JP6801264B2 - Ag alloy film and its manufacturing method, Ag alloy sputtering target and laminated film - Google Patents

Description

The present invention relates to an Ag alloy film, a method for producing the same, and an Ag alloy sputtering target that can be used for producing the Ag alloy film. The present invention also relates to a laminated film containing an Ag alloy film.

Since the Ag film exhibits high light reflectance and low resistance value, it is used as a reflective electrode film for organic EL elements, reflective liquid crystal displays, LEDs, solar cells, and the like. Further, since the Ag film exhibits high transmittance by thinning, the thinned Ag film is used as a translucent electrode film for a touch panel. The reflective electrode film and the translucent electrode film formed from the Ag film may be used as a laminated film with a conductive oxide such as an ITO film or an IZO film.

As described above, the Ag film has excellent optical properties such as high light reflectance and high light transmittance when thinned, and excellent conductivity having low resistance value. However, the Ag film tends to have poor optical properties and conductivity in a hot and humid environment (high temperature and high humidity environment), has high reactivity with chlorine and sulfur, that is, has low corrosion resistance to chlorine and sulfur. It is also known that it easily aggregates. Therefore, a metal element other than Ag is added to the Ag film for the purpose of stabilizing the optical properties and conductivity of the Ag film for a long period of time, improving the corrosion resistance, and preventing the occurrence of aggregation. Therefore, an Ag alloy film is used.

Patent Document 1 describes an Ag alloy for a reflective film to which various metal elements are added for the purpose of maintaining the reflectance for a long period of time. Patent Document 2 describes an Ag alloy to which various metal elements are added for the purpose of improving corrosion resistance, reflectance, resistance, heat resistance and the like. Patent Document 3 describes an Ag alloy reflective film to which various metal elements are added for the purpose of improving the reflectance and preventing the occurrence of Ag aggregation due to humidity and heat. Patent Document 4 describes an Ag-based alloy sputtering target to which various metal elements are added for the purpose of reducing the number of pre-sputtering and shortening the pre-sputtering time when used for sputtering.

International Publication No. 2005/056849 Japanese Unexamined Patent Publication No. 2004-2929 Japanese Unexamined Patent Publication No. 2008-46149 Japanese Patent No. 4833942

By the way, as described above, a metal element other than Ag is added to the Ag film to form an Ag alloy film. By adding the metal element, the excellent optical properties and conductivity of Ag are obtained. May be impaired. Further, the Ag alloy film used as the translucent electrode film is required to be further thinned in order to improve the transmittance. However, when the Ag film becomes thinner, it becomes an ultrathin film having a thickness of 20 nm or less. There is a problem that it tends to aggregate and form an island.

Further, when the Ag alloy film is laminated with a conductive oxide such as an ITO film or an IZO film, a potential difference is generated between the Ag alloy film and the conductive oxide film, so that the corrosion of the Ag alloy film is promoted. There is a problem.

The present invention has been made in view of the above-mentioned circumstances, and has excellent optical characteristics and conductivity immediately after film formation, and the optical characteristics and conductivity are large even in a hot and humid environment. Ag alloy membranes that do not change, are less likely to be corroded by chlorine and sulfur, and are less likely to aggregate even with ultra-thin films, their manufacturing methods, and Ag alloy sputtering targets that can be used to manufacture the Ag alloy membranes. To provide. Another object of the present invention is to provide a laminated film of an Ag alloy film and a transparent conductive oxide, which is less likely to cause corrosion of the Ag alloy film.

In order to solve the above problems, the Ag alloy film of the present invention contains Ti in the range of 0.1 atomic% or more and 5.0 atomic% or less, and Cu, Sn, Mg, In, Sb, Al, Zn, It contains at least one element selected from Ge and Ga in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the balance consists of Ag and unavoidable impurities. Si, V, Cr, Fe, I total content der than 100 ppm by mass of Co, is characterized that you have existed oxides of Ti surface or inside.

Since the Ag alloy film having this structure contains 0.1 atomic% or more of Ti, the sulfur resistance and chlorine resistance of the Ag alloy film are improved. The reason is not clear, but it is considered that when this Ag alloy film is formed by a sputtering method or the like, Ti is oxidized inside the film, and the oxide of Ti is self-formed, which contributes to the manifestation of the effect. Be done.
Further, since the Ti content of this Ag alloy film is limited to 5.0 atomic% or less, the excellent optical properties and conductivity of Ag can be ensured. Further, the Ag alloy film is limited to a total content of Na, Si, V, Cr, Fe and Co of 100 mass ppm or less. Due to this limitation, the amount of these metal elements present as oxides on the grain boundary surface of the Ag crystal is reduced, and the grain boundary surface of the Ag crystal in which the Ti oxide is present becomes wider, so that the resistance of the Ag alloy film is increased. Sulfur resistance and chlorine resistance are improved.

Further, since metal elements such as Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga suppress the movement (aggregation) of Ag atoms in the Ag alloy film, 0.1 atomic% of these metal elements are added. By containing the above, the Ag alloy film has improved optical characteristics and stability of conductivity in a hot and humid environment, and even if it is a thin film, aggregation is less likely to occur. Further, since the content of these metal elements is limited to a range of 10.0 atomic% or less in total with Ti, excellent optical characteristics and conductivity of the Ag alloy film immediately after film formation can be ensured. , It is possible to suppress a large change in optical properties and conductivity in a hot and humid environment.

Here, in the Ag alloy film of the present invention, the atomic ratio A / B of the Ti content A and the total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is determined. It is preferably in the range of 0.1 or more and 6.0 or less.
In this case, although the reason is not clear, the atomic ratio A / B of the Ti content A and the total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is 0. Since the range is 1 or more and 6.0 or less, Ti acts more effectively to improve the sulfur resistance and chlorine resistance of the Ag alloy film.

Further, in the Ag alloy film of the present invention, at least one element selected from Pd, Pt and Au is contained in an amount of 0.1 atomic% or more in total and Ti, Cu, Sn, Mg, In, Sb, Al, etc. It may be contained in a range of 10.0 atomic% or less in total of Zn, Ge, and Ga.
In this case, noble metal elements with high chemical stability such as Pd, Pt, and Au are added in total to 0.1 atomic% or more and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga. Since it is contained in a range of 10.0 atomic% or less, the chemical stability of the Ag alloy itself is improved, and the chlorine resistance and sulfur resistance of the Ag alloy film are improved.

Further, in the Ag alloy film of the present invention, the film thickness may be 20 nm or less.
In this case, the Ag alloy film is unlikely to aggregate and form an island shape even if it is an ultrathin film having a film thickness of 20 nm or less, so that the light transmittance is high.

The laminated film of the present invention is characterized by including the above-mentioned Ag alloy film and a conductive oxide film formed on one side or both sides of the Ag alloy film.
In the laminated film having this structure, the surface or grain boundary of the Ag crystal in the Ag alloy film is protected by the Ti oxide, so that the electrolytic corrosion action generated between the Ag alloy film and the transparent conductive oxide film is suppressed. Therefore, corrosion of the Ag alloy film is less likely to occur.

The Ag alloy sputtering target of the present invention contains Ti of 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga. It is contained in the range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the balance is composed of Ag and unavoidable impurities, and the total content of Na, Si, V, Cr, Fe and Co. amount Ri der than 100 mass ppm, a polycrystalline body including a plurality of Ag alloy crystal, the Ag particle size of the alloy crystal results measured at a plurality of locations, all the particle size of the Ag alloy crystal was measured Of the average crystal grain size C, which is the average value of, and the average value D of the particle size of the Ag alloy crystal at each measured location, the average value D _max, which maximizes the absolute value of the deviation of the average crystal grain size C. Ag alloy grain size variation _{E (%) = (D max} -C) / C × 100 is characterized der Rukoto within 20%, which is defined by the.

The Ag alloy film formed by the sputtering method using the Ag alloy sputtering target having this configuration has high light reflectance or transmittance and excellent optical characteristics, and also has a low resistance value and excellent conductivity. Moreover, its optical properties and conductivity do not change significantly even in a hot and humid environment, corrosion due to chlorine and sulfur is unlikely to occur, and even if it is an ultrathin film, aggregation is unlikely to occur. Further, since the Ag alloy sputtering target having this configuration has a total content of Na, Si, V, Cr, Fe, and Co limited to 100 mass ppm or less, abnormal discharge is less likely to occur during film formation by the sputtering method. .. Further, the Ag alloy sputtering target having this configuration is a polycrystal containing a plurality of Ag alloy crystals, and as a result of measuring the particle size of the Ag alloy crystals at a plurality of locations, all the measured Ag alloy crystal grains Of the average crystal grain size C, which is the average value of the diameters, and the average value D of the grain sizes of the Ag alloy crystals at each measured location, the average value D at which the absolute value of the deviation of the average crystal grain size C is maximum. The variation in the grain size of the Ag alloy crystal defined from _max E (%) = (D _max −C) / C × 100 is within 20%, and the variation in the particle size of the Ag alloy crystal is small. Abnormal discharge is less likely to occur during film formation.

Here, in the Ag alloy sputtering target of the present invention, the atomic ratio A / B of the Ti content A and the total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is , It is preferably in the range of 0.1 or more and 6.0 or less.
In this case, the Ag alloy film formed by using this Ag alloy sputtering target has improved sulfur resistance and chlorine resistance.

Further, in the Ag alloy sputtering target of the present invention, at least one element selected from Pd, Pt and Au is contained in an amount of 0.1 atomic% or more in total and Ti, Cu, Sn, Mg, In, Sb and Al. , Zn, Ge, and Ga may be contained in a range of 10.0 atomic% or less in total.
In this case, the Ag alloy film formed by using this Ag alloy sputtering target has improved salt water resistance and sulfurization resistance.

Further, in the Ag alloy sputtering target of the present invention, the total content of Na, Si, V, Cr, Fe and Co is preferably 10 mass ppm or less.
In this case, abnormal discharge is less likely to occur during film formation by the sputtering method.

Furthermore, in the Ag alloy sputtering target of the present invention, the average crystal particle size C is preferably 200 nm or less.
In this case, even if the target is consumed by the film formation by the sputtering method, the unevenness formed on the sputtered surface becomes small, so that the sputtering can be stably performed for a long period of time.

The method for producing an Ag alloy film of the present invention is characterized in that sputtering is performed using the above-mentioned Ag alloy sputtering target.
By using the method for producing an Ag alloy film of the present invention, it is possible to have excellent optical properties and conductivity immediately after film formation, and the optical properties and conductivity can be significantly changed even in a hot and humid environment. It is possible to produce an Ag alloy film which is less likely to be corroded by chlorine or sulfur and is less likely to aggregate even if it is an ultrathin film.

Here, in the method for producing an Ag alloy film of the present invention, it is preferable to perform sputtering in a gas atmosphere containing oxygen in an amount of 0.5 to 5% of the total pressure of the inert gas.
In this case, the oxide of Ti can be formed more reliably at the time of film formation. Therefore, it is possible to produce an Ag alloy film having a small change in optical characteristics and conductivity in a hot and humid environment and further improved chlorine resistance and sulfur resistance.

As described above, according to the present invention, the light reflectance or transmittance immediately after the film formation is high and the optical characteristics are excellent, the resistance value is low and the conductivity is excellent, and the environment is hot and humid. The optical properties and conductivity of the Ag alloy film do not change significantly, corrosion due to chlorine and sulfur is unlikely to occur, and aggregation is unlikely to occur even with an ultra-thin film, and the manufacturing method thereof, and the production of the Ag alloy film. It becomes possible to provide an Ag alloy sputtering target that can be used in the above. Further, according to the present invention, it is possible to provide a laminated film of an Ag alloy film and a conductive oxide, which is less likely to cause corrosion of the Ag alloy film.

<Ag alloy film>
The Ag alloy film according to the embodiment of the present invention will be described below.
The Ag alloy film of the present embodiment can be used as, for example, an organic EL element, a reflective liquid crystal display, an LED, a reflective electrode film of a solar cell, or a translucent electrode film of a touch panel. Further, the Ag alloy film of the present embodiment can be used as a laminated film with a conductive oxide film.

The Ag alloy film of the present embodiment is unlikely to aggregate and form an island shape even if it is an ultrathin film having a film thickness of 20 nm or less. Therefore, the Ag alloy film of the present embodiment can be particularly advantageously used as a translucent electrode film having a film thickness of 20 nm or less. The film thickness of the Ag alloy film is preferably 5 nm or more. If the thickness of the Ag alloy film is less than 5 nm, conductivity may not be ensured.

The Ag alloy film of the present embodiment contains Ti at 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga. Is contained in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the balance is composed of Ag and unavoidable impurities, and the total of Na, Si, V, Cr, Fe and Co. The content is 100 mass ppm or less. Further, at least one element selected from Pd, Pt, and Au is 0.1 atomic% or more in total, and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga are added in total. It may be contained in a range of 0 atomic% or less.
The reasons for defining the composition and film thickness of the Ag alloy film as described above will be described below.

(Ti)
It is preferable that Ti exists as an oxide of Ti on the surface or inside of the Ag alloy film. This Ti oxide has the effect of protecting the Ag alloy film from sulfur and chlorine. That is, Ti is an element having an action effect of improving the sulfur resistance and chlorine resistance of the Ag alloy film.
The Ti oxide may be present in layers on the surface of the Ag alloy film. If the Ag alloy film is thin, it may be difficult to confirm the presence of the Ti oxide layer by normal measurement, but even in this case, the Ag alloy film of the present embodiment has sufficient sulfur resistance and sufficient sulfur resistance. Shows chlorine resistance. Even a thin Ti oxide layer that is difficult to measure is considered to contribute to the development of the effect.
Here, when the Ti content of the Ag alloy film is less than 0.1 atomic%, the sulfur resistance and chlorine resistance are not sufficiently improved. On the other hand, when the Ti content exceeds 5.0 atomic%, the light transmittance or reflectance of the Ag alloy film immediately after film formation may decrease, and the resistance value may increase. Further, when the Ti content exceeds 5.0 atomic%, the self-formation of the Ti oxide may be inhibited, and the sulfur resistance and the chlorine resistance may not be sufficiently improved.
For this reason, in the Ag alloy film of the present embodiment, the Ti content is set in the range of 0.1 atomic% or more and 5.0 atomic% or less. In order to ensure the above-mentioned action and effect, the Ti content in the Ag alloy film is preferably in the range of 0.2 atomic% or more and 3.0 atomic% or less, and 0.5 atomic% or more. It is more preferably in the range of 2.0 atomic% or less.

(Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga)
Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga are mainly present in the Ag alloy film, and the optical properties and conductivity of the formed Ag alloy film are stable in a hot and humid environment. It has the effect of improving the properties and the effect of suppressing the occurrence of aggregation of the Ag alloy film.
Here, when the total content of at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is less than 0.1 atomic%, it is in a hot and humid environment. The optical properties and the stability of the conductivity are not sufficiently improved, and the Ag alloy film is likely to be aggregated. On the other hand, when the total content of these metal elements exceeds 10.0 atomic% with Ti, the light transmittance or reflectance of the Ag alloy film immediately after film formation decreases, and the resistance value increases. There is.
For this reason, the Ag alloy film of the present embodiment contains 0.1 atomic% of the total content of at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga. It is set in the range of 10.0 atomic% or less in total with Ti. In order to ensure the above-mentioned effects, the total content of the metal elements in the Ag alloy film shall be in the range of 0.2 atomic% or more and 7.0 atomic% or less in total with Ti. Is preferable, and the range is more preferably 0.5 atomic% or more and 5.0 atomic% or less in total with Ti.

(Na, Si, V, Cr, Fe, Co)
Na, Si, V, Cr, Fe, and Co are metal elements contained as unavoidable impurities. Since these metal elements have a low solid solubility in Ag, they are likely to segregate at the grain boundaries of the Ag alloy film, and the elements combine with residual oxygen in the dissolved atmosphere to form oxides, and these oxides become oxides. By interposing in the Ag alloy film structure, it inhibits the self-formation of Ti oxide film. Therefore, if the total content of these metal elements exceeds 100 mass ppm, the corrosion resistance due to Ti will not be sufficiently exhibited, and the chlorine resistance and sulfur resistance will be insufficient.
For this reason, in the Ag alloy film of the present embodiment, the total content of Na, Si, V, Cr, Fe, and Co among the unavoidable impurities is limited to 100 mass ppm or less.

(Pd, Pt, Au)
Pd, Pt, and Au are mainly present in the Ag alloy film, and have the effect of further improving the chlorine resistance and sulfur resistance of the formed Ag alloy film.
Here, when the total content of at least one element selected from Pd, Pt, and Au is less than 0.1 atomic%, the chlorine resistance and sulfur resistance may not be sufficiently improved. On the other hand, when the total content of these metal elements exceeds 10.0 atomic% in total with Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga, the Ag alloy film immediately after film formation The light transmittance or reflectance of the light may decrease, and the resistance value may increase.
For this reason, in the Ag alloy film of the present embodiment, the total content of at least one element selected from Pd, Pt, and Au is 0.1 atomic% or more and Ti, Cu, Sn, Mg, In. , Sb, Al, Zn, Ge, and Ga are set in a range of 10.0 atomic% or less in total. In order to ensure the above-mentioned action and effect, the total content of the metal elements in the Ag alloy film is preferably 0.2 atomic% or more, and more preferably 0.5 atomic% or more. preferable. Further, the total content of the metal elements in the Ag alloy film is preferably 7.0 atomic% or less in total with Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga. More preferably, it is 5.0 atomic% or less.

(Film thickness)
The Ag alloy film of the present embodiment is unlikely to aggregate and form islands even if it is an ultrathin film having a film thickness of 20 nm or less. Therefore, the Ag alloy film of the present embodiment can be advantageously used as a translucent electrode film having a film thickness of 20 nm or less.
The film thickness of the Ag alloy film is preferably 5 nm or more. If the thickness of the Ag alloy film is less than 5 nm, conductivity may not be ensured.

<Laminated film>
The laminated film of the present embodiment includes the Ag alloy film of the present embodiment described above and a conductive oxide film formed on one side or both sides of the Ag alloy film. In the laminated film having this structure, the Ti oxide layer is interposed between the Ag alloy film and the conductive oxide film, so that the electrolytic corrosion action generated between the Ag alloy and the conductive oxide is suppressed. Corrosion of Ag alloy film is unlikely to occur.

The conductive oxide film is preferably a transparent conductive oxide film. Examples of transparent conductive oxide films include ITO film (indium oxide + tin oxide), IZO film (indium oxide + zinc oxide), AZO film (aluminum oxide + zinc oxide), and GZO film (gallium oxide + zinc oxide). Can be mentioned.

<Ag alloy sputtering target>
The sputtering target of the present embodiment contains Ti of 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga. It is contained in the range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the balance is composed of Ag and unavoidable impurities, and the total content of Na, Si, V, Cr, Fe and Co. The amount is 100 mass ppm or less.

Since the total content of Si, V, Cr, Fe, and Co in the sputtering target of the present embodiment is limited to 100 mass ppm or less, abnormal discharge is less likely to occur during film formation by the sputtering method. In order to more reliably suppress abnormal discharge during film formation by this sputtering method, the total content of Na, Si, V, Cr, Fe, and Co is preferably 10 mass ppm or less.

The sputtering target of the present embodiment further contains at least one element selected from Pd, Pt, and Au in a total amount of 0.1 atomic% or more and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, It may be contained in a range of 10.0 atomic% or less in total with Ge and Ga. Since the sputtering target of the present embodiment contains Pd, Pt, and Au in the above range, the Ag alloy film formed by using this Ag alloy sputtering target has improved salt water resistance and sulfide resistance.

The sputtering target of the present embodiment is preferably a polycrystal containing a plurality of Ag alloy crystals. In this case, as a result of measuring the particle size of the Ag alloy crystal at a plurality of locations (for example, 16 locations), the average crystal particle size C, which is the average value of the particle sizes of all the measured Ag alloy crystals, was measured. Of the average value D of the grain size of the Ag alloy crystal at each location, the variation E (%) of the grain size of the Ag alloy defined from the average value Dmax at which the absolute value of the deviation of the average crystal grain size C is maximum. ) = (Dmax-C) / C × 100 is preferably within 20%. By reducing the variation in the crystal grain size of the Ag alloy, abnormal discharge is less likely to occur during film formation by the sputtering method. The average crystal grain size C is preferably 200 nm or less.

<Manufacturing method of Ag alloy sputtering target>
Next, a method for manufacturing the Ag alloy sputtering target according to the present embodiment will be described.
First, Ag having a purity of 99.9% by mass or more and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga having a purity of 99.9% by mass or more are prepared as melting raw materials.

Here, when reducing the total content of Na, Si, V, Cr, Fe, and Co among the unavoidable impurities, these elements contained in the Ag raw material are analyzed by ICP analysis or the like, and are selected and used. .. In order to surely reduce the total content of Na, Si, V, Cr, Fe, and Co, the Ag raw material is leached with nitric acid, sulfuric acid, or the like, and then electrorefined using an electrolytic solution having a predetermined Ag concentration. It is preferable to do so.

The selected Ag raw material and additive elements (Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga) are weighed so as to have a predetermined composition. Next, Ag is melted in a melting furnace in a high vacuum or an inert gas atmosphere, and a predetermined amount of additive elements and silver sulfide are added to the obtained molten metal. Then, it is dissolved in a vacuum or an inert gas atmosphere to dissolve Ti in 0.1 atomic% or more and 5.0 atomic% or less, and at least selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga. It contains one kind of element in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the balance consists of Ag and unavoidable impurities, Na, Si, V, Cr, Fe. , An Ag alloy ingot having a total content of Co of 100 mass ppm or less is produced.

It is preferable that the obtained Ag alloy ingot is cold-rolled and the rolled ingot is heat-treated. The heat treatment is preferably performed in the air at a temperature of 500 to 700 ° C. After performing the heat treatment, it is preferable to rapidly cool the rolled ingot to, for example, about 200 ° C. at a cooling rate of 200 ° C./min or more. As a method of quenching, there is a water shower for about 1 minute. By this quenching, the growth of crystal grains can be suppressed and the crystal grain size can be made finer. By machining the rolled plate of Ag alloy thus obtained, the Ag alloy sputtering target according to the present embodiment can be manufactured. The shape of the Ag alloy sputtering target is not particularly limited, and may be a disk type, a square plate type, or a cylindrical type.

<Manufacturing method of Ag alloy film>
In the method for producing an Ag alloy film of the present embodiment, sputtering is performed using an Ag alloy sputtering target. As the sputtering apparatus, a magnetron sputtering type apparatus is preferable. As the power source of the sputtering apparatus, a direct current (DC) power source, a high frequency (RF) power source, a medium frequency (MF) power source, or an alternating current (AC) power source can be used.

In the method for producing an Ag alloy film of the present embodiment, the gas atmosphere of the sputtering apparatus is preferably an Ar gas atmosphere. The gas atmosphere of the sputtering apparatus may contain oxygen. The amount of oxygen is preferably an amount that is 0.5 to 5% of the total pressure of Ar gas. By performing sputtering in a gas atmosphere containing oxygen, Ti oxide can be more reliably formed at the time of film formation. Therefore, it is possible to produce an Ag alloy film having a small change in optical characteristics and conductivity in a hot and humid environment and further improved chlorine resistance and sulfur resistance.

Example 1: Fabrication of Ag Alloy Sputtering Target [Examples 1-36 of the present invention, Comparative Examples 1-14]
As melting raw materials, Ag with a purity of 99.9% by mass or more and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt, Au having a purity of 99.9% by mass or more are prepared. did.
Here, in order to reduce the content of impurity elements, a method was adopted in which the Ag raw material was leached with nitric acid or sulfuric acid and then electrolytically purified using an electrolytic solution having a predetermined Ag concentration. Impurity analysis by the ICP method was carried out on the Ag raw material in which impurities were reduced by this purification method, and further, the Ag raw material having a total concentration of Na, Si, V, Cr, Fe and Co of 100 ppm or less was selected as a sputtering target. It was selected as a raw material for manufacturing.

The selected Ag raw material and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt, and Au to be added were weighed so as to have a predetermined composition. Next, using a melting furnace, Ag is melted in a high vacuum or an inert gas atmosphere, and in the obtained molten Ag, predetermined Ti and Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt and Au were added and dissolved in a vacuum or inert gas atmosphere. Then, hot water was poured into a mold to produce an Ag alloy ingot (ingot). Here, when the Ag was dissolved, the atmosphere was once evacuated (5 × ^10-2 Pa or less) and then replaced with Ar gas. Further, the addition of Ti and Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt and Au was carried out in an Ar gas atmosphere.

Next, the obtained Ag alloy ingot was cold-rolled at a rolling reduction of 70%, and then heat-treated at 500 to 700 ° C. for 1 hour in the air. After the heat treatment was performed, the rolled ingot was rapidly cooled to about 200 ° C. at a cooling rate of 200 ° C./min or more. The rolled plate of Ag alloy thus obtained is straightened by a straightening press, a roller leveler, or the like, and then machined such as milling and electric discharge machining to have a predetermined diameter of 152.4 mm and a thickness of 6 mm. An Ag alloy sputtering target having the composition of the above was prepared.

[Comparative Example 15]
As the dissolution raw materials, Ag having a purity of 99.9% by mass or more and Ti, Cu, and In having a purity of 99.9% by mass or more were prepared.
An Ag alloy sputtering target was prepared in the same manner as described above except that the Ag raw material was not electrorefined.

[Composition analysis]
For the composition of the target, a sample for analysis was taken from the Ag alloy ingot after casting, and the sample was analyzed by ICP emission spectroscopy. The results of this analysis are shown in Tables 1A and 1B.
In each of the following examples, it was confirmed by ICP emission spectroscopy that the composition of the film was almost the same as the composition of the target used.

[Organizational analysis]
The variation in the average crystal grain size and the crystal grain size of the Ag alloy sputtering target was analyzed by the following method. The analysis results are shown in Table 2.

(Measuring method of average crystal grain size and variation in crystal grain size)
A cubic sample piece having a side of about 10 mm is collected evenly from 16 points on the sputtered surface of the target. Next, the sputtered surface of each sample piece is polished. At this time, polishing is performed with water resistant paper # 180 to # 4000, and then buffing is performed with abrasive grains of 3 μm to 1 μm. Further, etching is performed so that the grain boundaries can be seen with an optical microscope. Here, a mixed solution of hydrogen peroxide solution and ammonia water is used as the etching solution, and the etching solution is immersed at room temperature for 1 to 2 seconds to reveal grain boundaries. Next, each sample is photographed with an optical microscope. For the magnification of the photograph, select a magnification that makes it easy to count the crystal grains. In each photograph, a total of four 60 mm line segments are drawn vertically and horizontally at intervals of 20 mm (as shown by the symbol #), and the number of crystal grains cut by each straight line is counted. The number of crystal grains at the end of the line segment is counted as 0.5. The average intercept length: L (μm) is determined by L = 60000 / (MN) (where M is the actual magnification and N is the average value of the number of cut crystal grains). Next, from the obtained average intercept length: L (μm), the average particle size of the sample: d (μm) is calculated by d = (3/2) · L. The average value of the average particle size of the samples sampled from 16 locations in this way is used as the crystal particle size of the target silver alloy crystal.
The variation in particle size is calculated as follows. Of the 16 average particle diameters obtained at 16 locations, the absolute value of the deviation from the average value of the average particle diameter (| [(average particle diameter at one location)-(average of 16 average particle diameters) Value)] |) is specified as the maximum. Next, using the specified average particle size (specific average particle size), the variation in particle size is calculated by the following formula.
{| [(Specific average particle size)-(Average value of average particle size at 16 locations)] | / (Average value of average particle size at 16 locations)} x 100 (%)

[Abnormal discharge test]
The Ag alloy sputtering targets prepared in the above-mentioned Examples of the present invention and Comparative Examples were soldered to a backing plate made of oxygen-free copper using indium solder to prepare a target composite.
After attaching the above-mentioned target composite to a normal magnetron sputtering device and exhausting to 1 × 10 ^-4 Pa, sputtering is performed under the conditions of Ar gas pressure: 0.5 Pa, input power: DC 1000 W, and target substrate distance: 60 mm. Was carried out. The number of abnormal discharges during sputtering was measured as the number of abnormal discharges for one hour from the start of discharge by the arc count function of a DC power supply (RPDG-50A) manufactured by MKS Instruments. Further, the target was consumed by repeating empty sputtering for 4 hours and replacement of the protective plate, and intermittently sputtering for 20 hours. After that, sputtering was further performed, and the number of abnormal discharges that occurred in 30 minutes after consumption (sputtering for 20 hours) was measured. Table 2 shows the number of abnormal discharges in 1 hour from the start of discharge as the "number of abnormal discharges after 1 hour" and the number of abnormal discharges occurring in 30 minutes after consumption as the "number of abnormal discharges after consumption".

In Comparative Example 15 in which the total content of Na, Si, V, Cr, Fe, and Co exceeds 100 mass ppm, the number of abnormal discharges after 1 hour is 34 times / h, and the number of abnormal discharges after consumption is 41 times / 30 min. The number has increased, and sputtering could not be performed stably. Further, in Examples 22 and 25 of the present invention in which the total content of Na, Si, V, Cr, Fe, and Co exceeds 10 mass ppm, the number of abnormal discharges after 1 hour and the number of abnormal discharges after consumption are slightly increased. Was confirmed. Further, it was confirmed that the number of abnormal discharges after consumption was slightly increased in Comparative Examples 1, 3 and 9 in which the variation in the crystal grain size of the Ag alloy exceeded 20%.

Example 2: Preparation of Ag alloy membrane (semi-transmissive membrane) [Examples 101 to 139 of the present invention, Comparative Examples 101 to 115]
The Ag alloy sputtering target produced in Example 1 was mounted on a sputtering apparatus, and sputtering was performed under the following conditions to form an Ag alloy film having a thickness of 10 nm on the surface of a glass substrate.

(Sputtering conditions)
Ag alloy sputtering target used for film formation: Reached vacuum degree: 5 × 10 ^-5 Pa or less Used gas: Ar (Examples 101 to 125 of the present invention, 129 to 139, Comparative examples 101 to 115)
Mixed gas of Ar and oxygen (Examples 126 to 128 of the present invention)
Ar gas pressure: 0.5Pa
Oxygen gas pressure: Table 3 as a percentage of Ar gas pressure (0.5 Pa) Power: DC 200 W
Target / board distance: 70 mm

[Evaluation]
(Sheet resistance after film formation)
The sheet resistance of the Ag alloy film obtained as described above was measured by a four-probe method using Mitsubishi Chemical's Loresta-GP. The obtained sheet resistance is shown in Table 3 as "sheet resistance after film formation".

(Transmittance after film formation)
The light transmittance of the Ag alloy film obtained as described above was measured using a spectrophotometer (Hitachi High-Tech U-4100). The obtained light transmittance is shown in Table 3 as “post-film transmittance”. The numerical value shown in the table is the transmittance of light having a wavelength of 550 nm.

(Constant temperature and humidity test)
The Ag alloy film obtained as described above was allowed to stand in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 85% for 250 hours, and then taken out from the constant temperature and humidity chamber. Then, the sheet resistance and the transmittance of the Ag alloy film were measured in the same manner as described above. Rate of change in sheet resistance [= (sheet resistance after constant temperature and humidity test-sheet resistance after film formation) / sheet resistance after film formation x 100] and amount of change in transmittance at wavelength 550 nm [= after constant temperature and humidity test Transmittance-transmittance after film formation] and the appearance of the film (presence or absence of discoloration / spots) were used to evaluate the stability in the constant temperature and humidity test. The appearance of the film was marked with "○" for those without discoloration or spots after the constant temperature and humidity test, and with "x" for those with spots. The results are shown in Table 4.

(Sulfurization test)
The Ag alloy film obtained as described above is immersed in a 0.01 wt% sodium sulfide aqueous solution at room temperature for 1 hour, then removed from the sodium sulfide aqueous solution, thoroughly washed with pure water, and then dried air is removed. Water was removed by spraying. Then, the sheet resistance and the transmittance of the Ag alloy film were measured in the same manner as described above. Sulfur resistance was evaluated based on the rate of change in sheet resistance, the amount of change in transmittance at a wavelength of 550 nm, and the appearance of the film. The appearance of the film was marked with "○" for those without discoloration or spots after the sulfurization test, and with "x" for those with spots. The results are shown in Table 4.

(Salt water test)
The Ag alloy film obtained as described above is immersed in a 5% NaCl aqueous solution at room temperature for 10 days, then removed from the NaCl aqueous solution, thoroughly washed with pure water, and then sprayed with dry air to obtain water. Was removed. Then, the sheet resistance and the transmittance of the Ag alloy film were measured in the same manner as described above. The salt water resistance was evaluated based on the rate of change in sheet resistance, the amount of change in transmittance at a wavelength of 550 nm, and the appearance of the film. Regarding the appearance of the film, those in which discoloration or spots did not occur after the salt water test were designated as “◯”, and those in which the Ag alloy film had disappeared were designated as “film disappeared”. The results are shown in Table 4.

In Comparative Example 101 using an Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the sheet resistance increased significantly before and after the sulfurization test, and the transmittance decreased significantly. Discoloration, spots, etc. were generated on the Ag alloy film after the sulfide test. Furthermore, after the salt water test, the Ag alloy film had disappeared.

In Comparative Example 102 using an Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the sheet resistance increased significantly before and after the sulfurization test, and the transmittance decreased significantly. Discoloration, spots, etc. were generated on the Ag alloy film after the sulfide test. Furthermore, after the salt water test, the Ag alloy film had disappeared.

Ag alloy sputtering targets having a total content of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga less than 0.1 atomic% (Comparative Examples 3, 5, 7, 9, 11, 13) In Comparative Examples 103, 105, 107, 109, 111, and 113 used, the sheet resistance increased significantly before and after the constant temperature and humidity test, the transmittance decreased significantly, and the Ag alloy film after the constant temperature and humidity test Discoloration and spots were occurring.

Ag alloy sputtering targets with a total content of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga greater than 10.0 atomic% in total with Ti (Comparative Examples 4, 6, 8, 10, 12) In Comparative Examples 104, 106, 108, 110, 112, and 114 using (14), the sheet resistance after film formation was larger than 30 Ω / □, and the transmittance was lower than 60%.

In Comparative Example 115 using an Ag alloy sputtering target (Comparative Example 15) in which the total content of Na, Si, V, Cr, Fe, and Co was more than 100 mass ppm, the sheet resistance increased significantly before and after the sulfurization test. However, the transmittance was greatly reduced, and discoloration, spots, etc. were generated on the Ag alloy film after the sulfide test. Furthermore, after the salt water test, the Ag alloy film had disappeared.

On the other hand, Ti is contained in the range of 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga. Is contained in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. In all of the examples 101 to 128 of the present invention using a certain Ag alloy sputtering target (Examples 1 to 25 of the present invention), the sheet resistance after film formation is smaller than 30Ω / □ and the transmittance exceeds 60%. It was. In addition, the sheet resistance and transmittance did not change significantly before and after the test in any of the constant temperature and humidity test, sulfurization test, and salt water test, and no discoloration or spots occurred on the Ag alloy film after the test. It was stable.

In particular, in Examples 126 to 128 of the present invention in which film formation was performed in a mixed gas atmosphere of Ar and oxygen, Example 124 of the present invention in which film formation was performed in an Ar gas atmosphere using the same Ag alloy sputtering target. Compared with, the sheet resistance after film formation is small and the transmittance is high, and the changes in sheet resistance and transmittance are generally small in any of the constant temperature and humidity test, the sulfurization test, and the salt water test, and the resistance is low. Improved corrosiveness.

In addition, at least one element selected from Pd, Pt, and Au is 0.1 atomic% or more in total, and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga are added in total. In Examples 129 to 139 of the present invention using Ag alloy sputtering targets (Examples 26 to 36 of the present invention) containing 0 atomic% or less, changes in sheet resistance and permeability before and after the sulfurization test and the salt water test. Has become generally smaller.

From the above, according to the present invention, an Ag alloy film having low resistance and high transmittance, excellent heat resistance, moisture resistance, sulfur resistance, and chlorine resistance, and suitable as a translucent electrode film can be obtained. It was confirmed that it could be provided.

Example 3: Preparation of Ag Alloy Film (Reflective Film) [Examples 140 to 141 of the present invention, Comparative Examples 116 to 117]
The Ag alloy sputtering target produced in Example 1 was mounted on a sputtering apparatus, and sputtering was carried out under the same conditions as in Example 2 to form a 100 nm-thick Ag alloy film on the surface of a glass substrate for evaluation. The contents are shown in Table 5.

In Comparative Example 116 using an Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the sheet resistance increased significantly before and after the sulfurization test, and the reflectance greatly decreased. Discoloration, spots, etc. were generated on the Ag alloy film after the sulfide test. Furthermore, after the salt water test, the Ag alloy film had disappeared.

In Comparative Example 117 using an Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the sheet resistance greatly increased before and after the sulfurization test, and the reflectance greatly decreased. Discoloration, spots, etc. were generated on the Ag alloy film after the sulfide test. Furthermore, after the salt water test, the Ag alloy film had disappeared.
In Comparative Example 117 using an Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the sheet resistance greatly increased before and after the sulfurization test, and the reflectance greatly decreased. Discoloration, spots, etc. were generated on the Ag alloy film after the sulfide test. Furthermore, after the salt water test, the Ag alloy film had disappeared.

On the other hand, Ti is contained in the range of 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga. Is contained in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. In Example 140 of the present invention using a certain Ag alloy sputtering target (Example 24 of the present invention), the sheet resistance and the reflectance changed significantly before and after the test in any of the constant temperature and humidity test, the sulfurization test, and the salt water test. Furthermore, the Ag alloy film after the test was stable without discoloration or spots.

In particular, in Example 141 of the present invention in which film formation was performed in a mixed gas atmosphere of Ar and oxygen, comparison with Example 140 of the present invention in which film formation was performed in an Ar gas atmosphere using the same Ag alloy sputtering target. As a result, changes in sheet resistance and permeability were small in all of the constant temperature and humidity tests, sulfurization tests, and salt water tests, and corrosion resistance was improved.

Based on the above, according to the present invention, an Ag alloy film having low resistance and high transmittance, excellent heat resistance, moisture resistance, sulfur resistance, and chlorine resistance, and suitable as a reflective electrode film is provided. It was confirmed that it was possible.

Example 4: Preparation of a translucent conductive laminated film (conductive oxide film / Ag alloy film / conductive oxide film) [Examples 201 to 217 of the present invention, Comparative Examples 201 to 208]
The Ag alloy sputtering target produced in Example 1 and the following conductive oxide film forming target were mounted on a sputtering apparatus, and sputtering was performed under the same conditions as in Example 2 to obtain a thickness of 20 nm on the surface of the glass substrate. A semitransparent conductive laminated film in which a film of a conductive oxide (A), a film of an Ag alloy having a thickness of 10 nm (semi-transparent film), and a film of a conductive oxide (B) having a thickness of 20 nm are laminated in this order. A film was formed and evaluated. The contents are shown in Tables 6 and 7.
(Composition of target for conductive oxide film formation)
ITO: Indium oxide 90 mol%, tin oxide 10 mol%
IZO: 70 mol% of indium oxide, 30 mol% of zinc oxide
AZO: Aluminum oxide 2 mol%, Zinc oxide 98 mol%
GZO: gallium oxide 2 mol%, zinc oxide 98 mol%
The conductive oxide film was formed in an Ar gas atmosphere containing 2% oxygen.

In Comparative Examples 201, 203, 205, and 207 using an Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the conductive oxides (A) and (B) were either. Even so, the sheet resistance was greatly increased before and after the sulfurization test, the transmittance was greatly reduced, and the edge of the Ag alloy film after the sulfurization test was discolored. Furthermore, after the salt water test, the Ag alloy film had disappeared.

In Comparative Examples 202, 204, 206, and 208 using an Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the conductive oxides (A) and (B) are any of them. Even so, the sheet resistance after film formation was large, exceeding 30 Ω / □, and the transmittance was lower than 80%. In addition, the sheet resistance increased significantly before and after the sulfurization test, the transmittance decreased significantly, and the edge of the Ag alloy film after the sulfurization test was discolored. Furthermore, after the salt water test, the Ag alloy film had disappeared.

On the other hand, Ti is contained in the range of 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga. Is contained in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. In Examples 2001 to 216 of the present invention using a certain Ag alloy sputtering target (Examples 2, 4, 5, 14, 15, 23, 25 of the present invention), the sheet resistance after film formation is 30 Ω / □ in all cases. Was small, and the permeability exceeded 80%. In addition, the sheet resistance and transmittance did not change significantly before and after the test in any of the constant temperature and humidity test, sulfurization test, and salt water test, and the laminated film after the test did not cause discoloration or spots. It was stable.

In particular, in Examples 208 to 210 of the present invention in which film formation was performed in a mixed gas atmosphere of Ar and oxygen, Example 204 of the present invention in which film formation was performed in an Ar gas atmosphere using the same Ag alloy sputtering target. The sheet resistance after film formation is low, the transmittance after film formation is generally high, and the changes in sheet resistance and transmittance are generally small in all the constant temperature and humidity tests, sulfurization tests, and salt water tests. , Stability has improved.

Further, in Example 217 of the present invention using an Ag alloy sputtering target containing Pd (Example 27 of the present invention), changes in sheet resistance and transmittance before and after the sulfurization test and the salt water test were substantially small.

From the above, it was confirmed that the Ag alloy film according to the present invention is stable because corrosion is not easily promoted even when it is used as a translucent conductive laminated film of a conductive oxide film and an electric oxide. It was.

Example 5: Preparation of a reflective conductive laminated film (conductive oxide film / Ag alloy film / conductive oxide film) [Examples 218 to 219 of the present invention, Comparative Examples 209 to 210]
The Ag alloy sputtering target produced in Example 1 and the following conductive oxide film forming target were mounted on a sputtering apparatus, and sputtering was performed under the same conditions as in Example 4, and the surface of the glass substrate was 20 nm thick. A reflective conductive laminated film was prepared by laminating a film of a conductive oxide (A), a film of an Ag alloy having a thickness of 100 nm (reflective film), and a film of a conductive oxide (B) having a thickness of 20 nm in this order. ,evaluated. The contents are shown in Table 8.

In Comparative Example 209 using an Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the sheet resistance increased before and after the sulfide test, the reflectance decreased, and after the sulfide test. The edge of the Ag alloy film was discolored. Furthermore, after the salt water test, the Ag alloy film had disappeared.

In Comparative Example 210 using an Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the sheet resistance after film formation was large and the reflectance was low. In addition, the sheet resistance increased before and after the sulfurization test, the reflectance decreased, and the edge of the Ag alloy film after the sulfurization test was discolored. Furthermore, after the salt water test, the Ag alloy film had disappeared.

On the other hand, Ti is contained in the range of 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga. Is contained in a range of 0.1 atomic% or more in total and 10.0 atomic% or less in total with Ti, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. In Examples 218 and 219 of the present invention using a certain Ag alloy sputtering target (Example 14 of the present invention), the sheet resistance after film formation was small and the reflectance exceeded 94%. Furthermore, in all of the constant temperature and humidity test, sulfurization test, and salt water test, the sheet resistance and transmittance did not change significantly before and after the test, and no discoloration or spots occurred on the Ag alloy film after the test. It was stable.

From the above, it was confirmed that the Ag alloy film according to the present invention is stable because corrosion is not easily promoted even when it is used as a reflective conductive laminated film laminated with a conductive oxide film.

Claims (13)

Ti is 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is 0.1 atomic% or more in total. incorporated within a range in which a total of Ti of 10.0 atomic% or less, the balance being Ag and unavoidable impurities, Na, Si, V, Cr, Fe, the total content of Co is Tsu der than 100 ppm by weight Te, Ag alloy film is characterized that you have existed oxides of Ti surface or inside. The atomic ratio A / B of the Ti content A and the total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is in the range of 0.1 or more and 6.0 or less. The Ag alloy film according to claim 1. Further, at least one element selected from Pd, Pt, and Au is 0.1 atomic% or more in total, and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga are added in total. The Ag alloy film according to claim 1 or 2, characterized in that it is contained in a range of 0 atomic% or less. The Ag alloy film according to any one of claims 1 to 3, wherein the film thickness is 20 nm or less. A laminated film comprising the Ag alloy film according to any one of claims 1 to 4, and a conductive oxide film formed on one side or both sides of the Ag alloy film. Ti is 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is 0.1 atomic% or more in total. incorporated within a range where total and Ti of 10.0 atomic% or less, the balance being Ag and unavoidable impurities, Na, Si, V, Cr, Fe, der total content less than 100 ppm by mass of Co Ri , A polycrystal containing a plurality of Ag alloy crystals, and as a result of measuring the particle size of the Ag alloy crystal at a plurality of locations, the average crystal grain size which is the average value of the particle size of all the measured Ag alloy crystals. Ag alloy crystal grains defined from C and the average value D _max that maximizes the absolute value of the deviation of the average crystal particle size C among the average value D of the particle size of the Ag alloy crystal at each measured location. diameter variations _{E (%) = (D max} -C) / C Ag alloy sputtering targets × 100 is characterized in der Rukoto within 20%. The atomic ratio A / B of the Ti content A and the total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is in the range of 0.1 or more and 6.0 or less. The Ag alloy sputtering target according to claim 6, wherein the Ag alloy sputtering target. Further, at least one element selected from Pd, Pt, and Au is 0.1 atomic% or more in total, and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga are added in total. The Ag alloy sputtering target according to claim 6 or 7, wherein the content is in a range of 0 atomic% or less. The Ag alloy sputtering target according to any one of claims 6 to 8, wherein the total content of Na, Si, V, Cr, Fe, and Co is 10 mass ppm or less. The Ag alloy sputtering target according to any one of claims 6 to 9, wherein the average crystal particle size C is 200 μm or less. A method for producing an Ag alloy film, which comprises performing sputtering using the Ag alloy sputtering target according to any one of claims 6 to 10 . The method for producing an Ag alloy film according to claim 11 , wherein sputtering is performed in a gas atmosphere containing an amount of oxygen that is 0.5 to 5% of the total pressure of the inert gas. Ti is 0.1 atomic% or more and 5.0 atomic% or less, and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge, and Ga is 0.1 atomic% or more in total. Ag containing in the range where the total content with Ti is 10.0 atomic% or less, the balance is composed of Ag and unavoidable impurities, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. using an alloy sputtering target, a method of manufacturing a be that a g alloy film and performing sputtering at a gas atmosphere containing an amount of oxygen to be 0.5% to 5% of the pressure to the total pressure of the inert gas ..