KR20180034334A - Ag ALLOY FILM AND METHOD FOR PRODUCING SAME, Ag ALLOY SPUTTERING TARGET AND LAMINATED FILM - Google Patents

Abstract

The Ag alloy film of the present invention contains at least 0.1 atomic% and not more than 5.0 atomic% of Ti and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, And the total amount of Ti and Si is 10.0 atomic percent or less, the balance of Ag and unavoidable impurities, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less.

Description

Ag alloy film and manufacturing method thereof, Ag alloy sputtering target and laminated film (Ag ALLOY FILM AND METHOD FOR PRODUCING SAME, Ag ALLOY SPUTTERING TARGET AND LAMINATED FILM)

The present invention relates to an Ag alloy film, a manufacturing method thereof, and an Ag alloy sputtering target usable for manufacturing the Ag alloy film. Further, the present invention relates to a laminated film including an Ag alloy film.

The present application claims priority based on Japanese Patent Application No. 2015-148474, filed on July 28, 2015, and Japanese Patent Application No. 2016-131593, filed on July 1, 2016, the contents of which are incorporated herein by reference I will.

Ag films are used as reflective electrode films for organic EL devices, reflective liquid crystal displays, LEDs, and solar cells in view of high reflectance and low resistance. Further, since the Ag film exhibits a high transmittance by making it thin, the Ag film that has been thinned is used as a semitransparent electrode film of a touch panel. The reflective electrode film and the semi-transparent 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 characteristics such as high reflectivity of light and high transmittance of light when it is made thin, and excellent conductivity when the resistance value is low. However, in the case of the Ag film, the optical characteristic and the conductivity are easily deteriorated in a heat-humid environment (high temperature and high humidity environment), the high reactivity with chlorine or sulfur, that is, the corrosion resistance against chlorine or sulfur is low, The point is known. Therefore, a metal element other than Ag is added to the Ag film for the purpose of stabilizing the optical characteristics and conductivity of the Ag film over a long period of time, improving the corrosion resistance, and preventing the occurrence of agglomeration, An alloy film is used.

Patent Document 1 discloses an Ag alloy for a reflective film to which various metal elements are added for the purpose of maintaining the reflectance in the long term. Patent Document 2 describes an Ag alloy to which various metal elements are added for the purpose of improving corrosion resistance, reflectance, resistance and heat resistance. Patent Document 3 discloses an Ag alloy reflective film to which various metal elements are added for the purpose of improving the reflectance and preventing agglomeration of Ag 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 free sputtering and shortening the free sputtering time when the sputtering is used.

International Publication No. 2005/056849 Japanese Patent Application Laid-Open No. 2004-2929 Japanese Laid-Open Patent Publication No. 2008-46149 Japanese Patent No. 4833942

However, as described above, an Ag alloy film is formed by adding a metal element other than Ag to the Ag film. However, by adding a metal element, excellent optical properties and conductivity of Ag may be impaired . Further, in the Ag alloy film used as the translucent electrode film, further thinning is required for the purpose of improving the transmittance. However, if the thickness of the Ag film becomes thin, especially when the thickness is 20 nm or less, there is a problem.

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, thereby causing corrosion of the Ag alloy film.

The present invention has been made in view of the above-described circumstances, and has as its object to provide an optical film which has excellent optical characteristics and conductivity immediately after film formation and that its optical characteristics and conductivity are not greatly changed even under an environment of heat and humidity and corrosion by chlorine or sulfur An Ag alloy film which does not easily agglomerate even if it is an ultra thin film, a method for producing the Ag alloy film, and an Ag alloy sputtering target which can be used for manufacturing the Ag alloy film. It is also an object of the present invention to provide a laminated film of an Ag alloy film and a transparent conductive oxide in which corrosion of the Ag alloy film does not occur well.

In order to solve the above problems, the Ag alloy film of the present invention contains Ti in an amount of 0.1 atomic% to 5.0 atomic% and is selected from Cu, Sn, Mg, In, Sb, Al, Zn, At least one element in a total amount of not less than 0.1 atomic% and not more than 10.0 atomic% in total with respect to Ti, the remainder being composed of Ag and inevitable impurities, and at least one element selected from the group consisting of Na, Si, V, Cr, And the total content is 100 mass ppm or less.

Since the Ag alloy film of this structure contains 0.1 atomic% or more of Ti, the sulfur content and the chlorine resistance of the Ag alloy film are improved. Although the reason is not clear, it is considered that when this Ag alloy film is formed by sputtering or the like, Ti is oxidized inside the film, and Ti oxide is self-formed and contributes to the manifestation of the effect.

Further, since the content of Ti is limited to 5.0 atomic% or less, the Ag alloy film can secure the excellent optical characteristics and conductivity possessed by Ag. The Ag alloy film is limited to a total content of Na, Si, V, Cr, Fe, and Co of 100 mass ppm or less. These limitations reduce the amount of these metal elements present as oxides on the grain boundary surface of the Ag crystal and widen the intergranular surface of the Ag crystal in which the Ti oxide is present so that the sulfur and chlorine resistance of the Ag alloy film .

In addition, metallic elements such as Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga suppress migration (aggregation) of Ag atoms in the Ag alloy film. The stability of the optical characteristics and conductivity of the Ag alloy film under a heat and humidity environment is improved and aggregation does not occur even if the Ag alloy film is a thin film. In addition, since the content of these metal elements is limited to the range of not more than 10.0 at% in total with respect to Ti, it is possible to secure the excellent optical characteristics and conductivity of the Ag alloy film immediately after the film formation, It is possible to inhibit a significant change in conductivity.

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, Is preferable.

In this case, although the reason is not clear, the content A of Ti and the atomic ratio A / B of the total content B of Cu, Sn, Mg, In, Sb, Al, , Ti acts more effectively and the sulfur content and chlorine resistance of the Ag alloy film are improved.

The Ag alloy film of the present invention may further contain at least one element selected from the group consisting of Pd, Pt, and Au in an amount of 0.1 atomic% or more in total, and at least one element selected from the group consisting of Ti, Cu, Sn, Mg, In, Sb, , Ge, and Ga in a total amount of 10.0 atom% or less.

In this case, a total of 10 atomic% or more of noble metal elements having high chemical stability such as Pd, Pt, and Au are added in a total amount of 0.1 atomic% or more and total of Ti, Cu, Sn, Mg, In, Sb, Or less, the chemical stability of the Ag alloy itself is improved, and the chlorine resistance and the 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, even though the Ag alloy film is an ultra thin film having a film thickness of 20 nm or less, it is difficult for the Ag alloy film to flocculate and become island-like, so that the light transmittance becomes high.

The laminated film of the present invention is characterized by comprising the above-described 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 such a constitution, since the surface or grain boundary of the Ag crystal in the Ag alloy film is protected by the Ti oxide, the electromagnetism generated between the Ag alloy film and the transparent conductive oxide film is suppressed, It does not happen very well.

The Ag alloy sputtering target of the present invention comprises 0.1 atom% or more and 5.0 atom% or less of Ti, at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, % Or more, and the total amount of Ti and Ti is 10.0 atomic% or less, the balance of Ag and unavoidable impurities, and the total content of Na, Si, V, Cr, Fe and Co is 100 mass ppm or less .

The Ag alloy film formed by the sputtering method using the Ag alloy sputtering target of this structure has high optical reflectance or transmittance because of its high optical reflectivity or transmittance and has a low resistance value so that it has excellent conductivity. The optical characteristics and the conductivity do not change greatly and corrosion due to chlorine or sulfur does not occur well and coagulation does not occur even if it is an ultra thin film. Further, since the Ag alloy sputtering target of this structure has a total content of Na, Si, V, Cr, Fe, and Co limited to 100 mass ppm or less, abnormal discharge does not occur at the time of film formation by the sputtering method .

In the Ag alloy sputtering target of the present invention, the atomic ratio A / B of the content A of Ti and the total content B of Cu, Sn, Mg, In, Sb, Al, Or less.

In this case, the sulfur resistance and the chlorine resistance of the Ag alloy film formed by using the Ag alloy sputtering target are improved.

The Ag alloy sputtering target of the present invention may further contain at least one element selected from the group consisting of Pd, Pt, and Au in an amount of 0.1 atomic% or more in total, and at least one element selected from the group consisting of Ti, Cu, Sn, Mg, In, Sb, Zn, Ge, and Ga in a total amount of 10.0 atomic percent or less.

In this case, the salt water resistance and the sulfidization resistance of the Ag alloy film formed by using the Ag alloy sputtering target are improved.

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, an abnormal discharge does not occur more easily at the time of film formation by the sputtering method.

Furthermore, in the Ag alloy sputtering target of the present invention, the grain size of the Ag alloy crystal is measured at a plurality of points as a polycrystalline body containing a plurality of Ag alloy crystals. As a result, The average crystal grain diameter C which is an average value and the average value D of the grain diameter of the Ag alloy crystals at the respective measured points and the average value D _max in which the absolute value of the deviation of the average crystal grain diameter C becomes maximum, (%) = (D _max - C) / C x 100 is preferably within 20%.

In this case, since the deviation of the Ag alloy grain diameter of the Ag alloy sputtering target is small, an abnormal discharge does not occur more easily at the time of film formation by the sputtering method.

Furthermore, in the Ag alloy sputtering target of the present invention, it is preferable that the average crystal grain diameter C is 200 m or less.

In this case, even if the target is consumed by the film formation by the sputtering method, the irregularities formed on the sputter surface become 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 Ag alloy sputtering target described above.

By using the method for producing an Ag alloy film of the present invention, it is possible to obtain a film having excellent optical properties and conductivity immediately after the film formation, and also exhibiting excellent optical characteristics and conductivity, An Ag alloy film which does not cause agglomeration even if it is an ultra-thin film can be produced.

Here, in the manufacturing method of the Ag alloy film of the present invention, it is preferable to perform sputtering in a gas atmosphere containing oxygen in a quantity of 0.5 to 5% of the total pressure of the inert gas.

In this case, 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 under a heat and humidity environment, and further improved resistance to chlorine and sulfur.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, since the reflectance or transmittance of light immediately after film formation is high, it has excellent optical characteristics, has a low resistance value and has excellent conductivity, and its optical characteristics and conductivity do not change greatly It is possible to provide an Ag alloy film in which corrosion due to chlorine or sulfur does not occur well and agglomeration does not occur even if it is an ultra thin film, a method for producing the Ag alloy film, and an Ag alloy sputtering target usable for manufacturing the Ag alloy film. Further, according to the present invention, it is possible to provide a laminated film of an Ag alloy film and a conductive oxide, in which corrosion of the Ag alloy film does not occur well.

<Ag alloy film>

Hereinafter, an Ag alloy film as an embodiment of the present invention will be described.

The Ag alloy film of the present embodiment can be used, for example, as a reflective electrode film of an organic EL element, a reflective liquid crystal display, an LED, a solar cell, or the like, or a translucent electrode film of a touch panel. Further, the Ag alloy film of this embodiment can be used as a laminated film with a conductive oxide film.

The Ag alloy film of this embodiment is difficult to aggregate even if it is an ultra-thin film with a thickness of 20 nm or less and become island-like. For this reason, the Ag alloy film of the present embodiment can be used particularly advantageously as a semi-transparent electrode film having a film thickness of 20 nm or less. The Ag alloy film preferably has a thickness of 5 nm or more. When the thickness of the Ag alloy film is less than 5 nm, there is a fear that the conductivity can not be ensured.

The Ag alloy film according to the present embodiment contains 0.1 atom% or more and 5.0 atom% or less of Ti and 0.1 atom% or more in total of at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, And the total amount of Na, Si, V, Cr, Fe and Co is less than or equal to 10.0 atomic percent, and the remainder is composed of Ag and unavoidable impurities. At least one element selected from the group consisting of Pd, Pt, and Au is added in a total amount of not less than 0.1 atomic percent and not more than 10.0 atomic percent of Ti, Cu, Sn, Mg, In, Sb, Al, Zn, By weight.

The reason why the composition and the film thickness of the Ag alloy film are defined as described above will be described below.

(Ti)

Ti is preferably present as an oxide of Ti on the surface or inside of the Ag alloy film. The Ti oxide has an action of protecting the Ag alloy film from sulfur or chlorine. That is, Ti is an element having an action effect of improving the sulfur content and chlorine resistance of the Ag alloy film.

The Ti oxide may exist as a layer on the surface of the Ag alloy film. Further, when the Ag alloy film is thin, it is difficult to confirm the presence of the Ti oxide layer in the ordinary measurement. In this case, however, the Ag alloy film of this embodiment exhibits sufficient sulfur resistance and chlorine resistance. It is considered that even a thin oxide layer of Ti which is difficult to measure contributes to the manifestation of the effect.

Here, when the Ti content of the Ag alloy film is less than 0.1 atom%, the sulfur content and the chlorine resistance are not sufficiently improved. On the other hand, when the content of Ti exceeds 5.0 at%, the transmittance or reflectance of light of the Ag alloy film immediately after the film formation decreases and the resistance value increases. When the content of Ti exceeds 5.0 at%, the self-formation of the Ti oxide is inhibited and the sulfur content and the chlorine resistance may not be sufficiently improved.

For this reason, in the Ag alloy film of this embodiment, the content of Ti is set in the range of 0.1 atomic% to 5.0 atomic%. The content of Ti in the Ag alloy film is preferably in the range of 0.2 atomic% or more and 3.0 atomic% or less, more preferably 0.5 atomic% or more and 2.0 atomic% or less, for ensuring the above- It is more preferable to set the range.

(Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga)

The Ag alloy film is present mainly in the Ag alloy film, and the effect of improving the optical characteristics and the stability of the conductivity of the Ag alloy film under the heat and humidity environment and the aggregation of the Ag alloy film And the like.

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%, the optical properties and stability of the conductivity And the agglomeration of the Ag alloy film is likely to occur.

On the other hand, if the content of these metal elements exceeds 10.0 atomic% in total with respect to Ti, the transmittance or reflectance of light of the Ag alloy film immediately after film formation may decrease, and the resistance value may increase.

For this reason, in the Ag alloy film of this embodiment, the total content of at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga is 0.1 atomic% Is set to a range in which the total amount is 10.0 atomic% or less. The total content of the metal elements in the Ag alloy film is preferably 0.2 atomic percent or more and more preferably 7.0 atomic percent or less in total with respect to Ti, Atomic% or more, and more preferably 5.0 atomic% or less in total with respect to Ti.

(Na, Si, V, Cr, Fe, Co)

Na, Si, V, Cr, Fe and Co are metal elements contained as inevitable impurities. These metal elements are liable to be segregated in the grain boundaries of the Ag alloy film because of their low solubility in Ag, and furthermore, the elements are combined with the residual oxygen in the dissolved atmosphere to become oxides, and these oxides are interposed in the Ag alloy film structure to form Ti Thereby inhibiting self-oxidation of the oxide film. Therefore, if the total content of these metal elements exceeds 100 mass ppm, the corrosion resistance due to Ti is not sufficiently exhibited, and the chlorine-resistant and sulfur-resistant properties become insufficient.

For this reason, in the Ag alloy film of this embodiment, the total content of Na, Si, V, Cr, Fe, and Co in the inevitable impurities is limited to 100 mass ppm or less. The total content of the metal element in the Ag alloy film is preferably in the range of 30 mass ppm or less and more preferably in the range of 10 mass ppm or less in order to reliably exhibit the above- But it is not limited thereto. In addition, since excessive reduction causes an increase in manufacturing cost, the lower limit of the total content of the metal elements in the Ag alloy film is preferably 1 mass ppm, more preferably 5 mass ppm, It is not limited.

Inevitable impurities other than Na, Si, V, Cr, Fe, and Co do not impair or substantially prevent the effect of improving the corrosion resistance by Ti. Therefore, it is not necessary to excessively reduce them, It is not limited to 1 ppm by mass or more and 1000 ppm by mass or less.

(Pd, Pt, Au)

Pd, Pt, and Au are present mainly in an Ag alloy film, which has the effect of further improving the chlorine resistance and the sulfur resistance of the Ag alloy film formed.

Here, when the total content of at least one element selected from Pd, Pt and Au is less than 0.1 at%, there is a fear that the chlorine resistance and the sulfur content are not sufficiently improved. On the other hand, when the total content of these metal elements exceeds 10.0 atomic% in total with respect to Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga in total, the light transmittance or reflectance of the Ag alloy film immediately after film formation 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, , Zn, Ge, and Ga in a total amount of 10.0 atomic percent or less. In order to reliably exhibit the above-mentioned action and effect, the total content of the metal element in the Ag alloy film is preferably 0.2 atomic% or more, more preferably 0.5 atomic% or more. The total content of the metal elements in the Ag alloy film is preferably 7.0 atomic% or less, more preferably 5.0 atomic% or less of the total amount of Ti, Cu, Sn, Mg, In, Sb, Is more preferable.

(Film thickness)

The Ag alloy film of the present embodiment is difficult to aggregate even if it is an ultra thin film having a film thickness of 20 nm or less and become island-like. Therefore, the Ag alloy film of this embodiment can be advantageously used as a semi-transparent electrode film having a film thickness of 20 nm or less.

The Ag alloy film preferably has a thickness of 5 nm or more. When the thickness of the Ag alloy film is less than 5 nm, there is a fear that the conductivity can not be ensured.

&Lt; Laminated film &

The laminated film of the present embodiment includes the Ag alloy film of the present embodiment and the conductive oxide film formed on one side or both sides of the Ag alloy film. In the laminated film of this structure, since the Ti oxide layer is interposed between the Ag alloy film and the conductive oxide film, the electromagnetism occurring between the Ag alloy and the conductive oxide is suppressed, so that corrosion of the Ag alloy film does not occur well.

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

<Ag alloy sputtering target>

The sputtering target of the present embodiment is a sputtering target which contains 0.1 atom% or more and 5.0 atom% or less of Ti and at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, And the total amount of Ti and Ti is not more than 10.0 atomic percent and the balance of Ag and unavoidable impurities, and the total content of Na, Si, V, Cr, Fe and Co is 100 mass ppm or less.

Since the total content of Si, V, Cr, Fe, and Co is limited to 100 mass ppm or less in the sputtering target of the present embodiment, abnormal discharge does not occur at the time of film formation by the sputtering method. It is preferable that the total content of Na, Si, V, Cr, Fe, and Co is 10 mass ppm or less in order to more reliably suppress the abnormal discharge during film formation by the sputtering method.

Cu, Sn, Mg, In, Sb, Al, Zn, Ge, or the like in total of at least one kind of element selected from Pd, Pt, Ga in a total amount of 10.0 atomic percent or less. Since the sputtering target of this embodiment contains Pd, Pt, and Au in the above-described range, the Ag alloy film formed by using the Ag alloy sputtering target has improved salt resistance and sulfidization resistance.

The sputtering target of the present embodiment is preferably a polycrystal including a plurality of Ag alloy crystals. In this case, when the particle diameter of the Ag alloy crystal was measured at a plurality of points (for example, 16 points), the average crystal grain diameter C, which is an average value of the particle diameters of all the Ag alloy crystals measured, (D _max - C) / C × (D _max ) of the Ag alloy grain diameter defined by the average value D _max in which the absolute value of the deviation of the average crystal grain diameter C becomes the largest among the average grain size D of the Ag alloy crystal 100 (absolute value) is preferably within 20%. By reducing the deviation of the Ag alloy grain diameter, an abnormal discharge does not occur more easily at the time of film formation by the sputtering method. The average crystal grain diameter C is preferably 200 nm or less.

In order to accurately obtain the deviation E of the Ag alloy grain diameter, it is preferable to measure the grain size of the Ag alloy crystal for a plurality of regions having a size of 500 탆 x 500 탆 to 1000 탆 x 1000 탆, But it is not limited thereto.

&Lt; Manufacturing method of Ag alloy sputtering target &gt;

Next, a method of manufacturing the Ag alloy sputtering target according to the present embodiment will be described.

First, 99% by mass or more of Ag and 99.9% by mass or more of purity of Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga are prepared as a dissolution raw material.

In order to reduce the total content of Na, Si, V, Cr, Fe and Co in unavoidable impurities, these elements contained in the Ag raw material are analyzed by ICP (inductively coupled plasma) An Ag raw material having a total content of these elements in a predetermined range is selected and used. In order to reliably reduce the total content of Na, Si, V, Cr, Fe, and Co, it is preferable to leach the Ag raw material with nitric acid or sulfuric acid and then electrolytically refine it using an electrolytic solution having a predetermined Ag concentration .

The selected Ag raw materials and the added elements (Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga) are weighed to have a predetermined composition. Next, in the melting furnace, Ag is dissolved in a high vacuum or an inert gas atmosphere, and a predetermined amount of the additive element and silver sulfide are added to the obtained molten metal. And at least one element selected from the group consisting of Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga is added in a total amount of 0.1 to 5.0 atomic% And a total content of Ti is 0.1 atomic% or more and a total amount of Ti is 10.0 atomic% or less, the balance of Ag and inevitable impurities, and the total content of Na, Si, V, Cr, Fe, Ag alloy ingot is manufactured.

The obtained Ag alloy ingot is preferably subjected to cold rolling and the ingot after the rolling is heat-treated. The heat treatment is preferably performed at a temperature of 500 to 700 ° C in the air. After the heat treatment, it is preferable to quench the rolling ingot to, for example, about 200 캜 at a cooling rate of 200 캜 / min or more. As a method of quenching, there is a water shower of about one minute. This quenching can suppress the growth of the crystal grains and make the crystal grain diameter small. The Ag alloy sputtering target according to the present embodiment can be manufactured by machining the rolled plate of the Ag alloy thus obtained. The shape of the Ag alloy sputtering target is not particularly limited, and may be a disc shape, a plate shape, or a cylindrical shape.

&Lt; Production method of Ag alloy film &gt;

In the manufacturing method of the Ag alloy film of the present embodiment, sputtering is performed using an Ag alloy sputtering target. As the sputtering apparatus, a magnetron sputtering 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 of manufacturing the 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 such that the pressure is 0.5 to 5% of the total pressure of the Ar gas. By performing the 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 under a heat and humidity environment, and further improved resistance to chlorine and sulfur.

Example

Example 1: Fabrication of Ag alloy sputtering target

[Inventive Examples 1 to 36, Comparative Examples 1 to 14]

Ag having a purity of 99.9% by mass or more and Ti, Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt and Au having a purity of 99.9% by mass or more were prepared as a dissolution raw material.

Here, in order to reduce the content of the impurity element, a method of electrolytically refining the Ag raw material after leaching with the nitric acid or sulfuric acid and using the electrolytic solution of the predetermined Ag concentration was adopted. An Ag raw material having impurities reduced by the refining method is subjected to impurity analysis by the ICP method and further an Ag raw material having a total concentration of Na, Si, V, Cr, Fe and Co of 100 ppm or less is sputtered As a raw material for the production of the target.

The selected Ag raw materials 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. Then, Ag was dissolved in a high-vacuum or inert gas atmosphere using a dissolution furnace, and a predetermined Ti and Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt , And Au were added and dissolved in a vacuum or an inert gas atmosphere. Thereafter, it was poured into a mold to prepare an Ag alloy ingot (ingot). Here, at the time of dissolving Ag, the atmosphere was once changed to a vacuum (5 x 10 &lt; ^-2 &gt; Pa or less) and then replaced with an Ar gas. The addition of Ti and Cu, Sn, Mg, In, Sb, Al, Zn, Ge, Ga, Pd, Pt and Au was performed in an Ar gas atmosphere.

Subsequently, the obtained Ag alloy ingot was cold-rolled at a reduction ratio of 70%, and then heat-treated at 500 to 700 ° C for 1 hour in the atmosphere. After the heat treatment, the ingot was quenched to about 200 캜 at a cooling rate of 200 캜 / min or more. The rolled plate of the Ag alloy thus obtained was calibrated by a calibration press, a roller leveler, etc., and then subjected to mechanical processing such as price processing and electric discharge machining to obtain Ag alloy sputtering with a predetermined composition having a diameter of 152.4 mm and a thickness of 6 mm The target was made.

[Comparative Example 15]

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 as a dissolution raw material.

An Ag alloy sputtering target was produced in the same manner as above except that the Ag raw material was not electrolytically purified.

[Composition analysis]

For the composition of the target, an analytical sample was collected from the Ag alloy ingot after casting, and the sample was analyzed by ICP emission spectrometry. The results of this analysis are shown in Tables 1A and 1B.

In each of the following examples, the composition of the film was confirmed to be substantially the same as the composition of the target used, by ICP emission spectroscopy.

[Organizational Analysis]

The deviation of the average grain diameter and the grain diameter of the Ag alloy sputtering target was analyzed by the following method. The results of the analysis are shown in Table 2.

(Method of measuring deviation of average crystal grain diameter and crystal grain diameter)

A sample piece of the legislative body having a width of about 10 mm from 16 points was evenly sampled in the sputter plane of the target. Next, the sputter surface of each sample piece was polished. At this time, polishing was carried out with water resistant papers # 180 to # 4000, followed by buff polishing with an abrasive of 3 mu m to 1 mu m. Further, etching was performed to such an extent that the grain boundary could be seen with an optical microscope. Here, as the etching solution, a mixed solution of aqueous hydrogen peroxide and aqueous ammonia was used and immersed at room temperature for 1 to 2 seconds, whereby the grain boundary appeared. Next, each sample was photographed with an optical microscope. The magnification of the photograph was selected to be easy to count crystal grains (60 to 120 times). In each of the photographs, a line segment of 60 mm was drawn four times in total in the form of a lattice (in the symbol #) at intervals of 20 mm, and the number of crystal grains cut into each straight line was counted. In addition, the crystal grain at the end of the line segment was counted at 0.5. For each point, an average slice length L (占 퐉) was obtained by L = 60000 / (M 占)) where M is the actual magnification and N is the average value of the number of crystal grains cut by each straight line. Next, the average particle diameter d (占 퐉) at each point of the sample was calculated from d = (3/2) 占 L from the average slice length L (占 퐉) of each of the obtained points. The average value of the average particle diameter d (占 퐉) of the samples sampled from the 16 points was defined as the diameter of the crystal grain of the target phosphorus.

The deviation of the particle diameter was calculated as follows. The absolute value of the deviation (| [(average particle diameter of any one point) - (average value of average particle diameters at 16 points)] of the 16 average particle diameters obtained at 16 points is the maximum . Subsequently, using the specific average particle diameter (specific average particle diameter), the deviation of the particle diameter was calculated by the following formula.

(Average of average particle diameters at 16 points) 占 100 (%) (specific average particle diameter) - (average value of average particle diameters at 16 points)

[Abnormal discharge test]

The Ag alloy sputtering target produced in the above-described Examples of the present invention and Comparative Example was brazed to a backing plate made of anoxic copper using indium solder to prepare a target composite.

The above-mentioned target composite was mounted on a conventional magnetron sputtering apparatus and evacuated to 1 x 10 &lt; ^-4 &gt; Pa. Thereafter, an Ar gas pressure of 0.5 Pa, an applied electric power of 1000 W and a target substrate distance of 60 mm Sputtering was performed. The number of abnormal discharges at the time of sputtering was measured by the arc count function of a DC power source (RPDG-50A) manufactured by MKS Instrument Co., Ltd. as the number of abnormal discharges for one hour from the start of discharge. The target was consumed by repeatedly exchanging the empty sputter and the antifouling plate for 4 hours and intermittently sputtering for 20 hours. Thereafter, further sputtering was performed to measure the number of abnormal discharges that occurred during 30 minutes after consumption (20 hours of sputtering). The number of abnormal discharges occurring one hour after the start of discharge is referred to as &quot; the number of abnormal discharges after one hour &quot;, and the number of abnormal discharges occurred during the last 30 minutes after consumption are shown as &quot; abnormal discharging times after consumption &quot;

[Table 1A]

[Table 1B]

[Table 2]

In Comparative Example 15 in which the total content of Na, Si, V, Cr, Fe, and Co exceeded 100 mass ppm, the number of discharges was more than 34 times / h after one hour and the number of discharges after consuming was 41 times / And the sputtering could not be performed stably. In Examples 22 and 25 in which the total content of Na, Si, V, Cr, Fe, and Co exceeded 10 mass ppm, it was confirmed that the number of discharges more than one hour and the number of abnormal discharges after consumption slightly increased . Further, in Comparative Examples 1, 3 and 9 in which the deviation of the Ag alloy grain diameter exceeded 20%, it was confirmed that the number of abnormal discharges after consumption slightly increased.

Example 2: Fabrication of Ag alloy film (semi-permeable film)

[Examples 101 to 139 and Comparative Examples 101 to 115]

The Ag alloy sputtering target prepared 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 the glass substrate.

(Conditions of sputtering)

Ag alloy sputtering target used for deposition: As shown in Table 3

Achieved vacuum degree: 5 × 10 ^-5 Pa or less

Use gas: Ar (Inventive Examples 101 to 125, 129 to 139, Comparative Examples 101 to 115)

A mixed gas of Ar and oxygen (Examples 126 to 128 in the present invention)

Ar gas pressure: 0.5 Pa

Oxygen Gas Pressure: As a percentage of the Ar gas pressure (0.5 Pa)

Power: DC 200 W

Target-substrate distance: 70 mm

[evaluation]

(Sheet resistance after film formation)

The sheet resistance of the thus obtained Ag alloy film was measured by a four-probe method using Loresta GP manufactured by Mitsubishi Chemical Corporation. The obtained sheet resistance is shown in Table 3 as &quot; sheet resistance after film formation &quot;.

(Transmittance after film formation)

The light transmittance of the Ag alloy film thus obtained was measured using a spectrophotometer (Hitachi High-Tech U-4100). The obtained light transmittance is shown in Table 3 as &quot; transmittance after film formation &quot;. The numerical values shown in the table are transmittance of light having a wavelength of 550 nm.

(Constant temperature and humidity test)

The Ag alloy film thus obtained was allowed to stand for 250 hours in a constant temperature and humidity bath having a temperature of 85 캜 and a humidity of 85% and then taken out from the constant temperature and humidity bath. Then, the sheet resistance and transmittance of the Ag alloy film were measured in the same manner as described above. (The sheet resistance after the constant temperature and humidity test - the sheet resistance after the film formation) / the sheet resistance after the film formation 100] and the change in the transmittance at a wavelength of 550 nm [= transmittance after constant temperature and humidity test - transmittance after film formation] , And the appearance of the film (presence or absence of discoloration or spots), the stability in the constant temperature and humidity test was evaluated. The appearance of the film was evaluated as &quot; o &quot; when no discoloration or spots occurred after the constant temperature and humidity test, and &quot; x &quot; Further, when a spot having a diameter of 0.5 mm or more was generated, it was judged that there was a spot. The results are shown in Table 4.

(Sulfation test)

The Ag alloy film obtained as described above was immersed in an aqueous solution of 0.01 wt% sodium sulfide for 1 hour at room temperature, then taken out of an aqueous sodium sulfide solution, sufficiently washed with pure water, and then dried to remove moisture. Then, the sheet resistance and transmittance of the Ag alloy film were measured as described above. The sulfur resistance was evaluated by the rate of change in sheet resistance, the amount of change in the transmittance at a wavelength of 550 nm, and the appearance of the film, as in the constant temperature and humidity test. The appearance of the film was evaluated as &quot; o &quot; when no discoloration or spots occurred after the sulfiding test, and &quot; x &quot; The results are shown in Table 4.

(Salt water test)

The Ag alloy film thus obtained was immersed in a 5% NaCl aqueous solution at room temperature for 10 days, thereafter taken out from the NaCl aqueous solution, sufficiently washed with pure water, and then dried to remove moisture. Then, the sheet resistance and transmittance of the Ag alloy film were measured as described above. Similarly to the constant temperature and humidity test, the rate of change in sheet resistance, the amount of change in the transmittance at a wavelength of 550 nm, and the appearance of the film were evaluated for flame resistance. The appearance of the film was evaluated as &quot; o &quot; when no discoloration or spots occurred after the salt water test, and &quot; disappearance of film &quot; The results are shown in Table 4.

[Table 3]

[Table 4]

In Comparative Example 101 using the Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the sheet resistance significantly increased before and after the sulphurization test, the transmittance was greatly decreased, and the Ag alloy film after the sulphurization test showed discoloration · There were spots. After the salt water test, the Ag alloy film disappeared.

In Comparative Example 102 using the Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the sheet resistance significantly increased before and after the sulphurization test, the transmittance was greatly decreased, and the Ag alloy film after the sulphide- · There were spots. After the salt water test, the Ag alloy film disappeared.

(Comparative Examples 3, 5, 7, 9, 11, and 13) in which the Ag alloy sputtering targets (Cu, Sn, Mg, In, Sb, Al, Zn, , 105, 107, 109, 111, and 113, the sheet resistance significantly increased before and after the constant temperature and humidity test, and the transmittance was greatly decreased, and the Ag alloy film after the constant temperature and humidity test had discoloration and spots.

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

In Comparative Example 115 using the 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 greatly increased before and after the sulfurization test, And discoloration and spots were observed in the Ag alloy film after the sulfidation test. After the salt water test, the Ag alloy film disappeared.

On the contrary, when Ti is contained in an amount 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, And the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less (Inventive Examples 1 to 25 of the Inventive Examples 1 to 25) In Examples 101 to 128 of the present invention, the sheet resistance after film formation was smaller than 30 Ω / □ and the transmittance exceeded 60%. Also, the sheet resistance and the transmittance did not significantly change before and after the test in the tests of the constant temperature and humidity test, the sulfidation test and the brine test, and the Ag alloy film after the test did not cause discoloration or spots.

Particularly in Inventive Examples 126 to 128 in which deposition was performed in a mixed gas atmosphere of Ar and oxygen, compared with Inventive Example 124 in which deposition was performed in an Ar gas atmosphere using the same Ag alloy sputtering target, And the transmittance was high. Further, in the tests of the constant temperature and humidity test, the sulfidation test and the brine test, the change of the sheet resistance and the transmittance was small, and the corrosion resistance was improved.

At least one element selected from the group consisting of Pd, Pt, and Au is added in a total amount of not less than 0.1 atomic percent and not more than 10.0 atomic percent of Ti, Cu, Sn, Mg, In, Sb, Al, Zn, , The changes in sheet resistance and transmittance before and after the sulfurization test and the salt water test were substantially reduced in the Inventive Examples 129 to 139 using the Ag alloy sputtering targets (Inventive Examples 26 to 36).

From the above, it was confirmed that according to the present invention, it is possible to provide an Ag alloy film which is low in resistance, high in transmittance, excellent in heat resistance, moisture resistance, sulfur resistance and chlorine resistance, and suitable as a translucent electrode film.

Example 3: Fabrication of Ag alloy film (reflective film)

[Inventive Examples 140 to 141, Comparative Examples 116 to 117]

An Ag alloy sputtering target prepared in Example 1 was mounted on a sputtering apparatus and sputtering was carried out under the same conditions as in Example 2 to form an Ag alloy film having a thickness of 100 nm on the surface of the glass substrate. To evaluate the Ag alloy film. The contents thereof are shown in Table 5.

Here, the &quot; reflectance after deposition &quot; in Table 5 is a value obtained by measuring the reflectance of the obtained Ag alloy film by using a spectrophotometer. The numerical values shown in the table are reflectance of light having a wavelength of 550 nm. The &quot; reflectance change amount &quot; is the change amount of the reflectance at a wavelength of 550 nm (= transmittance after each test-transmittance after film formation).

[Table 5]

In Comparative Example 116 using the Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the sheet resistance significantly increased before and after the sulphurization test, and the reflectance greatly decreased. In the Ag alloy film after the sulphurization test, · There were spots. After the salt water test, the Ag alloy film disappeared.

In Comparative Example 117 using the 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. In the Ag alloy film after the sulfuration test, · There were spots. After the salt water test, the Ag alloy film disappeared.

On the contrary, when Ti is contained in an amount 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, Of the total content of Na, Si, V, Cr, Fe and Co in the total amount of not more than 10.0 atomic% In Inventive Example 140, the sheet resistance and the reflectance did not largely change before and after the test in any of the tests of the constant temperature and humidity test, the sulfidation test and the brine test, and the discoloration and spots were not generated in the Ag alloy film after the test.

Particularly, in Inventive Example 141 in which film formation was performed in a mixed gas atmosphere of Ar and oxygen, compared with Inventive Example 140 in which film formation was performed in an Ar gas atmosphere using the same Ag alloy sputtering target, a constant temperature and humidity test, The changes in the sheet resistance and the transmittance were small and the corrosion resistance was improved in any test of the salt water test.

From the above, it was confirmed that according to the present invention, it is possible to provide an Ag alloy film suitable as a reflective electrode film because of its low resistance, high transmittance and excellent heat resistance, moisture resistance, sulfur resistance and chlorine resistance.

Example 4: Fabrication of semitransparent conductive laminated film (conductive oxide film / Ag alloy film / conductive oxide film)

[Examples 201 to 217 and Comparative Examples 201 to 208]

The Ag alloy sputtering target prepared in Example 1 and the following target for conductive oxide film formation were mounted on a sputtering apparatus and sputtering was performed under the same conditions as in Example 2. The surface of the glass substrate was coated with a conductive oxide (A ), A film of a Ag alloy (a translucent film) having a thickness of 10 nm and a film of a conductive oxide (B) having a thickness of 20 nm were laminated in this order on a copper foil. Similarly, the translucent conductive laminated film was evaluated. The contents are shown in Tables 6 and 7.

(Composition of target for conductive oxide film formation)

ITO: 90 mol% of indium oxide, 10 mol% of tin oxide,

IZO: indium oxide 70 mol%, zinc oxide 30 mol%

AZO: 2 mol% of aluminum oxide, 98 mol% of zinc oxide,

GZO: 2 mol% of gallium oxide, 98 mol% of zinc oxide,

Further, the conductive oxide film was formed in an Ar gas atmosphere containing 2% oxygen.

[Table 6]

[Table 7]

In Comparative Examples 201, 203, 205 and 207 using the Ag alloy sputtering target (Comparative Example 1) in which the content of Ti was smaller than 0.1 atomic%, the conductive oxides (A) and (B) The resistance greatly increased, the transmittance was greatly lowered, and the rim of the Ag alloy film after the sulfidation test discolored. After the salt water test, the Ag alloy film disappeared.

In Comparative Examples 202, 204, 206 and 208 using the Ag alloy sputtering target (Comparative Example 2) having a Ti content of more than 5.0 atomic%, the conductive oxide (A) and the conductive oxide (B) Was larger than 30? / ?, and the transmittance was lower than 80%. Further, the sheet resistance greatly increased before and after the sulfiding test, the transmittance was greatly decreased, and the rim of the Ag alloy film after the sulfidation test discolored. After the salt water test, the Ag alloy film disappeared.

On the contrary, when Ti is contained in an amount 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, And a total content of Na, Si, V, Cr, Fe, and Co of not more than 10.0 atomic percent based on the total amount of the Ag alloy sputtering target , 14, 15, 23, and 25), the sheet resistance after the film formation was smaller than 30 Ω / □ and the transmittance exceeded 80%. The sheet resistance and the transmittance did not significantly change before and after the test in the tests of the constant temperature and humidity test, the sulfidation test, and the brine test, and the laminated film after the test was stable without discoloration or spots.

Particularly, in Examples 208 to 210 in which deposition was performed in a mixed gas atmosphere of Ar and oxygen, compared with Inventive Example 204 in which deposition was performed in an Ar gas atmosphere using the same Ag alloy sputtering target, The transmittance after film formation was generally high, and the changes in sheet resistance and transmittance were substantially small even in the tests of the constant temperature and humidity test, the sulfidation test and the brine test, and the stability was improved.

In the present invention 217 using the Ag alloy sputtering target containing Pd (Inventive Example 27), changes in sheet resistance and transmittance before and after the sulfidation test and the salt water test were substantially reduced.

From the above, it was confirmed that the Ag alloy film according to the present invention is stable and does not promote corrosion well even when used as a semitransparent conductive laminated film with the conductive oxide film.

Example 5: Fabrication of reflective conductive laminated film (conductive oxide film / Ag alloy film / conductive oxide film)

[Examples 218 to 219 and Comparative Examples 209 to 210]

The Ag alloy sputtering target prepared in Example 1 and the following target for conductive oxide film formation were mounted on a sputtering apparatus and sputtering was carried out under the same conditions as in Example 4. The surface of the glass substrate was coated with a conductive oxide A ), A film of a 100 nm thick Ag alloy film (reflecting film) and a film of 20 nm thick conductive oxide (B) were laminated in this order, and the same evaluation as that of the Ag alloy film of Example 3 To evaluate the reflective conductive laminated film. Table 8 shows the contents.

[Table 8]

In Comparative Example 209 using the Ag alloy sputtering target (Comparative Example 1) having a Ti content of less than 0.1 atomic%, the sheet resistance was increased before and after the sulphurization test, the reflectivity was decreased, and the rim of the Ag alloy film after the sulphurization test was discolored . After the salt water test, the Ag alloy film disappeared.

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

On the contrary, when Ti is contained in an amount 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, Of the total content of Na, Si, V, Cr, Fe, and Co in the range of not more than 10.0 atomic percent based on the total amount of the Ag alloy sputtering target (the present invention example 14) In Inventive Examples 218 and 219, the sheet resistance after film formation was small, and the reflectance exceeded 94%. Also, the sheet resistance and the transmittance did not significantly change before and after the test in the tests of the constant temperature and humidity test, the sulfidation test and the brine test, and the Ag alloy film after the test did not cause discoloration or spots.

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

Industrial availability

The Ag alloy film of the present invention has excellent optical characteristics and conductivity immediately after the film formation and also does not significantly change its optical characteristics and conductivity even under a heat and humidity environment and does not cause corrosion by chlorine or sulfur. It is preferable to use a reflective electrode film or a semitransparent electrode film because aggregation does not occur well.

Claims (13)

At least one element selected from the group consisting of Ti, Ti, and Ti in an amount of not less than 0.1 atomic% and not more than 5.0 atomic%, a total of at least one element selected from Cu, Sn, Mg, In, Sb, Al, And the balance of Ag and inevitable impurities, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. The method according to claim 1,
Wherein an atomic ratio A / B of a content A of Ti and a total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga is in a range of 0.1 to 6.0. . 3. The method according to claim 1 or 2,
In addition, the total amount of at least one element selected from the group consisting of Pd, Pt and Au in total of at least 0.1 atomic% and at most 10.0 atomic% of Ti, Cu, Sn, Mg, In, Sb, Al, Zn, By weight based on the total weight of the Ag alloy film. 4. The method according to any one of claims 1 to 3,
Wherein the Ag alloy film has a film thickness of 20 nm or less. A laminated film characterized by comprising the Ag alloy film according to any one of claims 1 to 4 and a conductive oxide film formed on one or both surfaces of the Ag alloy film. 0.1 atom% or more and 5.0 atom% or less of Ti, 0.1 atom% or more in total of at least one element selected from Cu, Sn, Mg, In, Sb, Al, Zn, And the balance of Ag and inevitable impurities, and the total content of Na, Si, V, Cr, Fe, and Co is 100 mass ppm or less. The method according to claim 6,
Wherein an atomic ratio A / B of a content A of Ti and a total content B of Cu, Sn, Mg, In, Sb, Al, Zn, Ge and Ga is in a range of 0.1 to 6.0. target. 8. The method according to claim 6 or 7,
In addition, the total amount of at least one element selected from the group consisting of Pd, Pt and Au in total of at least 0.1 atomic% and at most 10.0 atomic% of Ti, Cu, Sn, Mg, In, Sb, Al, Zn, By weight based on the total weight of the Ag alloy sputtering target. 9. The method 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. 10. The method according to any one of claims 6 to 9,
A polycrystalline body comprising a plurality of Ag alloy crystals, wherein a particle diameter of the Ag alloy crystal is measured at a plurality of points, and the average crystal grain diameter C, which is an average value of the particle diameters of all the Ag alloy crystals measured, (D _max - C) / C × (D _max ) of the Ag alloy grain diameter defined by the average value D _max in which the absolute value of the deviation of the average crystal grain diameter C becomes the largest among the average grain size D of the Ag alloy crystal 100 is 20% or less. 11. The method of claim 10,
Wherein the average grain diameter C is 200 占 퐉 or less. A method of manufacturing an Ag alloy film, wherein sputtering is performed using the Ag alloy sputtering target according to any one of claims 6 to 11. 13. The method of claim 12,
Wherein the sputtering is carried out in a gas atmosphere containing oxygen in an amount of 0.5 to 5% of the total pressure of the inert gas.