provide a low resistance even if high power is applied to a target, and spatter can be suppressed, and corrosion resistance and heat resistance are excellent, and low resistance can be formed. The conductive model of the film is a silver alloy sputtering target and a method of manufacturing the same.

In the case of the inventors of the present invention, it has been found that the average particle diameter of the crystal grains of the silver alloy sputtering target for forming a conductive film is 120 to 400 μm by a specific production method, and spatter can be suppressed even if a large amount of electric power is input. In addition, it has been found that adding an appropriate amount of gallium or tin to silver can improve the corrosion resistance and heat resistance of the film.

In addition, the inventors of the present invention have found that by adding an appropriate amount of indium, gallium or tin to silver and making the average particle diameter of the crystal grains 120 to 250 μm, it is possible to suppress splash even if large electric power is supplied.

That is, the present invention has been obtained from the above findings, and the following configuration has been adopted to solve the above problems.

A silver alloy sputtering target for forming a conductive film according to the first aspect of the invention is characterized in that it has 0.1 to 1.5 in total of one or two of gallium and tin. The mass percentage (hereinafter also referred to as "% by mass"), and the remainder is composed of a silver alloy composed of silver and an unavoidable impurity, and the average grain size of the crystal grains of the silver alloy is 120 to 400 μm. The dispersion of the particle diameter of the particles is 20% or less of the average particle diameter.

In the above-mentioned content range, the silver alloy sputtering target for forming a conductive film is composed of one or two of gallium and tin in a total amount of 0.1 to 1.5% by mass, and the balance being silver and inevitable impurities. The composition of the composition of the silver alloy is such that the average particle diameter of the crystal grains of the silver alloy is 120 to 400 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter. Therefore, even if large electric power is supplied during sputtering, Suppresses abnormal discharge and suppresses the occurrence of splash. Further, by using the silver alloy sputtering target for forming a conductive film to perform sputtering, a conductive film having good corrosion resistance and heat resistance and further low resistance can be obtained.

In the silver alloy sputtering target for forming a conductive film according to the second aspect of the invention, it is characterized in that one or two of gallium and tin are contained in an amount of 0.1 to 1.5% by mass, and one of copper and magnesium or Two types of silver alloys each having a composition of 1.0% by mass or less and a balance of silver and an unavoidable impurity, the average particle diameter of the crystal grains of the silver alloy being 120 to 400 μm, and the particle size of the crystal grains The dispersion is less than 20% of the average particle diameter.

In other words, in the silver alloy sputtering target for forming a conductive film, one or two or more of copper and magnesium are contained in the above range, so that coarsening of crystal grains can be further suppressed, and the film can be further suppressed. The reflectance caused by corrosion is reduced.

In the silver alloy sputtering target for forming a conductive film according to the third aspect of the invention, it is characterized in that it contains 0.1 to 1.5% by mass of one or two of gallium and tin, and further, cerium (Ce) and cerium (Eu). One or two of them are contained in a total amount of 0.8% by mass or less, and the remainder is a silver alloy having a composition of silver and an unavoidable impurity, and the average particle diameter of the crystal grains of the silver alloy is 120 to 400 μm. The dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter.

In other words, in the silver alloy sputtering target for forming a conductive film, one or two or more of cerium and lanthanum are contained in the above range, so that coarsening of crystal grains can be further suppressed, and the film can be further suppressed. The reflectance caused by corrosion is reduced.

The silver alloy sputtering target for forming a conductive film according to the fourth aspect of the invention is characterized in that it contains 0.1 to 1.5% by mass of indium, and further contains 0.1 to 1.5% by mass of one or two of gallium and tin. It is composed of a silver alloy having a composition of silver and an unavoidable impurity. The average particle diameter of the crystal grains of the silver alloy is 120 to 250 μm, and the dispersion of the particle diameter of the crystal grains is 20 of the average particle diameter. %the following.

In the above-mentioned content range, the silver alloy sputtering target is contained in an amount of indium, and one or two of gallium and tin are contained in an amount of 0.1 to 1.5% by mass, and the balance is silver and inevitable impurities. A silver alloy having a composition of components, wherein the average grain size of the crystal grains of the silver alloy is 120 to 250 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter, so even in sputtering When large power is supplied, it is possible to suppress abnormal discharge and suppress the occurrence of splash. In addition, by By using this conductive film to form a silver alloy sputtering target for sputtering, a conductive film having good corrosion resistance and heat resistance and further low resistance can be obtained.

A silver alloy sputtering target for forming a conductive film according to the fifth aspect of the invention is characterized in that it contains 0.1 to 1.5% by mass of indium, and further contains 0.1 to 1.5% by mass of one or two of gallium and tin. One or two of copper and magnesium are contained in a total amount of 1.0% by mass or less, and the remainder is composed of a silver alloy having a composition of silver and unavoidable impurities. The average grain size of the crystal grains of the silver alloy is 120. ~250 μm, the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter.

In other words, in the silver alloy sputtering target for forming a conductive film, one or two or more of copper and magnesium are contained in the above range, so that coarsening of crystal grains can be further suppressed, and the film can be further suppressed. The reflectance caused by corrosion is reduced.

The silver alloy sputtering target for forming a conductive film according to the sixth aspect of the invention is characterized in that it contains 0.1 to 1.5% by mass of indium, and further contains 0.1 to 1.5% by mass of one or two of gallium and tin. One or two of cerium and lanthanum are contained in a total amount of 0.8% by mass or less, and the remainder is composed of a silver alloy having a composition of silver and unavoidable impurities. The average grain size of the crystal grains of the silver alloy is 120. ~250 μm, the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter.

In other words, in the silver alloy sputtering target for forming a conductive film, one or two or more of cerium and lanthanum are contained in the above range, so that coarsening of crystal grains can be further suppressed, and the film can be further suppressed. The reflectance caused by corrosion is reduced.

The silver alloy sputtering target for forming a conductive film according to the seventh aspect of the invention is any one of the first to sixth inventions, characterized in that the surface of the target has an area of 0.25 m ² or more.

That is, in the case where the silver alloy sputtering target for forming a conductive film is used for a large-sized sputtering target, the above-described effects are remarkable.

A method for producing a silver alloy sputtering target for forming a conductive film according to the eighth aspect of the invention is characterized in that the method for producing a silver alloy sputtering target for forming a first conductive film is one or two of gallium and tin. A molten casting ingot consisting of 0.1 to 1.5% by mass of the total, and the remaining part is composed of silver and unavoidable impurities, sequentially: 6 to 20 times of hot-up upsetting forging, cold room The step of calendering, the step of heat treatment, and the step of performing mechanical processing.

In other words, in the method for producing a silver alloy sputtering target for forming a conductive film, by repeating the step of upsetting forging between 6 and 20 times, the particle size of the crystal grains can be made even for a large target. The dispersion is less than 20% of the average particle diameter.

A method for producing a silver alloy sputtering target for forming a conductive film according to the ninth aspect of the invention is characterized in that the method for producing a silver alloy sputtering target for forming a second conductive film is one of gallium and tin. A molten casting ingot containing a composition of 1.5% by mass or less, and a total of 1.0% by mass or less of the total amount of copper and magnesium, and a component of silver and an unavoidable impurity, in a total amount of 1.5% by mass or less. : a step of repeating upsetting forging 6 to 20 times, a step of cold rolling, a step of heat treatment, and a step of performing mechanical processing.

In other words, in the method for producing a silver alloy sputtering target for forming a conductive film, the molten ingot is melted, and one or a combination of copper and magnesium is contained in an amount of 1.0% by mass or less in total, so that crystal grains can be further suppressed. The silver alloy sputtering target of the second invention described above is coarsened.

The method for producing a silver alloy sputtering target for forming a conductive film according to the tenth aspect of the invention is characterized in that the method for producing a silver alloy sputtering target for forming a third conductive film is one of gallium and tin. A molten casting ingot containing a composition of 1.5% by mass or less, and a total of 0.8% by mass or less, and the remaining part being silver and unavoidable impurities, in a total amount of 1.5% by mass or less. : a step of repeating upsetting forging 6 to 20 times, a step of cold rolling, a step of heat treatment, and a step of performing mechanical processing.

In other words, in the method for producing a silver alloy sputtering target for forming a conductive film, the molten ingot is melted, and one or a combination of one or two of cerium and lanthanum is contained in an amount of 0.8% by mass or less. The silver alloy sputtering target of the third invention described above is coarsened.

In the method for producing a silver alloy sputtering target for forming a conductive film according to the eleventh aspect of the invention, the method for producing a silver alloy sputtering target for forming a fourth conductive film is characterized in that it contains 0.1 to 1.5% by mass of indium and further has gallium One or two kinds of tins containing 0.1 to 1.5% by mass in total, and the remaining part is a molten casting ingot composed of silver and unavoidable impurities, which are sequentially carried out: 6 to 20 times of hot upset The step of forging, the step of cold rolling, the step of heat treatment, and the step of performing machining.

In other words, in the method for producing a silver alloy sputtering target for forming a conductive film, by repeating the step of upsetting forging between 6 and 20 times, the particle size of the crystal grains can be made even for a large target. The dispersion is less than 20% of the average particle diameter.

In the method for producing a silver alloy sputtering target for forming a conductive film according to the twelfth aspect of the invention, the method for producing a silver alloy sputtering target for forming a fifth conductive film is characterized in that it contains 0.1 to 1.5% by mass of indium and further has gallium One or two of the tins are contained in an amount of 0.1 to 1.5% by mass in total, and one or two of copper and magnesium are contained in a total amount of 1.0% by mass or less, and the remainder is composed of silver and unavoidable impurities. The melted cast ingot of the composition is sequentially carried out: a step of repeating upsetting forging 6 to 20 times, a step of cold rolling, a step of heat treatment, and a step of performing mechanical processing.

In other words, in the method for producing a silver alloy sputtering target for forming a conductive film, the molten ingot is melted, and one or a combination of copper and magnesium is contained in an amount of 1.0% by mass or less in total, so that crystal grains can be further suppressed. The silver alloy sputtering target of the fifth invention described above is coarsened.

In the method for producing a silver alloy sputtering target for forming a conductive film according to the thirteenth aspect of the invention, the method for producing a silver alloy sputtering target for forming a sixth conductive film is characterized in that it contains 0.1 to 1.5% by mass of indium and further has gallium One or two of the tins are contained in an amount of 0.1 to 1.5% by mass in total, and are contained in a total of 0.8% by mass or less in combination with one or two of cerium and lanthanum, and the remainder is composed of silver and unavoidable impurities. The composition of the melt casting ingot, in sequence: repeat 6 to 20 times of hot upsetting forging steps The step of rolling, the step of cold rolling, the step of heat treatment, and the step of performing mechanical processing.

In other words, in the method for producing a silver alloy sputtering target for forming a conductive film, the molten ingot is melted, and one or a combination of one or two of cerium and lanthanum is contained in an amount of 0.8% by mass or less. The silver alloy sputtering target of the sixth invention described above is coarsened.

The method for producing a silver alloy sputtering target for forming a conductive film according to claim 14 is the invention of any one of the eighth to thirteenth aspects, characterized in that the temperature of the upsetting forging is 750 to 850. °C.

That is, in the method for producing a silver alloy sputtering target for forming a conductive film, since the temperature of the upsetting forging is 750 to 850 ° C, the dispersion of the particle size of the crystal grains can be made the average particle diameter. 20% or less, and the average particle diameter of the crystal grains is 400 μm or less. Further, in the method for producing a silver alloy sputtering target for forming a conductive film containing 0.1 to 1.5% by mass of indium, the average particle diameter of the crystal grains can be 250 μm or less.

According to the present invention, the following effects can be achieved.

The silver alloy sputtering target for forming a conductive film according to the present invention comprises one or two kinds of silver alloys containing gallium and tin in the above content range, and the average grain size of the crystal grains of the silver alloy is 120~ 400 μm, the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter. Therefore, it is possible to suppress the occurrence of splash during sputtering, and at the same time, it has good corrosion resistance and heat resistance, and can obtain low-resistance electric conduction. membrane.

Further, the silver alloy sputtering target for forming a conductive film according to the present invention comprises indium contained in the above-mentioned content range, and one or two kinds of silver alloys of gallium and tin, and the average of the crystal grains of the silver alloy. The particle diameter is 120 to 250 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter. Therefore, it is possible to suppress the occurrence of splash during sputtering and to have good corrosion resistance and heat resistance. A low-resistance conductive film is obtained.

Further, according to the method for producing a silver alloy sputtering target for forming a conductive film of the present invention, it is possible to suppress the occurrence of splash even in a large-sized target, and it is possible to manufacture a silver alloy sputtering target which can form a favorable conductive film.

Hereinafter, an embodiment of a silver alloy sputtering target for forming a conductive film according to the present invention and a method for producing the same will be described with reference to FIG. Further, "%" means % by mass unless otherwise specified.

The silver alloy sputtering target for forming a conductive film of the present embodiment is composed of one or two of gallium and tin in a total amount of 0.1 to 1.5% by mass, and the balance being silver and inevitable impurities. In the silver alloy of the composition, the average grain size of the crystal grains of the silver alloy (hereinafter referred to as silver alloy crystal grains) is 120 to 400 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter. .

In addition, the silver alloy sputtering target for forming a conductive film of the present embodiment may have a total of 0.1 to 1.5% by mass of one or two of gallium and tin, and one of copper and magnesium. 2 kinds of totals contain 1.0 mass Below %, the rest is composed of a silver alloy composed of silver and an inevitable impurity.

In addition, the copper or magnesium may be used instead of one or two of ruthenium and osmium in a total amount of 0.8% by mass or less.

In addition, the silver alloy sputtering target for forming a conductive film of the present embodiment contains 0.1 to 1.5% by mass of indium, and further contains 0.1 to 1.5% by mass of one or two of gallium and tin, and the rest. It is composed of a silver alloy having a composition of silver and an unavoidable impurity, and the crystal grain of the silver alloy (hereinafter referred to as a silver alloy crystal grain) has an average particle diameter of 120 to 250 μm, and the particle diameter of the crystal grain is The dispersion is 20% or less of the average particle diameter.

In addition, the silver alloy sputtering target for forming a conductive film of the present embodiment may have an indium content of 0.1 to 1.5% by mass, and a total of 0.1 to 1.5% by mass of one or two of gallium and tin, and copper. One or two of the total amount of magnesium is 1.0% by mass or less, and the remainder is composed of a silver alloy having a composition of silver and an unavoidable impurity.

In addition, the copper or magnesium may be used instead of one or two of ruthenium and osmium in a total amount of 0.8% by mass or less.

In the sputtering target of this embodiment, the target surface (the surface on which the target is to be sputtered) has an area of 0.25 m ² or more, and in the case of a rectangular target, at least one side is 500 mm or more, and the upper limit of the length is operated by the target. From a sexual point of view, it is better to use 2500mm. On the other hand, the upper limit of the width is preferably 1700 mm from the viewpoint of the upper limit of the size which can be generally rolled by the calender used in the cold rolling step. Further, from the viewpoint of the frequency of exchange of the target, the thickness of the target is preferably 6 mm or more, and from the viewpoint of discharge stability of magnetron sputtering, it is preferably 20 mm or less.

The silver has an effect of reducing the electric resistance of the reflective electrode film of the organic EL element formed by sputtering or the wiring film of the touch panel.

The gallium, tin, and indium have an effect of increasing the hardness of the target, and can suppress warpage during machining. In particular, warpage at the time of machining of a large target having an area of 0.25 m ² or more on the target surface can be suppressed. Further, an appropriate amount of addition of gallium, tin, and indium also has an effect of improving the corrosion resistance and heat resistance of the conductive film formed by sputtering. This is because gallium, tin, and indium have crystal grains in the fine film, and at the same time reduce the surface roughness of the film. Further, solid solution in silver increases the strength of crystal grains, suppresses heat, causes coarsening of crystal grains, and suppresses film. The increase in surface roughness or the suppression of corrosion of the film leads to a decrease in reflectance. In other words, the reflective electrode film or the wiring film formed by the silver alloy sputtering target for forming a conductive film of the present embodiment can improve the corrosion resistance and heat resistance of the film, and contribute to the improvement of the luminance or the improvement of the organic EL element. Reliability of wiring such as touch panels.

In addition, the reason why the total content of one or two of gallium and tin is limited to the above range is that one or two of gallium and tin are contained in a total amount of less than 0.1% by mass, and the above description cannot be obtained. When the effect of adding gallium or tin is contained, and one or two of gallium and tin are more than 1.5% by mass in total, the electrical resistance of the film increases, or the corrosion resistance of the film formed by sputtering is lowered, and it is not desirable to see the result of. In other words, the composition of the film depends on the target composition. Therefore, the total content of one or two of gallium and tin contained in the silver alloy sputtering target is set to 0.1 to 1.5% by mass, and more preferably 0.2~1.0 quality%.

In addition, the reason why the indium content is limited to the above range is that the effect of adding indium described above cannot be obtained even if the indium content is less than 0.1% by mass, and if the indium content exceeds 1.5% by mass, the electric resistance of the film is increased or sputtering is performed. The corrosion resistance of the formed film is rather lowered, which is a result that is not desired to be seen. That is, since the composition of the film depends on the target composition, the content of indium contained in the silver alloy sputtering target is set to 0.1 to 1.5% by mass, and more preferably 0.2 to 1.0% by mass.

The copper and magnesium described above are solid-solubilized in silver and have an effect of preventing coarsening of crystal grains. In particular, as the size of the target is increased, the silver alloy crystal grains are easily coarsened in the target, and splashes during sputtering are induced. Therefore, the coarsening of the silver alloy crystal grains is suppressed by the addition of copper or magnesium. Brings remarkable results. Further, in the film formed by sputtering, the addition of an appropriate amount of copper or magnesium further suppresses the coarsening of crystal grains caused by heat, suppresses an increase in the surface roughness of the film, or further suppresses the corrosion of the film to cause reflectance. The effect of the reduction.

In addition, when the content of copper or magnesium is limited to the above range, when one or more of copper and magnesium are contained in a total amount of more than 1.0% by mass, the corrosion resistance of the film formed by sputtering may be lowered, or The resistance of the film increases, so it is not suitable for the electrode film or the wiring film. In other words, the composition of the film formed by the sputtering depends on the target composition. Therefore, the total content of one or two of copper and magnesium contained in the silver alloy sputtering target is set to 1.0% by mass or less, more preferably It is set at 0.3 to 0.8% by mass.

The above-mentioned ruthenium, osmium, and silver form an intermetallic compound, intermetallicization The compound segregates at the grain boundary and has an effect of preventing coarsening of the crystal grains. In particular, as the size of the target increases, the alloy crystal grains are easily coarsened in the target, and splashes during sputtering are induced. Therefore, the coarsening of the silver alloy crystal grains is suppressed by the addition of cerium and lanthanum. Come to a significant effect. Further, in the film formed by the sputtering, it is possible to further suppress the increase in the surface roughness of the film due to the coarsening of the crystal grains caused by the heat, or to further suppress the decrease in the reflectance due to the corrosion of the film.

In addition, when the content of cerium and lanthanum is limited to the above range, when one or two of cerium and lanthanum are contained in a total amount of more than 0.8% by mass, precipitation of intermetallic compounds of these elements and silver is observed in the target structure. As the amount increases, the particle size of the precipitate becomes coarse, which causes an abnormal discharge at the time of sputtering to increase, which is not preferable. In other words, the composition of the film formed by the sputtering depends on the target composition. Therefore, the total content of one or two of the lanthanum and cerium contained in the silver alloy sputtering target is set to 0.8% by mass or less, more preferably It is set at 0.3 to 0.5% by mass.

Here, the quantitative analysis of gallium, tin, indium, copper, magnesium, lanthanum and cerium is carried out by inductively coupled plasma analysis (ICP method).

The average particle diameter of the silver alloy crystal grains in the sputtering target of the present embodiment is 120 to 400 μm, preferably 150 to 350 μm. The reason why the average particle diameter of the silver alloy crystal grains is limited to the above range is that when the average particle diameter is smaller than 120 μm, the dispersion of the crystal grain size becomes large, and in the sputtering of large electric power, abnormal discharge is likely to occur and it may occur. The reason for the splash. On the other hand, if the average particle diameter exceeds 400 μm, the target material is consumed by sputtering, and the crystal orientation of each crystal grain is different to cause a sputtering rate. The difference is that the unevenness of the sputtering surface is increased, and in the sputtering of large electric power, abnormal discharge is likely to occur, and splashing is likely to occur.

The average particle diameter of the silver alloy crystal grains in the sputtering target of the present embodiment containing indium is 120 to 250 μm, preferably 150 to 220 μm. The reason why the average particle diameter of the silver alloy crystal grains is limited to the above range is that when the average particle diameter is smaller than 120 μm, the dispersion of the crystal grain size becomes large, and in the sputtering of large electric power, abnormal discharge is likely to occur and it may occur. The reason for the splash. On the other hand, when the average particle diameter exceeds 250 μm, the target material is consumed by sputtering, and the crystal orientation of each crystal grain is different to cause a difference in sputtering rate, which causes the unevenness of the sputtering surface to increase, and the large power splashes. During plating, abnormal discharge is likely to occur, and splashing is likely to occur.

Here, the average particle diameter of the silver alloy crystal grains was measured as described below.

First, a square sample having a side of about 10 mm was taken from the 16 points in the sputtering surface of the sputtering target. Specifically, the sputtering target is divided into 16 positions of 4 in the vertical direction and 4 in the horizontal direction, and is taken from the central portion of each part.

Further, in the present embodiment, a sputtering target of 500 × 500 (mm) or more, that is, a large target having an area of 0.25 m ² or more on the target surface is used, and therefore, it is generally used from a large target. The rectangular target takes the method of taking the sample, but in the present embodiment, of course, the suppression of the occurrence of splash on the circular target can also exert an effect. At this time, according to the sample taking method of the large rectangular target, 16 places are equally divided in the sputtering surface of the sputtering target.

Next, the side of the sputtering surface of each test piece was ground. At this time, take #180~ After the water-resistant paper of #4000 was ground, polishing was performed with abrasive grains of 3 μm to 1 μm.

Further, it is etched to the extent that the grain boundary can be seen by an optical microscope. Here, the etching liquid was immersed at room temperature for 1 to 2 seconds using a mixed solution of hydrogen peroxide and ammonia water to reveal grain boundaries. Next, for each sample, a photograph with a magnification of 30 times by an optical microscope was taken.

In each of the photographs, the line of 60 mm was drawn in a shape of 20 mm at intervals of 20 mm, and the number of crystal grains cut by the respective straight lines was calculated. Further, the crystal grains at the end of the line segment were calculated in 0.5. Next, the average slice degree L (μm) was determined by L = 60000 / (M.N) (where M is the actual magnification and N is the average value of the number of crystal grains cut).

Next, from the average slice length L (μm) obtained, d = (3 / 2). L calculates the average particle diameter d (μm) of the sample.

Thus, the average value of the average particle diameters of the samples sampled at 16 points was taken as the average particle diameter of the target silver alloy crystal grains. The average particle diameter of the silver alloy crystal grains of the sputtering target of this embodiment is in the range of 120 to 400 μm. The average particle diameter of the silver alloy crystal grains of the sputtering target of the present embodiment containing indium is in the range of 120 to 250 μm.

When the dispersion of the particle diameter of the silver alloy crystal grains is 20% or less of the average particle diameter of the silver alloy crystal grains, the splash at the time of sputtering can be more reliably suppressed.

Here, the discrete value of the particle diameter is the absolute value of the deviation from the average particle diameter among the 16 average particle diameters determined at 16 places (|[(average particle diameter of one place)-(16 places) Average particle size)]|) becomes the most Larger, the specific average particle diameter (specific average particle diameter) was calculated as described below.

[(Specific average particle diameter) - (average particle diameter at 16 places)] | / (average particle diameter at 16 places) × 100 (%)

In this way, the silver alloy sputtering target for forming a conductive film according to the present embodiment has 0.1 to 1.5% by mass in total of one or two of gallium and tin in the above-mentioned range, and the rest is silver and not The composition of the constituents of the impurities to be avoided is such that the average grain size of the crystal grains of the silver alloy is 120 to 400 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter, so even in sputtering When large power is supplied, it is possible to suppress abnormal discharge and suppress the occurrence of splash. Furthermore, the silver alloy sputtering target for forming a conductive film according to the present embodiment has 0.1 to 1.5% by mass in total of one or two of indium, gallium and tin in the above-mentioned range, and the rest is a silver alloy having a composition of silver and an unavoidable impurity, wherein the average grain size of the crystal grains of the silver alloy is 120 to 250 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter. Therefore, even if a large amount of electric power is supplied during sputtering, abnormal discharge can be suppressed, and the occurrence of splash can be suppressed. Further, by using the silver alloy sputtering target for forming a conductive film to perform sputtering, a conductive film having good corrosion resistance and heat resistance and further low resistance can be obtained. The sputtering target of the present embodiment is particularly suitable for a large-sized target having a sputtering target size of 500 mm, a length of 500 mm, and a thickness of 6 mm or more. It is vaild.

Next, a method of producing a silver alloy sputtering target for forming a conductive film of the present embodiment will be described.

In the silver alloy sputtering target for forming a conductive film of the present embodiment, silver having a purity of 99.99% by mass or more and gallium or tin having a purity of 99.9% by mass or more are used as a raw material. When indium is used, indium having a purity of 99.9% by mass or more is used.

First, silver and gallium are melted in a high vacuum or an inert gas atmosphere, and a specific amount of tin is added to the obtained melt, and then melted in a vacuum or an inert gas atmosphere to produce one of gallium and tin or Two kinds of silver alloy melt-cast ingots which are composed of a total of 0.1 to 1.5% by mass and the balance being silver and unavoidable impurities.

In addition, silver and gallium are melted under a high vacuum or an inert gas atmosphere, and a specific content of indium and tin is added to the obtained melt, and then melted in a vacuum or an inert gas atmosphere to prepare 0.1 to 1.5% by mass of indium. Further, one or two of gallium and tin are contained in a total amount of 0.1 to 1.5% by mass, and the remainder is a silver alloy melt-cast ingot composed of silver and unavoidable impurities.

Here, the melting of silver is carried out in an atmosphere substituted with argon after the atmosphere is evacuated, and after the melting, tin or silver is added to the melt of silver and gallium in an argon atmosphere, or a fusion of silver and gallium. The addition of indium and tin is preferable from the viewpoint of the composition ratio of stabilized silver to gallium and tin, or the composition ratio of silver to indium, gallium, and tin. Further, gallium and tin may be added in the form of a mother alloy of silver gallium, silver tin or silver gallium tin prepared in advance.

Next, in order to set the average particle diameter of the silver alloy crystal grains to a specific value, the molten cast ingot is subjected to hot forging. Hot forging, after heating for 1-3 hours at 750~850 °C, it is better to carry out the upsetting forging after 6~20 times of forging forming than 1/1.2~1/2. The heat is intermittently formed, and it is more preferable to perform free forging. For example, it is particularly preferable to rotate the forging direction by 90 degrees one by one while repeating it. More specifically, as shown in Fig. 1, when the cylindrical ingot 1 is used, the ingot 2 is first forged into an angular shape.

Thereafter, the ingot 2 is repeatedly forged in such a manner that the forging direction is rotated by 90 degrees after each forging. At this time, the average shape of the silver alloy crystal grains of the entire ingot is made by forging in the longitudinal direction, the horizontal direction, and the high direction (the x, y, and z directions of FIG. 2) in all directions. From a point of view of a particular value, it is better. Here, the dotted arrows shown in FIG. 1 each show a forging direction, z is a casting direction, x is a direction rotated by 90 degrees for z, and y is a direction of 90 degrees for z and x.

The step of repeating is to make the average particle diameter of the silver alloy crystal grains of the sputtering target of the present embodiment into a desired value, and to make the dispersion of the particle diameter of the silver alloy crystal grains within a desired range. Good practice. When the number of times of repetition is less than six, the aforementioned effect becomes insufficient. On the other hand, the number of times of repetition is more than 20 times, and the effect of suppressing the particle size dispersion of the crystal grains of the silver alloy is not enhanced.

In addition, when the temperature of the upsetting forging in the hot zone is less than 750 °C, the microcrystals are present, so that the effect of suppressing the dispersion of the particle diameter is not sufficiently exhibited, and if it exceeds 850 ° C, the coarse crystals remain. It is not preferable to give full play to the effect of suppressing the dispersion of the particle diameter. also, In order to alleviate the rapid cooling of the ribs and/or the corners formed by the hot forging, the edge of the ingot and/or the corner portion are appropriately subjected to the extent that the movement of the ingot body is not affected. The so-called knocking practice is preferred.

Next, the ingot 3 after forging is cold-pressed to a desired thickness to form the sheet 4. In the case where the rolling ratio of the cold rolling (1 pass) is 5 to 10%, it is preferable from the viewpoint of suppressing the particle diameter dispersion. Repeat this cold rolling, so that the total reduction ratio ((thickness of the ingot before cold rolling - thickness of ingot after cold rolling) / thickness of ingot before cold rolling) becomes 60 to 75% continuously In the case where the total reduction ratio is a specific value and the effect of suppressing the dispersion of the particle diameter is maintained, it is preferable from the viewpoint of refining the crystal grain size. In addition, it is better to perform the above effects for 10 to 20 times.

The heat treatment after the cold rolling is preferably carried out at 550 to 650 ° C for 1 to 2 hours, from the viewpoint of controlling the recrystallization to a specific average particle diameter.

The heat-treated sheet material 4 is machined to a desired size by milling, electric discharge machining or the like to produce a silver alloy sputtering target for forming a conductive film of the present embodiment. The arithmetic mean surface roughness (Ra) of the sputtered surface of the target after machining is preferably 0.2 to 2 μm from the viewpoint of suppressing splash at the time of sputtering.

[Examples]

Next, silver alloy sputtering for forming a conductive film according to the present invention is produced. An example of a target illustrating the results of the evaluation.

(Example 1) [Manufacture of silver alloy sputtering target]

As a raw material, silver having a purity of 99.99% by mass or more and gallium having a purity of 99.9% by mass or more is used, and in a high-frequency vacuum melting furnace, silver and gallium are charged as a raw material so that the respective components have a mass ratio shown in Table 1. The total mass at the time of melting is about 300 kg.

The vacuum processing chamber was evacuated and replaced with argon gas, silver and gallium were melted, and the alloy melt was cast into a graphite mold. The sprue portion of the upper portion of the ingot produced by casting is cut off, and an ingot of about 260 kg is obtained as a sound portion ( 290 × 370mm).

After the obtained ingot was heated at 800 ° C for 1 hour, the forging direction was sequentially rotated by 90 degrees, and the casting direction: z, any direction of z to 90 degrees: x, direction of z and x 90 degrees: y Forging in all directions. The shaping ratio of each exercise is 1/1.2~1/2, and the direction is changed to continue the upsetting forging for 19 times. In the 20th forging, it is formed into a size of about 600 × 910 × 45 (mm).

The forged ingot was cold-rolled to obtain a sheet of approximately 1200 x 1300 x 16 (mm). The reduction ratio per cold rolling was 5 to 10%, and the total was 13 times. The total reduction of this cold rolling is 70%.

After this rolling, the sheet was heated at 640 ° C for 1 hour, and subjected to recrystallization treatment.

Next, the plate is machined to 1000 × 1200 × 12 (mm) The size is the sputtering target of the first embodiment of the present invention.

[Evaluation of Sputter Target] (1) Warpage after machining

The warpage of the sputter target of Example 1 after the above machining was measured. The results are shown in Table 2.

(2) Average particle size of silver alloy crystal grains

The particle size of the silver alloy crystal grain was measured from the sputtering target of 1000 × 1200 × 12 (mm) of Example 1 manufactured as described above, as described in the above-described embodiment, and the location of the 16 places was equally Taking a sample, measuring the average particle diameter of the surface seen from the sputtering surface of each sample, calculating the average particle diameter of the silver alloy crystal grains and the average particle diameter of the silver alloy crystal grains by the average value of the average particle diameter of each sample Dispersion. The measurement results of the dispersion of the average particle diameter are shown in Table 1. As a result, in the sputtering target of the first embodiment, the average particle diameter of the silver alloy crystal grains is in the range of 120 to 400 μm, and the dispersion of the particle diameter of the silver alloy crystal grains is 20% of the average particle diameter of the silver alloy crystal grains. Within.

(3) Determination of the number of abnormal discharges during sputtering

From any portion of the 1000 × 1200 × 12 (mm) sputtering target of the present Example 1, a disk having a diameter of 152.4 mm and a thickness of 6 mm was cut out and welded to a back plate made of copper. This soldered sputtering target was used as a target for evaluation of splash during sputtering, and the number of abnormal discharges during sputtering was measured. The results are shown in Table 2.

In addition, in the normal magnetron sputtering apparatus, the target for evaluation of the welding is mounted, and after exhausting to 1 × 10 ^-4 Pa, the argon gas pressure is 0.5 Pa, and the electric power is input: DC 1000 W. Sputtering was carried out under the condition that the distance between the target substrates was 60 mm. The number of abnormal discharges at the time of sputtering was measured by the arc counting function of a DC power source (model: RPDG-50A) manufactured by MKS Instruments, and the number of abnormal discharges was counted for 30 minutes from the start of discharge. The results are shown in Table 2. As a result, in the sputtering target of the first embodiment, the number of abnormal discharges was 10 or less.

(4) Evaluation of basic characteristics as a conductive film (4-1) Surface roughness of the film

Using the evaluation target shown in the above (3), sputtering was carried out under the same conditions as in the above (2), and a film thickness of 100 nm was formed on a glass substrate of 20 × 20 (mm) to obtain a silver alloy film. Further, in order to evaluate the heat resistance, the silver alloy film was subjected to heat treatment at 250 ° C for 10 minutes, and thereafter, the average surface roughness (Ra) of the silver alloy film was measured by an atomic force microscope. The results are shown in Table 2. As a result, the average surface roughness Ra of the film produced by the sputtering target of the first embodiment was 1 nm or less.

(4-2) Reflectance

In order to evaluate the corrosion resistance, the reflectance of the silver alloy film formed as in the above (4-1) was maintained at a temperature of 80 ° C and a humidity of 85% in a constant temperature and high humidity bath for 100 hours, and then carried out by a spectrophotometer. Determination. The results are shown in Table 2. As a result, the silver plating produced by the sputtering target of the first embodiment is shown. The absolute reflectance of the gold film at a wavelength of 550 nm is 90% or more.

(4-3) specific resistance of the film

The results of measuring the specific resistance of the silver alloy film formed in the same manner as in the above (4-1) are shown in Table 2. As a result, the specific resistance of the silver alloy film produced by the sputtering target of the first embodiment was 3.34 μΩ. A fairly low value for cm.

(Examples 2 to 9 and Comparative Examples 1 to 5)

A sputtering target was produced in the same manner as in Example 1 except that the component composition and the production conditions described in Table 1, and the sputtering targets of Examples 2 to 9 and Comparative Examples 1 to 5 were obtained, and then treated in the same manner as in Example 1. Perform the various assessments described above. These results are shown in Tables 1 and 2.

(Previous Technical Examples 1, 2)

The components of gallium and tin described in Table 1 were melted in the same manner as in Example 1, and cast in an angular graphite mold to prepare an ingot of about 400 × 400 × 150 (mm), and the ingot was heated at 600 ° C. After 1 hour, the inter-heat rolling was carried out to prepare a sputtering target of the prior art example 1. Further, in the same manner as in the prior art example 1, after the ingot was hot-rolled, a sputtering target of the prior art example 2 which was further subjected to heat treatment at 600 ° C for 2 hours was produced. The sputtering targets of the prior art example 1 and the prior art example 2 were used in the same manner as the evaluation of the first embodiment, and the various evaluations described above were carried out. These results are shown in Tables 1 and 2.

(Reference example 1)

The alloying weight of the gallium described in Table 1 was 7 kg, and the alloy was melted in graphite casting. Ingots of 80 × 110 (mm), the obtained ingots were subjected to the same upsetting forging times (5 times) as in Comparative Example 7, and the reduction ratio of the cold rolling was processed, and 220 x 220 × was obtained by heat treatment. 11 (mm) sheet. With respect to this Reference Example 1, the above various evaluations were carried out in the same manner as in the above-described Examples and Comparative Examples. These results are shown in Tables 1 and 2. However, the size of the sputtering target of Reference Example 1 was smaller than that of the sputtering targets produced in the above Examples and Comparative Examples, so that warpage after machining was not evaluated.

As is clear from Table 1, in Examples 1 to 9, the average grain size of the silver alloy crystal grains was 190 to 340 μm, and the dispersion of the particle diameter was 12 to 19%, which was quite good. On the other hand, in Comparative Example 1 in which gallium was 0.05% by mass, the average particle diameter was 410 μm outside the desired range. Further, in Comparative Example 3 in which the hot forging temperature was 700 ° C, the dispersion of the particle diameter was as large as 29%, and in Comparative Example 4 in which the forging temperature was 900 ° C, the average particle diameter was as large as 450 μm, and the particle diameter was discrete. The degree is also as large as 35%.

As is clear from Table 2, in Examples 1 to 9, the number of abnormal discharges, the warpage after machining, the surface roughness of the film, the absolute reflectance at a wavelength of 550 nm, and the specific resistance of the film were all good results. On the other hand, in Comparative Example 1 in which gallium was 0.05% by mass, the warpage after machining was as large as 1.4 mm, the surface roughness of the film was as large as 2 nm, and the absolute reflectance at a wavelength of 550 nm was as small as 87.5%. In Comparative Example 2 in which tin was 1.7% by mass, the absolute reflectance at a wavelength of 550 nm was as small as 88.5%. In addition, Comparative Example 1, comparison In Examples 3 to 5 and the prior art examples 1 and 2, the number of abnormal discharges was as many as 22 or more. Further, in Comparative Example 2 in which tin was 1.7% by mass, the specific resistance of the film was as high as 7.93 μΩ. Cm.

(Examples 10 to 20, Comparative Example 6)

A sputtering target was produced in the same manner as in Example 1 except that the composition and production conditions of gallium, tin, copper, and magnesium described in Table 3 were obtained, and the sputtering targets of Examples 10 to 20 and Comparative Example 6 were obtained. In the same manner as in Example 1, the above various evaluations were carried out. These results are shown in Tables 3 and 4.

As is clear from Table 3, in Examples 10 to 20, the average grain size of the silver alloy crystal grains was 130 to 260 μm, and the dispersion of the particle diameter was 11 to 17%, which was quite good.

Further, as is clear from Table 4, in Examples 10 to 20, the number of abnormal discharges, the warpage after machining, the surface roughness of the film, the absolute reflectance at a wavelength of 550 nm, and the specific resistance of the film were all good results. In this regard, magnesium was 1.7% by weight of Comparative Example 6, and other characteristics were good, but the absolute reflectance at a wavelength of 550 nm was 88.4%, and the specific resistance of the film was as high as 7.81 μΩ. Cm.

(Examples 21 to 28, Comparative Example 7)

Except for the composition and production conditions of gallium, tin, antimony and bismuth described in Table 5, a sputtering target was produced in the same manner as in Example 1, and the sputtering targets of Examples 21 to 28 and Comparative Example 7 were obtained, and In the same manner as in Example 1, the above various evaluations were carried out. These results are shown in Tables 5 and 6.

As is clear from Table 5, in Examples 21 to 28, the average grain size of the silver alloy crystal grains was 130 to 270 μm, and the dispersion of the particle diameter was 15 to 18%, which was quite good.

Further, as is clear from Table 6, in Examples 21 to 28, the number of abnormal discharges, the warpage after machining, the surface roughness of the film, the absolute reflectance at a wavelength of 550 nm, and the specific resistance of the film were all good results. On the other hand, in Comparative Example 7 in which 铕 was 09% by weight, although the other characteristics were good, the number of abnormal discharges was as many as 12 times.

(Example 29) [Manufacture of silver alloy sputtering target]

As a raw material, silver having a purity of 99.99% by mass or more, indium having a purity of 99.9% by mass or more, and gallium having a purity of 99.9% by mass or more are used, and silver is mixed in a high-frequency vacuum melting furnace so that each component has a mass ratio shown in Table 7. Indium and gallium are used as raw materials. The total mass at the time of melting is about 300 kg.

The vacuum processing chamber was evacuated, replaced with argon gas, and silver and gallium were melted, and then indium was added to cast the alloy melt into a graphite mold. The sprue portion of the upper portion of the ingot produced by casting is cut off, and an ingot of about 260 kg is obtained as a sound portion ( 290 × 370mm).

The obtained ingot was heated and forged in the same manner as in Example 1.

The forged ingot was cold-rolled in the same manner as in Example 1.

After rolling, the sheet was heated at 580 ° C for 1 hour, and subjected to recrystallization treatment.

Next, the sheet was machined to a size of 1000 × 1200 × 12 (mm) to become a sputtering target of Example 29 of the present invention.

[Evaluation of Sputter Target]

The above various evaluations (1) to (4) were carried out on the sputtering target of the present Example 29 in the same manner as in the first embodiment. The results are shown in Tables 7 and 8.

(Examples 30 to 42 and Comparative Examples 8 to 14)

A sputtering target was produced in the same manner as in Example 29 except that the component composition and the production conditions described in Table 7 were obtained, and sputtering targets of Examples 30 to 42 and Comparative Examples 8 to 14 were obtained, and then treated in the same manner as in Example 29, Carry out the aforementioned Various assessments. These results are shown in Tables 7 and 8.

(Previous Technical Examples 3 and 4)

The composition of the components of indium, gallium, and tin described in Table 7 was melted in the same manner as in Example 29, and cast in an angular graphite mold to prepare an ingot of about 400 × 400 × 150 (mm), and the ingot was further in 600. After heating at ° C for 1 hour, the film was transferred between the heat and the sputtering target of the prior art example 3 was produced. Further, in the same manner as in the prior art example 3, after the ingot was hot-rolled, a sputtering target of the prior art example 4 which was further subjected to heat treatment at 600 ° C for 2 hours was produced. The sputtering targets of the prior art example 3 and the prior art example 4 were used in the same manner as the evaluation of the example 29, and the various evaluations described above were carried out. These results are shown in Tables 7 and 8.

(Reference example 2)

The incorporation of indium and gallium described in Table 7 was carried out at a mixing weight of 7 kg, and the alloy melt was cast in graphite casting. Ingots of 80 × 110 (mm), the obtained ingots were subjected to the same upsetting forging times (5 times) as in Comparative Example 7, and the reduction ratio of the cold rolling was processed, and 220 x 220 was obtained by heat treatment. ×11 (mm) sheet. With respect to this Reference Example 2, the above various evaluations were carried out in the same manner as in the above-described Examples and Comparative Examples. These results are shown in Tables 7 and 8. However, the size of the sputtering target of Reference Example 2 was smaller than that of the sputtering targets produced in the above Examples and Comparative Examples, and therefore the warpage after the machining was not evaluated.

As is clear from Table 7, in Examples 29 to 42, the average grain size of the silver alloy crystal grains was 120 to 250 μm, and the dispersion of the particle diameter was 12 to 20%, which was quite good. On the other hand, in Comparative Example 8 in which indium was 0.05% by mass, the average particle diameter was 260 μm outside the intended range. Further, in Comparative Example 12 in which the hot forging temperature was 700 ° C, the dispersion of the particle diameter was as large as 23%, and in Comparative Example 13 in which the temperature for hot forging was 900 ° C, the average particle diameter was as large as 300 μm, and the particle diameter was discrete. The degree is also as large as 22%.

In Comparative Example 14, the number of upsetting forgings was 5, and the dispersion of the particle diameter was as large as 26%. Further, the dispersion of the particle diameter of the prior art example 3 is as large as 86%. Further, in the prior art example 4, not only the average particle diameter was as large as 330 μm, but also the dispersion of the particle diameter was as large as 28%.

In Reference Example 2, compared with the large-sized target which is particularly effective in the present invention, the evaluation of the case of manufacturing a small target was carried out under the same conditions as in Comparative Example 14 except that the upsetting forging was 5 times. The dispersion of the particle size is also 14%, which is quite good.

As is clear from Table 8, in Examples 29 to 42, the number of abnormal discharges, the warpage after machining, the surface roughness of the film, the absolute reflectance at a wavelength of 550 nm, and the specific resistance of the film were all good results. On the other hand, in Comparative Example 8 in which the indium was 0.05% by mass, the warpage after the machining was as large as 1.9 mm, and the surface roughness of the film was as large as 1.7 nm. In Comparative Example 9 in which indium was 1.7% by mass, the absolute reflectance at a wavelength of 550 nm was as small as 89.1%. Further, in Comparative Example 8, Comparative Example 10, Comparative Examples 12 to 14, and the prior art examples 3 and 4, the number of abnormal discharges was as large as 22 or more. Further, in Comparative Example 9 in which indium was 1.7% by mass and Comparative Example 11 in which tin was 1.8% by mass, the specific resistance of the film was high. Up to 7μΩ. More than cm.

(Examples 43 to 52, Comparative Example 15)

A sputtering target was produced in the same manner as in Example 29 except that the composition and the production conditions of indium, gallium, tin, copper, and magnesium described in Table 9 were obtained, and the sputtering targets of Examples 43 to 52 and Comparative Example 15 were obtained. The same treatment as in Example 29 was carried out, and the various evaluations described above were carried out. These results are shown in Tables 9 and 10.

As is clear from Table 9, in Examples 43 to 52, the average grain size of the silver alloy crystal grains was 130 to 180 μm, and the dispersion of the particle diameter was 12 to 17%, which was quite good.

Further, as is clear from Table 10, in Examples 43 to 52, the number of abnormal discharges, the warpage after machining, the surface roughness of the film, the absolute reflectance at a wavelength of 550 nm, and the specific resistance of the film were all good results. On the other hand, in Comparative Example 15 in which magnesium was 1.7% by weight, other characteristics were good, but the absolute reflectance at a wavelength of 550 nm was slightly lower at 89.8%, and the specific resistance of the film was as high as 8.20 μΩ. Cm.

(Examples 53 to 62, Comparative Example 16)

A sputtering target was produced in the same manner as in Example 29 except that the composition and manufacturing conditions of indium, gallium, tin, antimony and bismuth described in Table 11 were carried out, and sputtering targets of Examples 53 to 62 and Comparative Example 16 were obtained. The same treatment as in Example 29 was carried out, and the various evaluations described above were carried out. These results are shown in Table 11 and Table 12.

As is clear from Table 11, in Examples 53 to 62, the average grain size of the silver alloy crystal grains was 130 to 200 μm, and the dispersion of the particle diameter was 13 to 18%, which was quite good.

Further, as is clear from Table 12, in Examples 53 to 62, the number of abnormal discharges, the warpage after machining, the surface roughness of the film, the absolute reflectance at a wavelength of 550 nm, and the specific resistance of the film were all good results. On the other hand, in Comparative Example 16 in which 0.9% by weight was used, although the other characteristics were good, the number of abnormal discharges was as many as 12 times.

From the above, it is understood that the alloy sputtering target for forming a conductive film of Examples 1 to 62 of the present invention can suppress abnormal discharge, and the sputtering target can be sputtered to increase the reflectance, and the surface roughness of the film is also small. A reflective electrode film for organic EL having excellent performance can be obtained. Further, the specific resistance of the film is also low, and good characteristics can be obtained as a wiring film of the touch panel.

Further, the technical scope of the present invention is not limited to the above-described embodiments and the above-described embodiments, and various modifications can be made without departing from the scope of the invention.

1‧‧‧ cylindrical ingot

2‧‧‧ angular ingot

3‧‧‧Ingots after forging

4‧‧‧ plates

Fig. 1 is an explanatory view showing an embodiment of a method for producing a silver alloy sputtering target for forming a conductive film according to the present invention, and showing a method of hot forging.

Fig. 2 is a view showing a simple layer configuration of an organic EL element having a top emission structure in which a reflective electrode is used as an anode.

1‧‧‧ cylindrical ingot

2‧‧‧ angular ingot

3‧‧‧Ingots after forging

4‧‧‧ plates

Claims (14)

A silver alloy sputtering target for forming a conductive film, which is characterized in that it contains 0.1 to 1.5% by mass (% by mass) of one or two of gallium and tin, and the rest is silver and unavoidable impurities. The silver alloy having a component composition is composed of a silver alloy having an average particle diameter of 120 to 400 μm, and a dispersion degree of the crystal grain size of the crystal grain is 20% or less of the average particle diameter. The silver alloy sputtering target for forming a conductive film according to the first aspect of the invention, wherein one or a combination of copper and magnesium is contained in an amount of 1.0% by mass or less in place of a part of the silver. In the silver alloy sputtering target for forming a conductive film according to the first aspect of the invention, the total amount of one or two of cerium and lanthanum is 0.8% by mass or less in place of a part of the silver. A silver alloy sputtering target for forming a conductive film, which comprises 0.1 to 1.5% by mass of one or two of gallium and tin, further contains 0.1 to 1.5% by mass of indium, and the rest is silver and It is composed of a silver alloy having a component composition composed of an unavoidable impurity, and the average grain size of the crystal grains of the silver alloy is 120 to 250 μm, and the dispersion of the particle diameter of the crystal grains is 20% or less of the average particle diameter. A silver alloy sputtering target for forming a conductive film according to the fourth aspect of the invention, wherein a part of the silver is contained in an amount of 0.1 to 1.5% by mass of indium, and one or a combination of copper and magnesium is 1.0% by mass or less. . A silver alloy sputtering target for forming a conductive film according to the fourth aspect of the invention, wherein a part of the silver is contained in an amount of 0.1 to 1.5% by mass of indium, and one or a combination of one or two of cerium and lanthanum is 0.8% by mass or less. . A silver alloy sputtering target for forming a conductive film according to the first aspect of the invention, wherein the surface of the target has an area of 0.25 m ² or more. A method for producing a silver alloy sputtering target for forming a conductive film, characterized in that the method for producing a silver alloy sputtering target for forming a conductive film according to the first aspect of the invention is characterized by having gallium or tin One or two types of melt-casting ingots containing 0.1 to 1.5% by mass in total, and the remainder being composed of silver and unavoidable impurities, are sequentially carried out: 6 to 20 times of hot upsetting forging Step, step of cold rolling, step of heat treatment, step of mechanical processing. A method for producing a silver alloy sputtering target for forming a conductive film, characterized in that the method for producing a silver alloy sputtering target for forming a conductive film according to the second aspect of the invention is characterized by having gallium or tin One or two types of melt-cast ingots containing 0.1 to 1.5% by mass in total, and one or two of copper and magnesium are contained in a total amount of 1.0% by mass or less, and the remainder is composed of silver and unavoidable impurities. In sequence, the steps of the upsetting forging, the step of cold rolling, the step of heat treatment, and the step of mechanical processing are repeated 6 to 20 times. A method for producing a silver alloy sputtering target for forming a conductive film, characterized in that the method for producing a silver alloy sputtering target for forming a conductive film according to claim 3 is to have gallium or tin One or two types of melt-cast ingots containing 0.1 to 1.5% by mass in total, and one or two of the total of yttrium and lanthanum are contained in a total amount of 0.8% by mass or less, and the remainder is composed of silver and unavoidable impurities. In sequence, the steps of the upsetting forging, the step of cold rolling, the step of heat treatment, and the step of mechanical processing are repeated 6 to 20 times. A method for producing a silver alloy sputtering target for forming a conductive film, characterized in that the method for producing a silver alloy sputtering target for forming a conductive film according to claim 4 is to have gallium or tin One or two types of melt-cast ingots containing 0.1 to 1.5% by mass in total, further containing 0.1 to 1.5% by mass of indium, and the remainder being composed of silver and unavoidable impurities, sequentially: 6 to 20 times The step of hot upsetting forging, the step of cold rolling, the step of heat treatment, and the step of mechanical processing. A method for producing a silver alloy sputtering target for forming a conductive film, the method for producing a silver alloy sputtering target for forming a conductive film according to claim 5, It is contained in an amount of 0.1 to 1.5% by mass in total of one or two types of gallium and tin, and further contains 0.1 to 1.5% by mass of indium, and one or two of copper and magnesium are contained in a total amount of 1.0% by mass or less. The remaining part is a molten casting ingot composed of silver and inevitable impurities, which are sequentially carried out: 6 to 20 times of hot upsetting forging step, cold rolling step, heat treatment step, and proceeding The steps of machining. A method for producing a silver alloy sputtering target for forming a conductive film, characterized in that the method for producing a silver alloy sputtering target for forming a conductive film according to claim 6 is to have gallium or tin One or two types in total contain 0.1 to 1.5% by mass, further contain 0.1 to 1.5% by mass of indium, and one or two of cerium and lanthanum are contained in a total amount of 0.8% by mass or less, and the rest are silver and unavoidable impurities. The molten cast ingot of the constituent composition is sequentially carried out: a step of repeating upsetting forging 6 to 20 times, a step of cold rolling, a step of heat treatment, and a step of performing mechanical processing. The method for producing a silver alloy sputtering target for forming a conductive film according to the eighth aspect of the invention, wherein the temperature of the upsetting forging is 750 to 850 °C.