JP2013077547A - Conductive film and manufacturing method thereof, and silver alloy sputtering target for conductive film formation and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive film which has characteristics of low resistance and high reflectance, reduces surface roughness and is provided with both high sulfuration resistance and chloridation resistance, and a manufacturing method thereof.SOLUTION: A conductive film is comprised of a silver alloy having a component composition containing one or two of In and Sn in 0.1 to 1.5 atom% in total, containing Sb in 0.1 to 1.5 atom%, containing one or two of Ga and Mg in 0.5 to 3 atom% in total, and containing the remainder comprised of Ag and inevitable impurities. The conductive film is appropriate as a reflection electrode film for an organic EL element in which a transparent conductive film of an organic EL element is laminated on a surface thereof and an electric field light-emitting layer including an organic EL layer is further laminated thereon.

Description

  The present invention relates to a conductive film suitable for a reflective electrode film of an organic electroluminescence (EL) element, a wiring film of a touch panel, a manufacturing method thereof, a silver alloy sputtering target for forming a conductive film, and a manufacturing method thereof.

  In general, in an organic EL display device, an anode (anode) and a cathode (cathode) are arranged on both sides of an electroluminescent layer including an organic EL layer on a TFT active matrix substrate on which TFTs (thin film transistors) as switching elements are arranged. The organic EL element thus formed is formed in each pixel region.

  There are two types of light extraction methods for organic EL elements: a bottom emission method that extracts light from the transparent substrate side, and a top emission method that extracts light from the opposite side of the substrate. A top emission method with a high aperture ratio provides high brightness. It is advantageous to make. Conventionally, in a top emission type organic EL element, a reflective electrode film of Al or Al alloy or Ag or Ag alloy is used as an anode metal film, and an ITO film is interposed between the reflective electrode film and the electroluminescent layer. A transparent conductive film such as (Indium Tin Oxide: Indium Tin Oxide) or AZO (Aluminum doped Zinc Oxide) is provided (see Patent Document 1). This transparent conductive film is provided for injecting holes into the organic EL layer because of its high work function.

Here, the reflective electrode film desirably has a high reflectance in order to efficiently reflect the light emitted from the organic EL layer. It is also desirable that the electrode has a low resistance. As such a material, an Ag alloy and an Al alloy are known. However, in order to obtain an organic EL element with higher luminance, the Ag alloy is excellent because of its high visible light reflectance.
Here, a sputtering method is employed for forming the reflective electrode film on the organic EL element, and a silver alloy sputtering target is used (see Patent Document 2).

  In addition to the reflective electrode film for organic EL elements, an Ag alloy film has been studied for conductive films such as lead wires for touch panels. As such a wiring film, for example, when pure Ag is used, migration occurs and a short circuit failure is likely to occur. Therefore, adoption of an Ag alloy film has been studied.

JP 2006-236839 A International Publication No. 2002/077317

However, the following problems remain in the above-described conventional technology.
The Ag alloy film used as the anode of the organic EL element is required to have low resistance and high reflectance characteristics as a reflective electrode, and in order to ensure the soundness of the transparent conductive film formed in the upper layer, the surface roughness Is required to be small. That is, when the surface roughness of the Ag alloy film is large, defects are generated in the electroluminescent layer including the upper transparent conductive film and further the organic EL layer formed in a later step due to the unevenness of the Ag alloy film. As a result, the production yield of the organic EL panel is lowered. Further, the sulfur content contained in the process atmosphere sulfidizes the Ag alloy film, and the sulfidized region becomes a defect, which also causes a decrease in yield.
Thus, conventionally, it has been impossible to obtain an Ag alloy film having sufficiently low resistance and high reflectivity, and having a small surface roughness and high sulfidation resistance.
In addition, the organic EL panel is often used as a mobile display in combination with a touch panel such as a smartphone, and is likely to be affected by chlorine components such as sweat from the human body in addition to chlorine components from the environment. For this reason, the tolerance with respect to chlorine is calculated | required, and this is the same also about the reflective electrode film which uses Ag alloy which is a component of an organic electroluminescent panel.
Furthermore, low resistance, smoothness and environmental resistance (sulfuration resistance, chlorination resistance) are also required when an Ag alloy is used as the lead-out wiring for the touch panel, but as described above, the touch panel is close to the human body. Since it is used, chlorination resistance is particularly important.

  The present invention has been made in view of the above-described problems, and has a low resistance and high reflectance characteristics, a small surface roughness, a high sulfidation resistance and a high chlorination resistance, a method for manufacturing the same, and a conductive film. An object of the present invention is to provide a silver alloy sputtering target for forming a conductive film and a method for producing the same.

  As a result of earnest research on the conductive film of the Ag alloy, the present inventors have added one or two kinds of In and Sn, Sb, Ga, and Mg to an appropriate amount of Ag. It has been found that sulfidation resistance and chlorination resistance can be improved.

Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems.
The conductive film according to the first invention contains one or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, Furthermore, one or two of Ga and Mg are contained in a total of 0.5 to 3 atomic%, and the balance is composed of a silver alloy having a component composition composed of Ag and inevitable impurities. To do.
This conductive film contains one or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, and further contains Ga and Mg. One or two of them are contained in a total of 0.5 to 3 atomic%, and the balance is composed of a silver alloy having a component composition composed of Ag and inevitable impurities, so that it has low resistance and high reflectance. While having the characteristics, one or two of In and Sn contained, and Sb have a small surface roughness and high sulfidation resistance, and Ga or Mg has high chlorination resistance.

Here, the reason for limiting the content ratio of the metal component element in the sputtering target of the present invention as described above is as follows.
In and Sn:
In and Sn are added because they have the effect of reducing the surface roughness and increasing the resistance to sulfidation. However, if the amount is less than 0.1 atomic%, this effect is not sufficient, while one of In and Sn is added. Alternatively, if the total content of the two types exceeds 1.5 atomic%, the reflectance decreases, which is not preferable. Therefore, the total content of one or two of In and Sn in the total metal component elements contained in the sputtering target of the present invention is set to 0.1 to 1.5 atomic%.
Sb:
Sb has an extremely large effect of reducing the surface roughness, and has a lower degree of lowering the reflectance and specific resistance than In and Sn. If Sb is less than 0.1 atomic%, the effect of reducing the surface roughness is reduced. On the other hand, if Sb is contained in excess of 1.5 atomic%, the reflectivity decreases. It is not preferable. Therefore, the content ratio of Sb in all the metal component elements contained in the sputtering target of the present invention is set to Sb: 0.1 to 1.5 atomic%.
One or two of Ga and Mg:
Ga or Mg is added because it has an effect of improving the chlorination resistance. However, if one or two of Ga and Mg are less than 0.5 atomic% in total, this effect is not sufficient. If the content exceeds 3 atomic%, the specific resistance increases and the reflectance decreases, which is not preferable. Therefore, the total content ratio of one or two of Ga and Mg in all metal component elements contained in the sputtering target of the present invention is set to 0.5 to 3 atomic%.

A conductive film according to a second invention is for the organic EL element according to the first invention, wherein a transparent conductive film of an organic EL element is laminated on the surface, and an electroluminescent layer including an organic EL layer is further laminated thereon. It is characterized by being a reflective electrode film.
That is, in this conductive film, since the transparent conductive film of the organic EL element is laminated on the surface, the soundness of the upper transparent conductive film is ensured by the small surface roughness, and further, the organic EL layer is further formed thereon. Defects can be prevented from occurring. In addition, generation of defects due to sulfurization of the reflective electrode film can be suppressed, yield reduction can be prevented, and the influence of chlorine is hardly affected.

A method for producing a conductive film according to a third invention is a method for producing a conductive film according to the first or second invention, wherein one or two of In and Sn are combined: 0.1 -1.5 atomic%, Sb: 0.1-1.5 atomic%, and further containing one or two of Ga and Mg in a total of 0.5-3 atomic%, the balance being The film formation is performed by sputtering using a sputtering target composed of a silver alloy having a component composition composed of Ag and inevitable impurities.
That is, in this method for producing a conductive film, sputtering is performed using a silver alloy sputtering target having the same composition as that of the conductive film of the present invention, so that the conductive film has a small surface roughness and high sulfidation resistance and chlorination resistance. A stable membrane can be obtained.

In the silver alloy sputtering target for forming a conductive film according to the fourth invention, one or two of In and Sn are added in total: 0.1 to 1.5 atom%, Sb: 0.1 to 1.5 atom. Further, it is composed of a silver alloy having a component composition composed of Ag and inevitable impurities, with a total of 0.5 to 3 atomic percent of one or two of Ga and Mg. It is characterized by being.
That is, by sputtering using this silver alloy sputtering target for forming a conductive film, a conductive film having a low electrical resistance and a small surface roughness and having a high sulfidation resistance and chlorination resistance can be stabilized. Can be obtained.

A method for producing a silver alloy sputtering target for forming a conductive film according to a fifth invention is a method for producing a silver alloy sputtering target for forming a conductive film according to the fourth invention, wherein one of In and Sn or 2 types in total: 0.1 to 1.5 atom%, Sb: 0.1 to 1.5 atom%, and further one or two of Ga and Mg in total 0.5 to 3 It is characterized in that a step of rolling and a step of machining are performed in this order on a melt-cast ingot containing an atomic% and the balance being composed of Ag and inevitable impurities.
That is, in this method for producing a silver alloy sputtering target for forming a conductive film, one or two of In and Sn are added in total: 0.1 to 1.5 atom%, Sb: 0.1 to 1.5 atom. A molten casting ingot containing 0.5% to 3 atomic% in total of one or two of Ga and Mg, with the balance being composed of Ag and inevitable impurities. The sputtering target of the present invention can be obtained by performing the process of machining and the process of machining in this order.

The present invention has the following effects.
According to the conductive film and the manufacturing method thereof of the present invention, the film contains one or two of In and Sn in the above content range, Sb, and one or two of Ga and Mg. In addition, since the balance is composed of a silver alloy having a component composition composed of Ag and inevitable impurities, it has a low surface resistance and a high reflectivity, while having a small surface roughness, high sulfidation resistance and chlorination resistance. Can be combined. Moreover, the electroconductive film of the said characteristic can be stably obtained by sputtering using the silver alloy sputtering target for electroconductive film formation of this invention.
Therefore, by adopting the conductive film of the present invention as a reflective electrode film of the organic EL element, it is possible to suppress the occurrence of defects caused by defects or sulfidation in the transparent conductive film and the organic EL layer caused by unevenness, and the production of organic EL panels. Yield can be improved. Moreover, it is difficult to be influenced by the chlorine component, and good film characteristics can be maintained.
Furthermore, by adopting the conductive film of the present invention as a lead-out wiring for the touch panel, it is possible to obtain a low resistance and sufficient smoothness and good environmental resistance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing a layer structure of an organic EL element in one embodiment of a conductive film and a manufacturing method thereof, a silver alloy sputtering target for forming a conductive film and a manufacturing method thereof according to the present invention.

  Hereinafter, an embodiment of a conductive film and a manufacturing method thereof, a silver alloy sputtering target for forming a conductive film and a manufacturing method thereof according to the present invention will be described with reference to FIG.

The conductive film of the present embodiment contains one or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, Ga, One or two of Mg is contained in a total of 0.5 to 3 atomic%, and the balance is made of a silver alloy having a component composition composed of Ag and inevitable impurities.
For example, as shown in FIG. 1, the conductive film 1 has an organic EL element in which a transparent conductive film 2 of an organic EL element 10 is laminated on the surface, and an electroluminescent layer 3 including an organic EL layer 3b is further laminated thereon. It is a reflective electrode film for elements.

  That is, an organic EL element 10 provided with the conductive film 1 includes an anode 5 formed on a film formation substrate 4, an electroluminescent layer 3 including an organic EL layer 3 b formed on the anode 5, An organic EL device including a cathode 6 formed on an electroluminescent layer 3, wherein an anode 5 is formed between the conductive film 1 and the conductive film 1 and the electroluminescent layer 3. And a transparent conductive film 2.

For example, in the case where an organic EL element is formed on a TFT substrate, the film formation substrate 4 is a glass substrate or a heat resistant resin on which a plurality of insulating films such as a SiN film and a SiO ₂ film serving as a gate insulating film are stacked. An insulating substrate such as a substrate is used.
For example, the electroluminescent layer 3 has a thickness of 100 to 200 nm, the transparent conductive film 2 has a thickness of 10 to 20 nm, and the conductive film 1 has a thickness of 100 nm.
The electroluminescent layer 3 has a three-layer structure in which a hole (hole) transport layer 3a, an organic EL layer 3b, and an electron transport layer 3c are laminated on the anode 5 in this order.

As the organic polymer material (hole injection / transport material) constituting the hole transport layer 3a, it has the ability to transport holes, the hole injection effect from the anode 5, the organic EL layer 3b or the light emitting material. On the other hand, a compound that has an excellent hole injection effect, prevents exciton generated in the organic EL layer 3b from moving to the electron transport layer 3c, and has excellent thin film forming ability is preferable.
Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyaryl Alkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, polyvinylcarbazole, polymers such as polysilane, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), polymer materials such as polyaniline / camphorsulfonic acid (PANI / CSA) and other conductive polymers And the like.

Examples of the light emitting material used for the organic EL layer 3b include olefin-based light emitting materials such as 4,4 ′-(2,2-diphenylvinyl) biphenyl, 9,10-di (2-naphthyl) anthracene, and 9,10−. Bis (3,5-diphenylphenyl) anthracene, 9,10-bis (9,9-dimethylfluorenyl) anthracene, 9,10- (4- (2,2-diphenylvinyl) phenyl) anthracene, 9,10 '-Bis (2-biphenylyl) -9,9'-bisanthracene, 9,10,9', 10'-tetraphenyl-2,2'-bianthryl, 1,4-bis (9-phenyl-10-anthracenyl) ) Anthracene-based luminescent materials such as benzene, spiro-based luminescent materials such as 2,7,2 ′, 7′-tetrakis (2,2-diphenylvinyl) spirobifluorene, 4,4′-dica Carbazole-based light-emitting materials such as bazolylbiphenyl and 1,3-dicarbazolylbenzene, low-molecular light-emitting materials typified by pyrene-based light-emitting materials such as 1,3,5-tripyrenylbenzene, polyphenylene vinylenes, Examples thereof include polymer light-emitting materials such as polyfluorenes and polyvinylcarbazoles.
The organic EL layer 3b may be doped with a fluorescent dye or a phosphorescent dye.

The electron injecting / transporting material used for the electron transporting layer 3c has the ability to transport electrons, has an electron injecting effect from the cathode 6, and has an excellent electron injecting effect with respect to the organic EL layer 3b or the light emitting material. A compound that prevents the excitons generated in the EL layer 3b from moving to the hole injection layer and has an excellent thin film forming ability is preferable. Specifically, for example, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone and the like And derivatives thereof.
The transparent conductive film 2 is made of ITO or AZO.

  The conductive film 1 of the present embodiment contains one or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, and Ga. Sputtering is performed using a sputtering target composed of a silver alloy containing one or two of Mg and 0.5 to 3 atomic% in total, with the balance being composed of Ag and inevitable impurities. To form a film. For example, the conductive film 1 is manufactured by the following steps.

  First, as a raw material, Ag having a purity of 99.9% by mass or more, one or two of In and Sn having a purity of 99.9% by mass or more, and one or two of Sb, Ga, and Mg are used. Weigh so that a predetermined composition is obtained. Next, Ag is melted in a high vacuum or an inert gas atmosphere, and one or two of In and Sn having a predetermined content and one or two of Sb, Ga, and Mg are added to the obtained molten metal. Add seeds. Then, it melt | dissolves in a vacuum or inert gas atmosphere, 1 type or 2 types in In and Sn are total: 0.1-1.5 atomic%, Sb: 0.1-1.5 atomic% In addition, a molten cast ingot of a silver alloy having a composition of 0.5 to 3 atomic% in total of one or two of Ga and Mg, the balance being composed of Ag and inevitable impurities is produced. To do.

  Here, Ag is melted in an atmosphere in which the atmosphere is once evacuated and then replaced with Ar, and after melting, in the Ar atmosphere, one or two of In and Sn, Sb and Ga are added to the molten Ag. Addition of one or two of Mg, stable composition ratio of one or two of Ag, In, and Sn and one or two of Sb, Ga, and Mg From the viewpoint of obtaining. Further, one or two of In and Sn and one or two of Sb, Ga and Mg are added in the form of a master alloy such as AgIn, AgSn, AgSb, AgMg and AgGa prepared in advance. Also good.

After the obtained ingot is cold-rolled, it is subjected to a heat treatment at 600 ° C. for 2 hours in the atmosphere, and then machined to produce a sputtering target having a predetermined dimension.
This sputtering target is soldered to a backing plate made of oxygen-free copper, and this is attached to a DC magnetron sputtering apparatus.

Next, after the inside of the DC magnetron sputtering apparatus is evacuated to, for example, 5 × 10 ⁻⁵ Pa or less with a vacuum evacuation apparatus, Ar gas is introduced to obtain a predetermined sputtering gas pressure. Apply DC sputtering power. Furthermore, the conductive film 1 is formed on the film formation substrate 4 by generating plasma between the film formation substrate 4 facing the target and provided in parallel with the target at a predetermined interval. Form a film.

  In the conductive film 1 of the present embodiment formed in this way, one or two of In and Sn are combined: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 It is composed of a silver alloy containing atomic percent, further containing one or two of Ga and Mg in a total amount of 0.5 to 3 atomic percent, with the balance being composed of Ag and inevitable impurities. Therefore, while having low resistance and high reflectance characteristics, it contains small surface roughness and high sulfidation resistance due to the contained In, Sn and Sb, and also has high chlorination resistance due to Ga or Mg. ing.

  In particular, since the transparent conductive film 2 of the organic EL element 10 is laminated on the surface, the soundness of the upper transparent conductive film 2 is ensured by the small surface roughness of the conductive film 1, and further the organic film thereon It is possible to prevent a defect from occurring in the EL layer 3b. Moreover, generation | occurrence | production of the defect by sulfuration of a reflective electrode film (conductive film 1) can be suppressed, and a yield fall can be prevented. Furthermore, it is difficult to be influenced by the chlorine component, and good film characteristics can be maintained.

The result evaluated about the Example of the electroconductive film formed into a film based on the said embodiment is demonstrated below.
First, in order to produce a sputtering target for a conductive film, as raw materials, Ag having a purity of 99.9% by mass or more and In, Sn, Sb, Ga, Mg having a purity of 99.9% by mass or more are shown in Table 1. It weighed so that it might become the predetermined composition shown. Next, Ag was melted in a high vacuum or an inert gas atmosphere, and a predetermined content of In, Sn, Sb, Ga, Mg was added to the resulting molten metal. Then, it melt | dissolves in a vacuum or inert gas atmosphere, 1 type or 2 types in In and Sn are total: 0.1-1.5 atomic%, Sb: 0.1-1.5 atomic% In addition, a molten cast ingot of a silver alloy having a composition of 0.5 to 3 atomic% in total of one or two of Ga and Mg, the balance being composed of Ag and inevitable impurities is produced. did.

Here, Ag is melted in an atmosphere in which the atmosphere is once evacuated and then replaced with Ar, and after melting, in the Ar atmosphere, one or two of In and Sn, Sb and Ga are added to the molten Ag. 1 or 2 of Mg was added.
The obtained ingot was cold-rolled, then subjected to heat treatment at 600 ° C. for 2 hours in the atmosphere, and then machined to have dimensions of 152.4 mm in diameter and 6 mm in thickness, as shown in Table 1. Inventive Example Sputtering Targets 1 to 26 were produced.
This sputtering target was soldered to an oxygen-free copper backing plate, and this was attached to a DC magnetron sputtering apparatus.

Next, after the inside of the DC magnetron sputtering apparatus is evacuated to 5 × 10 ⁻⁵ Pa or less with a vacuum evacuation apparatus, Ar gas is introduced to a sputtering gas pressure of 0.5 Pa, and then 250 W is applied to the target with a DC power supply. A direct current sputtering power was applied. Furthermore, by generating a plasma between the Si wafer substrate with an oxide film having a diameter of 4 inches (10.16 cm) disposed opposite to the target and parallel to the target with a distance of 70 mm, the plasma is generated. A conductive film was formed on a Si wafer substrate with an oxide film.

Thus, as an example of the conductive film of the present invention, the conductive film of Examples 1 to 26 having the component composition shown in Table 1 was formed by the above manufacturing method. Two types of samples having a thickness of 1000 nm were prepared. In addition, the Example number of Table 1 shows both a sputtering target and the electroconductive film | membrane formed into a film by this, and is the mutually same component composition.
Moreover, as a comparative example, comparative example sputtering targets 1 to 9 having the component compositions shown in Table 1 were similarly produced. And as a comparative example of the conductive film formed using the targets of these comparative examples, those having a component composition containing In, Sn, Sb, Mg, Ga exceeding the content range of the present invention (Comparative Examples 1 to 9) The other conditions were the same as in the examples of the present invention, and a film was formed with the component composition shown in Table 1.
In addition, the component composition of each Example and each Comparative Example in the conductive film was confirmed by measuring the composition of a sample having a film thickness of 1000 nm using an electron beam microprobe analyzer (EPMA).

<Evaluation of conductive film>
The specific resistance of the conductive film of each example and each comparative example was measured by a four-probe method for a sample having a thickness of 100 nm. Next, the surface roughness (Ra) of the conductive films of each Example and each Comparative Example was measured by an atomic force microscope (AFM). In addition, the measurement of Ra was also performed after performing heat treatment for 10 minutes at a temperature of 250 ° C. in a nitrogen atmosphere.

Moreover, the reflectance in wavelength 550nm of the electroconductive film of each Example and each comparative example was measured with the spectrophotometer. Next, after immersing this sample in a 0.01 wt% Na ₂ S aqueous solution for 1 hour, the reflectance at a wavelength of 550 nm of each conductive film was again measured with a spectrophotometer to obtain a sulfur resistance index.

  Further, the evaluation of chloride resistance was performed according to the following procedure. First, an Ag alloy film having a thickness of 100 nm was formed on a glass substrate (30 mm × 30 mm × thickness: 1.1 mm) under the same conditions as described above. Next, a 5 wt% NaCl aqueous solution was sprayed on the film surface of the formed Ag alloy film. Spraying was performed in a direction parallel to the film surface from a position of 20 cm in height from the film surface and a distance of 10 cm from the edge of the substrate, so that the NaCl aqueous solution sprayed on the film fell as freely as possible and adhered to the film. After spraying 5 times every minute, rinsing with pure water was repeated 3 times, and dry air was sprayed to blow off moisture and dry. The surface of the Ag alloy film was visually observed after the above salt water spraying, and the surface condition was evaluated in two stages.

These results are shown in Table 1.
Note that the evaluation criteria for determining good are specific resistance of less than 9 μΩ · cm, surface roughness Ra immediately after film formation is less than 0.8 nm, surface roughness Ra after heat treatment is less than 0.8 nm, and film formation immediately after film formation. The reflectivity at a wavelength of 550 nm exceeds 94%, and the reflectivity at a wavelength of 550 nm after immersion in a Na ₂ S aqueous solution exceeds 55%.
In addition, as an evaluation standard for chloride resistance, white turbidity or spots can not be confirmed or can be confirmed only partly as good `` ○ '', and white turbidity or spots can be confirmed on the entire surface as bad `` x '', The surface condition was evaluated in two stages.

  As can be seen from Table 1, in Comparative Example 1 and Comparative Example 7 in which the total content of one or two of In and Sn is less than the range of the present invention, the sulfidation resistance is low, and among In and Sn In Comparative Example 2, Comparative Example 8, and Comparative Example 9 in which the total content of one or two types is larger than the range of the present invention, the reflectance is low. Also. In Comparative Example 3 in which the Sb content is less than the range of the present invention, the surface roughness immediately after film formation and after heat treatment is large and the flatness is low, and in Comparative Example 4 in which the Sb content is greater than the range of the present invention. Low reflectivity. Further, in Comparative Example 5 in which the total content of Ga and Mg is less than the range of the present invention, the resistance to chlorination is low, and in Comparative Example 6 in which the total content of Ga and Mg is greater than the range of the present invention, the specific resistance is Is high and reflectivity is low. Therefore, these comparative examples are insufficient as a reflective electrode film.

On the other hand, each of Examples 1 to 26 of the present invention has a low specific resistance and is suitable as an electrode film, and the surface roughness is small and high flatness both immediately after film formation and after heat treatment. Yes. In these examples, both high reflectance and good chlorination resistance are obtained both immediately after film formation and after immersion in an aqueous Na ₂ S solution.
Therefore, the examples of the present invention have specific resistance, surface roughness, reflectivity, sulfidation resistance and chlorination resistance suitable as a reflective electrode film of an organic EL element.

The technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.
For example, in the above-described embodiment, the conductive film of the present invention is employed as the reflective electrode film of the organic EL element. However, the conductive film of the present invention has a low specific resistance and a small surface roughness, which is even better. Since it has environmental resistance (sulfuration resistance, chlorination resistance), it is also suitable as a wiring film of a touch panel.

  DESCRIPTION OF SYMBOLS 1 ... Conductive film, 2 ... Transparent conductive film, 3 ... Electroluminescent layer, 4 ... Film-forming substrate, 5 ... Anode, 6 ... Cathode, 10 ... Organic EL element

Claims (5)

  One or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, and one or two of Ga and Mg A conductive film comprising a total of 0.5 to 3 atomic percent of seeds, the balance being composed of a silver alloy having a component composition composed of Ag and inevitable impurities. The conductive film according to claim 1,
A conductive film, which is a reflective electrode film for an organic EL element, wherein a transparent conductive film of an organic EL element is laminated on a surface, and an electroluminescent layer including an organic EL layer is further laminated thereon. A method for producing the conductive film according to claim 1, wherein:
One or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, and one or two of Ga and Mg It is characterized in that the film is formed by sputtering using a sputtering target composed of a silver alloy having a total of 0.5 to 3 atomic% of seeds and the balance being composed of Ag and inevitable impurities. A method for producing a conductive film.   One or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, and one or two of Ga and Mg A silver alloy sputtering target for forming a conductive film, comprising a total of 0.5 to 3 atomic percent of seeds, the balance being composed of a silver alloy having a component composition composed of Ag and inevitable impurities. A method for producing a silver alloy sputtering target for forming a conductive film according to claim 4,
One or two of In and Sn in total: 0.1 to 1.5 atomic%, Sb: 0.1 to 1.5 atomic%, and one or two of Ga and Mg It is characterized in that a step of rolling and a step of machining a melt-cast ingot containing a total of 0.5 to 3 atomic% of seeds and having a component composition consisting of Ag and inevitable impurities in this order are performed in this order. A method for producing a silver alloy sputtering target for forming a conductive film.

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