TW201426831A - Electrode used in display device or input device, and sputtering target for use in electrode formation - Google Patents

Abstract

This electrode for use in a display device or input device has a laminate film which includes a first layer formed on the substrate side and containing an Al alloy, and a second layer formed on top of the first layer and containing an Ag alloy. The electrode film thickness is 100-800nm, the second layer thickness is 60-480nm, the proportion of the second layer thickness to the electrode film thickness is 10-70%, and the proportion of the first layer thickness to the electrode film thickness is 30% or greater. The Al alloy contains a prescribed amount of a prescribed alloy element.

Description

Electrode for display device or input device, and sputtering target for electrode formation

The present invention relates to an electrode of a display device or an input device, and a sputtering target for electrode formation. More specifically, the present invention relates to an electrode for an input device such as a display device such as a liquid crystal display or an organic EL display, a touch panel, or the like, and a sputtering target for forming the electrode.

The Ag alloy is mainly used as an electrode material. Examples of the electrode include a gate for a thin film transistor in a liquid crystal display (LDC), a source drain, a gate for a thin film transistor in an organic EL (OELD), a source drain, a reflective electrode, and a field. The cathode and gate in the emission display (FED), the anode in the fluorescent vacuum tube (VFD), the address electrode in the plasma display (PDP), the back electrode in the inorganic EL, and the like. Further, the Ag alloy is also used as an electrode in an input device having a display function such as a touch panel or the like in a display device such as a liquid crystal display or an organic EL, and an input device independent of a display device such as a touch panel.

Hereinafter, the display device is typically an organic electroluminescence which is one of the light-emitting flat panel displays (hereinafter, described as The "organic EL" display is for illustrative purposes, and is not limited to this.

The organic EL display is an all-solid-state flat panel display in which organic EL elements are arranged in a matrix on a substrate such as a glass plate. In an organic EL display, an anode and a cathode are formed in a stripe shape, and a portion where the intersection thereof corresponds to a pixel (organic EL element). The organic EL element applies a voltage of several V from the outside to cause a current to flow, and the organic molecule is promoted to an excited state, and the energy generated when the excited organic molecule returns to the original ground state (steady state) is emitted in the form of light. . This luminescent color is unique to organic materials.

The organic EL element is a self-luminous type and a current-driven type, and the driving method is passive or active. Although passive, the structure is simple, but it is difficult to fully color. On the other hand, although the active type can be enlarged, it is also suitable for full color, but a TFT substrate is required. As the TFT substrate, a TFT such as low-temperature polycrystalline Si (p-Si) or amorphous Si (a-Si) is used.

In the case of an active organic EL display, a plurality of TFTs and wirings become obstacles, and the area for organic EL pixels can be made small. If the driving circuit becomes complicated, the TFT increases, and the influence is greatly changed. Therefore, recently, the light is not taken out from the glass substrate, but the method of extracting light from the upper side (top emission) to improve the aperture ratio is focused.

In such an active top-emitting organic EL display, an anode (anode) under the organic layer (on the TFT substrate side) is implanted with a good hole injecting ITO (indium tin oxide) and IZO (indium zinc oxide). A transparent oxide conductive film. Further, at the same time as the purpose of reflecting the light radiated from the light-emitting layer, the anode adopts the above transparent oxide conductive film A laminated structure with a reflective film. As the reflective film, a reflective metal film such as molybdenum (Mo), chromium (Cr), aluminum (Al), or silver (Ag) is often used. For example, in the case of a reflective anode in an organic EL display of a mass-produced top emission type, a laminated structure of ITO and an Ag alloy film containing a pure Ag film or Ag as a main body is used.

A pure Ag film or an Ag alloy film is useful because of its high reflectance. However, since the pure Ag or Ag alloy film has a high etching rate at the time of wet etching, there is a problem in the pick-up etching characteristics. For example, the Ag alloy film is etched by a wet etching solution such as phosphoric acid or the like, and it is difficult to perform micromachining particularly in a large-area substrate. In particular, when the side etching of the isotropically etched Ag alloy film is increased, there is a problem in etching accuracy such as unevenness of the formed side surface, and it is difficult to perform micromachining with good dimensional accuracy. Therefore, since the Ag alloy film is difficult to process with a desired dimensional accuracy and shape, it is a cause of poor light emission, light leakage, and electrical contact failure, and the reliability of the display device itself such as an organic EL display is lowered.

Further, the adhesion between the pure Ag film or the Ag alloy film and the underlayer (for example, a substrate, an insulating film, a planarization layer, etc.) is insufficient, and there is a problem in that the product is peeled off from the underlayer during the production process and at the time of use, and the reliability of the product is low. In addition, in order to suppress the wiring resistance, it is preferable to increase the film thickness of the Ag alloy film by a high-valence noble metal of Ag, and it is practically insufficient to increase the amount of Ag used from the viewpoint of production cost.

As a technique for solving such a problem, Patent Document 1 controls the size of an anode made of an Ag alloy as high precision and The following is an organic EL device comprising: an adhesive layer comprising an anode made of Al; and a reflective layer provided on the upper surface of the adhesive layer and made of an Ag alloy, wherein an end surface of the reflective layer and an end surface of the adhesive layer are continuous, The thickness of the reflective layer is 50 nm or more and 80 nm or less.

In the technique of Patent Document 1, the Ag alloy film is laminated with another metal film, and the amount of Ag used can be reduced while improving the adhesion of the Ag alloy film.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-113758

The present invention has been made in view of the above circumstances, and an object thereof is to provide an electrode for a display device or an input device having a good electrical resistivity, and a high-precision micromachining in the case of an Ag alloy single-layer film. It is easy and has a high reflectance in the same grade as the Ag alloy film (single layer).

Further, it is an object of the invention to provide an electrode for a display device or an input device which has good electrical conductivity (low wiring resistance) and high reflectance.

In addition, an object of the present invention is to provide an electrode for a display device or an input device, which has good adhesion to an underlying layer (for example, a substrate, an insulating film, a planarization layer, etc.), and has wiring resistance and Good reflectivity.

According to a first aspect of the invention, there is provided an electrode for a display device or an input device, wherein the electrode is mainly provided with a laminated film, comprising a first layer containing an Al alloy formed on a substrate side, and a first layer formed on the substrate In the second layer containing the Ag alloy, the film thickness of the electrode is 100 nm or more and 800 nm or less, and the thickness of the second layer is 60 nm or more and 480 nm or less, and the film thickness of the electrode is the same as the above-mentioned The film thickness ratio of the two layers is 10% or more and 70% or less, and the film thickness ratio of the first layer in the film thickness of the electrode is 30% or more, and the Al alloy contains, as an alloy element, the following composition. At least one selected from the group: (1-A) the rare earth element is 0.05 atom% or more and 1.0 atom% or less, and (1-B) is selected from the group consisting of Si, Cu, and Ge. At least one of 0.5 atom% or more and 1.5 atom% or less, and (1-C) at least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 atom% or more and 0.7 atom% or less. .

The Ag alloy preferably contains Ag at 98 atom% or more and 99.98 atom% or less.

The Ag alloy as an alloying element preferably contains the following At least one selected from the group consisting of: (2-A) having a rare earth element of 0.05 atom% or more and 1.0 atom% or less, and (2-B) making Bi and/or Cu 0.05 atom% or more and 1.0 atom. % or less, (2-C): at least one selected from the group consisting of Pd, Pt, and Au is 0.1 atom% or more and 1.5 atom% or less, and (2-D) is Zn and/or In 0.1 atom% or more and 1.5 atom% or less.

The rare earth element of the above (1-A) or the above (2-A) is preferably at least one selected from the group consisting of Nd, La, Gd, and Ce.

Further, the second invention which solves the above problems is an electrode, and an important point is that the electrode has a third layer containing an oxide of an Al alloy or a nitride of an Al alloy between the first layer and the second layer, the first layer The film thickness of the three layers is 1 nm or more and 10 nm or less.

The Al alloy of the third layer preferably contains, as an alloying element, (3-A) a rare earth element of 0.05 atom% or more and 1.0 atom% or less, or (3-B) from Ti, Ta, W, and Nb. At least one selected from the group consisting of is 0.05 atom% or more and 0.7 atom% or less.

Further, a third invention which solves the above problems is an electrode, and it is important that the electrode has a gap between the first layer and the second layer. There is a fourth layer containing a conductive oxide, the conductive oxide comprising: (a) at least one selected from the group consisting of Mo, Mo alloy, Ti, Ti alloy, Ta, W, and Nb. Or (b) at least one of an In oxide and a Zn oxide, wherein the fourth layer has a film thickness of 3 nm or more and 50 nm or less.

Further, the conductive oxide of the fourth layer is preferably ITO (indium tin oxide) or IZO (indium zinc oxide).

Similarly, in the first aspect of the invention, there is provided an Al alloy sputtering target for electrode formation, the sputtering target focusing on at least one selected from the group consisting of: (1-A) to make a rare earth The element is 0.05 atom% or more and 1.0 atom% or less, and (1-B) is at least one selected from the group consisting of Si, Cu, and Ge, and is 0.5 atom% or more and 1.5 atom% or less, and (1) -C) At least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 atom% or more and 0.7 atom% or less.

The rare earth element is preferably selected from at least one selected from the group consisting of Nd, La, Gd, and Ce.

Similarly, in the first aspect of the invention, there is provided an Ag alloy sputtering target for electrode formation, the sputtering target focusing on at least one selected from the group consisting of: (2-A) to make a rare earth The element is 0.05 atom% or more and 1.0 atom% or less, and the (2-B) Cu is 0.05 atom% or more and 1.0 atom% or less, and / or Bi is 0.25 at% or more and 5.0 at% or less, and (2-C) is at least one selected from the group consisting of Pd, Pt, and Au, and is 0.1 atom% or more and 1.5 atom% or less, and 2-D) Zn and/or In is made 0.1 atom% or more and 1.5 atom% or less.

The rare earth element is preferably selected from at least one selected from the group consisting of Nd, La, Gd, and Ce.

The electrode of the first aspect of the invention exhibits an excellent etching by having a laminated film including a first layer (substrate side) composed of an Al alloy and a second layer made of an Ag alloy, and appropriately controlling the film thickness and composition. Features and high reflectivity while exhibiting good resistivity. As a result, in the case of the conventional Ag alloy single-layer film, it is difficult to perform high-precision micromachining in a difficult manner, and it is possible to exhibit a high reflectance equivalent to that of the Ag alloy single layer.

In the electrode of the second aspect of the invention, the third layer including the oxide of the Al alloy or the nitride of the Al alloy is provided between the first layer (substrate side) composed of the Al alloy and the second layer made of the Ag alloy. Since the film thickness is appropriately controlled, it exhibits high reflectance while exhibiting good contact resistance between the first layer and the third layer. As a result, the electrode according to the second aspect of the invention has a high reflectance which is difficult and a good wiring resistance in the case where the conventional Ag alloy single layer film can be provided.

The electrode of the third invention is composed of an Al alloy. A fourth layer containing a conductive oxide between the first layer (substrate side) and the second layer made of an Ag alloy, the conductive oxide containing (a) from Mo, Mo alloy, Ti, Ti alloy, At least one selected from the group consisting of Ta, W, and Nb, or (b) at least one of an In oxide and a Zn oxide, and appropriately controlling the film thickness, thereby having good adhesion and exhibiting High reflectivity and good resistivity. As a result, the electrode according to the third aspect of the invention has characteristics of excellent adhesion, reflectance, and wiring resistance.

Further, according to the first to third inventions, it is possible to provide a sputtering target suitable for the formation of electrodes for a display device or an input device according to the above invention.

1, 21, 31‧‧‧ substrates

2, 32‧‧‧TFT

3, 33‧‧‧ Passivation film

4, 34‧‧‧ flattening layer

5, 35‧‧‧ contact holes

6, 36‧‧‧1st layer (Al alloy film)

7‧‧‧2nd layer (Ag alloy film)

9, 29, 39‧ ‧ organic layers

10, 30, 40‧‧‧ cathode

27‧‧‧Second layer (oxide film or nitride film of Al alloy)

28, 38‧‧‧3rd layer (Ag alloy film)

37‧‧‧Layer 2 (anti-diffusion film)

Fig. 1 is a schematic view showing an example of an organic EL display including the reflective electrode of the first invention.

FIG. 2 is a schematic cross-sectional view showing an example of a liquid crystal display.

FIG. 3 is a schematic cross-sectional view showing an example of an organic EL display. FIG.

Fig. 4 is a schematic cross-sectional view showing an example of a field emission display.

Fig. 5 is a schematic cross-sectional view showing an example of a fluorescent vacuum tube.

Fig. 6 is a schematic cross-sectional view showing an example of a plasma display.

FIG. 7 is a schematic cross-sectional view showing an example of an inorganic EL display. FIG. Figure.

FIG. 8 is a schematic view showing an example of an organic EL display including the reflective electrode of the second invention.

FIG. 9 is a schematic view showing an example of an organic EL display including the reflective electrode of the third invention.

[First Invention]

Hereinafter, the first invention will be described in detail.

The present inventors have made intensive studies in order to solve the above problems. As a result, the inventors of the present invention have found that the first invention is such that the electrode used for the display device or the input device includes the first layer composed of an Al alloy and the Ag alloy formed thereon from the substrate side. The laminated film formed of the second layer (which may be in direct contact with the first layer or not directly in contact with each other) appropriately controls the electrode and the first layer (Al alloy film) and the second layer (which constitute the electrode) The film thickness of the Ag alloy film) and the composition of the first layer (Al alloy) may be used.

The reason for achieving the first invention is as follows. First, the problem of the conventional Ag alloy film (single layer), that is, the problem of poorly etching precision microfabrication when the photoresist is patterned by wet etching of the mask, is known to use an Al film. The laminated structure with the Ag alloy film can be solved by adjusting the etching rate (Patent Document 1). This is because the etching rate of the Al film is slower than the etching rate of the Ag alloy film, and the Al film exhibits an etching rate control function. root According to this technique, if the electrode is a laminated structure of the Ag alloy film and the Al film and the etching rate is adjusted, excessive etching of the Ag alloy film can be suppressed, and the size can be processed with high precision.

However, in recent years, the electrodes of the display device require the refinement of the wiring and the suppression of the opposite characteristics of the resistivity. Further, in addition to the refinement of the wiring and the suppression of the resistivity, the reflective electrode such as an organic EL display requires high reflectance. In the prior art disclosed in Patent Document 1, although the wiring can be etched with high precision, the film thickness of the target anode is as thin as 100 to 300 nm, so it is difficult to suppress the resistivity when the wiring is made fine. In addition, since the Ag alloy film is also as thin as 50 to 80 nm, it is difficult to ensure stable high reflectance. Further, the Al film is useful not only in the above-described etching rate control function but also in adhesion to the lower layer (planar film), but it is difficult to ensure high reflectance because it does not have sufficient reflectance.

Patent Document 1 does not disclose any high-precision micromachining and reflectance in the case of thick film formation, and has a problem of low reflectance and the like in the configuration of Patent Document 1 as will be described later.

As a result of review by the present inventors, it was found that pure Al (or Al oxide and Al intermetallic compound) is used in order to ensure good electrical resistivity and micro-workability while thick film formation is considered while considering the reflectance. It is difficult to use an Al alloy film containing a specific amount of alloying elements. Then, the inventors of the present invention made a reflective electrode having a laminated film of an Al alloy film (substrate side) and an Ag alloy film, and were concerned with reflectance, film thickness, and micromachinability (dimension accuracy at the time of patterning). As a result of the review, the following findings were obtained from Table 1 of the examples described later.

That is, it is understood that when the film thickness of the Ag alloy film is reduced, the reflectance of the Ag alloy film is lowered, and the light reflected by the Al alloy film is increased by the Ag alloy film. It is learned that although the proportion of light reflected by the Al alloy film increases as the transmittance of the Ag alloy film increases, the reflectance of the Al alloy film is lower than that of the Ag alloy film, and the light reflected by the Al alloy film A part of the reflection is not transmitted through the Ag alloy film, so the reflectance of the reflective electrode is lowered (No. 1). On the other hand, it has been found that the reflectance of the reflective electrode is also improved (90% or more) when the film thickness of the Ag alloy film is increased, but high-precision micromachining becomes difficult (No. 12). Further, it has been found that in the laminated film of the Al alloy film and the Ag alloy film, the film thickness ratio of the Al alloy film and the Ag alloy film with respect to the film thickness of the laminated film affects the micro workability. In other words, when the film thickness ratio of the Ag alloy film exceeds 70%, the amount of the Ag alloy film to be etched increases, so that the micro workability is deteriorated (No. 5, 9, and 12). Similarly, when the film thickness ratio of the Al alloy film is less than 30%, the etching rate control function cannot be sufficiently exhibited, and the micro workability is deteriorated (No. 5, 9, and 12). This tendency is irrelevant to the film thickness of the Ag alloy film and occurs when the ratio with respect to the laminated film exceeds 70% (or when the Al alloy film is less than 30%). It is learned from these results that if it is desired to ensure good micromachining and reflectivity, it is necessary to laminate not only the Ag alloy film and the Al alloy film, but also to control the film thickness relative to the laminated film within a predetermined film thickness range. The ratio of the film thickness of the Ag alloy film and the Al alloy film. By appropriately controlling the film thickness in this manner, even if the electrode is thickened (to, for example, the 800 nm level) in order to obtain a good electrical resistivity, good reflectance and micro-workability can be ensured.

Next, the inventors reviewed the influence of the composition of the first layer (Al alloy film) and the second layer (Ag alloy film) constituting the electrode on reflectance, micro-workability, and electrical resistivity. First, when various alloying elements were added to the first layer (Al alloy film) and the relationship with the above characteristics was investigated, it was found that as shown in Table 2, rare earth elements, Si, Cu, Ge, Ti, Ta, W, and Nb is effective for the improvement of micromachinability. Further, in the case where these alloying elements are added, there is a preferable content in terms of the relationship between the reflectance and the specific resistance. That is, the pure Al film (No. 21) which does not contain an alloying element has a good electrical resistivity, but has a low reflectance and cannot satisfy the reflectance required for the reflective electrode. Further, it has been found that even if the alloy element is added, if the content is too large, the electrical resistivity is deteriorated, and the reflectance of the Al alloy film is lowered, and the reflectance of the reflective electrode is also lowered (No. 25, 29, 32).

In addition, when the alloy layer was added to the second layer (Ag alloy film) in the same manner as the first layer (Al alloy film), and the relationship with the above characteristics was investigated, it was found that, as shown in Table 3, the rare earth element and Bi were Cu, Pd, Pt, Au, Zn, and In are effective for improving micromachinity. Further, regarding these alloying elements, there is a preferable content in terms of the relationship between the reflectance and the specific resistance. In other words, it is understood that the pure Ag film (No. 51; the embodiment of the adhesive layer of the patent document 1) in which the alloying element is not added has a low reflectance and cannot satisfy the reflectance required for the reflective electrode, even if the above alloying element is added, once If the content is too large, the resistivity will decrease and the reflectance will decrease (No. 55, 60, 64, 70, 74).

According to the results of these experiments, it is learned that the resistivity is due to thick film formation. The tendency to exhibit is good, and the micro-machining property is enhanced by the addition of specific alloying elements. On the other hand, as a result of experiments by the present inventors, it has been found that the electrical resistivity and the reflectance are deteriorated by the alloying elements added to the first layer (Al alloy film) and the second layer (Ag alloy film), and the content thereof. Therefore, it is necessary to appropriately control the alloying elements and their contents. Then, in the present invention, based on such a result, the alloying elements and their contents are specified as described later.

Further, in terms of the characteristics of the electrode of the present invention, the specific resistance is preferably about 7.0 μΩcm or less, more preferably 5 μΩcm or less.

Hereinafter, an electrode for a display device or an input device of the present invention will be described.

(composition of electrodes)

The electrode used for the display device or the input device is composed of a laminated film comprising a first layer made of an Al alloy formed on the substrate side and a second layer made of an Ag alloy formed thereon.

In the laminated film of the present invention, it is preferable that the first layer (Al alloy film) and the second layer (Ag alloy film) are sequentially laminated in this order from the substrate side.

Further, the laminated film of the present invention is preferably a laminated film composed of the first layer (Al alloy film) and the second layer (Ag alloy film), but is not limited thereto, and may further include any layer (third) Floor). Therefore, an arbitrary third layer may be formed between the first layer (Al alloy film) and the second layer (Ag alloy film). As the third layer, the illustration helps with the first layer Synthetic lifting film.

(film thickness of the electrode)

In the present invention, the thickness of the electrode (layered film) is set to 100 to 800 nm. When the film thickness is less than 100 nm, there is a problem in that the wiring resistance is increased and a stable reflectance or the like is not obtained. On the other hand, when it exceeds 800 nm, the deterioration of the micro-workability and the coverage of the upper film (passivation film or the like) are deteriorated to cause a problem such as a fracture. The film preferably has a film thickness of 120 nm or more, more preferably 150 nm or more, more preferably 700 nm or less, still more preferably 500 nm or less. According to the present invention, even if the electrode is made thick as described above, good electrical resistivity, reflectance, and micro-workability can be exhibited.

(film thickness of the first layer (Al alloy film))

The first layer (Al alloy film) reflects light transmitted through the second layer (Ag alloy film) and serves as a layer of the role of the control layer of the etching rate at the time of wet etching. In order to exert such an effect, the film thickness of the first layer (Al alloy film) is preferably 50 nm or more, and more preferably 100 nm or more. On the other hand, when the film thickness of the first layer (Al alloy film) is too thick, the film thickness of the second layer (Ag alloy film) is too small and the reflectance is lowered in accordance with the film thickness of the electrode. Therefore, the film thickness of the first layer (Al alloy film) is preferably 650 nm or less, and more preferably 450 nm or less.

(film thickness of the second layer (Ag alloy film))

The second layer (Ag alloy film) particularly plays the role of a reflective film in the reflective electrode. In order to secure high reflectance, the film thickness of the second layer needs to be 60 nm or more, preferably 90 nm or more, and more preferably 100 nm or more. On the other hand, when the film thickness of the second layer (Ag alloy film) is too large, the amount of etching during wet etching increases, and a desired wiring width cannot be obtained, and micro workability is deteriorated. Therefore, the film thickness of the second layer needs to be 480 nm or less, preferably 400 nm or less, and more preferably 300 nm or less.

Further, the relationship between the thickness of the first layer (Al alloy film) and the second layer (Ag alloy film) is not particularly limited. The film thickness of the first layer (Al alloy film) and the second layer (Ag alloy film) may be the same or different. In the case of a difference, the film of the first layer (Al alloy film) may be thicker than the second layer (Ag alloy film), or may be thin. In order to achieve more precise micromachining, it is preferable that the film thickness of the first layer (Al alloy film) is thicker than that of the second layer (Ag alloy film) (first layer > second layer), Or the same film thickness (1st layer = 2nd layer). In other words, the film thickness of the first layer (Al alloy film) is preferably set to be equal to or greater than the film thickness of the second layer (Ag alloy film) (first layer ≧ second layer).

The second layer (Ag alloy film) accounts for 10 to 70% of the film thickness (100 to 800 nm) of the electrode (laminated film) of the present invention. When the film thickness ratio of the second layer (Ag alloy film) is lowered, a desired reflectance cannot be obtained. Therefore, the film thickness ratio of the second layer (Ag alloy film) needs to be 10% or more, preferably 15% or more. More preferably, it is more than 20%. On the other hand, when the ratio of the second layer (Ag alloy film) is too high, the above etching rate control effect by the first layer (Al alloy film) cannot be sufficiently obtained, and the wet film is not sufficiently obtained. The above-described etching rate control effect by the first layer (Al alloy film) is obtained, and the amount of etching during wet etching is increased, and high-precision micromachining becomes difficult. Therefore, the film thickness ratio of the second layer (Ag alloy film) needs to be 70% or less, preferably 50% or less, more preferably 40% or less, still more preferably 30% or less.

Further, in order to find the etching rate control effect of the first layer (Al alloy film), the film thickness ratio of the first layer (Al alloy film) is required to be 30% or more, preferably 50% or more, and more preferably 60%. More preferably, it is 70% or more. The upper limit of the film thickness ratio of the first layer (Al alloy film) is not particularly limited, and may be defined in accordance with the relationship between the film thickness ratio of the second layer (Ag alloy film).

(component of the first layer (Al alloy film))

In the present invention, in order to exhibit a good reflectance, electrical resistivity, and micro-workability while thickening the electrode, the first layer (Al alloy film) needs to contain the following alloy elements within a predetermined range.

The alloying element added to the Al alloy is at least one selected from the group consisting of Si, Cu, and Ge from [(1-A) such that the rare earth element is 0.05 to 10 atom%, and (1-B) 0.5 to 1.5 atom%, (1-C) at least one selected from the group consisting of at least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 to 0.7 atom%. These elements can be added individually or in combination of any two. That is, in the (1-A) group, the (1-B) group, and the (1-C) group, any group may be used alone, or a combination of any two groups may be used in combination, or all of them may be used together. group). Further, the elements constituting each group may be used alone or in combination of two or more kinds.

Further, the content of each group is a single content when it is separately contained, and is a total amount when a plurality of elements are included. The same is true for the second layer (Ag alloy film).

In a more preferable embodiment, the Al alloy is preferably adjusted so that Al is preferably 90 atom% or more, and more preferably 95 atom% or more is Al.

The Al alloy constituting the first layer preferably contains the above elements, and the residual portion is Al and unavoidable impurities.

(1-A) makes the rare earth element 0.05~1.0 atom%

The rare earth element is an element which suppresses the coarsening of the structure of the Al alloy and contributes to the suppression of the decrease in reflectance. In order to exert such an effect, the content of the rare earth element is 0.05 atom% or more, preferably 0.1 atom% or more, and more preferably 0.15 atom% or more. From the viewpoint of suppression of coarsening of the structure, the higher the content of the rare earth element, the better, but if the content is too large, the resistivity may be deteriorated, and the reflectance may be lowered. For this reason, the content is 1.0 atom% or less, preferably 0.8 atom% or less, more preferably 0.6 atom% or less.

The above rare earth element means a lanthanoid element (a total of 15 elements of Lu of atomic sequence 57 to Lu of atomic sequence 71 in the periodic table) plus an element group of Sc (钪) and Y (钇). A preferred rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce. (Better rare earth elements are Nd, La).

(1-B) making at least one selected from the group consisting of Si, Cu, and Ge 0.5 to 1.5 atom%

Si, Cu, and Ge are elements which suppress the coarsening of the structure of the Al alloy and contribute to the suppression of the decrease in reflectance. In order to exert such an effect, the content of at least one selected from the group consisting of Si, Cu, and Ge is 0.5 atom% or more, preferably 0.6 atom% or more, and more preferably 0.7 atom% or more. From the viewpoint of the above-described roughening suppression, the content of Si, Cu, and Ge is preferably as high as possible, but when the content is too large, the electrical resistivity is deteriorated and the reflectance is also lowered. For this reason, the content is 1.5 atom% or less, preferably 1.2 atom% or less, more preferably 1.0 atom% or less. The preferred element among these is Cu.

(1-C) making at least one selected from the group consisting of Ti, Ta, W, and Nb 0.05 to 0.7 at%

Ti, Ta, W, and Nb are the same as the above-described rare earth element and Si, Cu, and Ge, and are elements which suppress the coarsening of the structure and contribute to the suppression of the decrease in reflectance. In order to exert such an effect, the content of at least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 atom% or more, preferably 0.1 atom% or more, and more preferably 0.15 atom% or more. . From the viewpoint of the above-described roughening suppression, the content of Ti, Ta, W, and Nb is preferably as high as possible, but when the content is too large, the electrical resistivity is deteriorated and the reflectance is also lowered. For this reason, the content is 0.7 atom% or less, preferably 0.5 original. The sub-% is below, more preferably 0.4 atom% or less. The preferred elements among these are Ti and Ta.

As a component of the preferable first layer (A alloy film) containing the alloy elements of the above (1-A) to (1-C) group, Al-0.2Nd and Al-0.2Nd-0.3Ta are exemplified.

(component of the second layer (Ag alloy film))

In the present invention, the composition of the second layer (Ag alloy film) is not particularly limited, and a constituent component of a conventionally used Ag alloy film can be used. However, in order to exhibit excellent reflectance, electrical resistivity, and micro-workability while thickening the electrode, it is preferred that the following alloy elements are within a predetermined range.

The second layer as the alloying element preferably contains 0.05 to 1.0 atomic % of the rare earth element from [(2-A), (2-B) such that Bi and/or Cu is 0.05 to 1.0 atomic %, (2-C). A group consisting of at least one selected from the group consisting of Pd, Pt, and Au is 0.1 to 1.5 atom%, and (2-D) is Zn and/or In is 01 to 1.5 atom%. Choose at least one of them. These elements may be added singly or in combination of any two in the same manner as the first layer (Al alloy film). Further, the content of each group is a single content or a total amount as described above.

In a more preferred embodiment, the Ag alloy is adjusted so that 98 atom% or more and 99.98 atom% or less of the Ag alloy are Ag. When the Ag content is too small, the reflectance of the Ag alloy film may be lowered.

The Ag alloy constituting the second layer preferably contains the above elements, and the residual portion is Ag and unavoidable impurities.

(2-A) making the rare earth element 0.05~1.0 atom%

The rare earth element suppresses the element which suppresses the decrease of the reflectance according to the growth of the Ag crystal grain in the thermal history and contributes to the aggregation inhibition (halogen resistance) by the halogen ion. In order to exert such an effect, the content of the rare earth element is preferably 0.05 atom% or more, more preferably 0.1 atom% or more, still more preferably 0.15 atom% or more. From the viewpoint of the improvement of the above effects, the higher the content of the rare earth element, the better, but if the content is too large, the reflectance may be lowered. For this reason, the content is preferably 1.0 atom% or less, more preferably 0.7 atom% or less, still more preferably 0.5 atom% or less.

The rare earth element is the same as the first layer, and means a lanthanoid element, Sc, and Y. A preferred rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce (better The rare earth elements are Nd, La).

(2-B) making Bi and/or Cu 0.05 to 1.0 atom%

Bi and Cu are the same as the above-mentioned rare earth elements, and are elements which contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance. In order to exert such an effect, the content of Bi and/or Cu is preferably 0.05 atom% or more, more preferably 0.07 atom% or more, still more preferably 0.1 atom% or more. From the viewpoint of the improvement of the above effects, the higher the content of Bi and Cu, the better, but if the content is too large, the reflectance may be lowered. Bi and / or Cu The content is preferably 1.0 atom% or less, more preferably 0.7 atom% or less, still more preferably 0.5 atom% or less. The preferred element among these is Bi.

(2-C) making at least one selected from the group consisting of Pd, Pt, and Au 0.1 to 1.5 atom%

Pd, Pt, and Au are the same as the above-mentioned rare earth elements, Bi and Cu, and are elements which contribute to suppression of growth of Ag crystal grains and improvement of halogen resistance. In order to exert such an effect, the content of at least one selected from the group consisting of Pd, Pt, and Au is preferably 0.1 atom% or more, more preferably 0.15 atom% or more, still more preferably 0.2 atom%. the above. From the viewpoint of the above effects, the higher the content of Pd, Pt, and Au, the better, but if the content is too large, the reflectance may be lowered. For this reason, the content is preferably 1.5 atom% or less, more preferably 1.0 atom% or less, still more preferably 0.8 atom% or less. The preferred elements among these are Pd, Pt.

(2-D) making Zn and/or In 0.1 to 1.5 atom%

Zn and In are the same as the above-mentioned elements, and contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance while contributing to the improvement of oxidation resistance and sulfur resistance. In order to exert such an effect, the content of Zn and/or In is preferably 0.1 atom% or more, more preferably 0.3 atom% or more, still more preferably 0.5 atom% or more. From the viewpoint of the improvement of the above effects, the higher the content of Zn and In, the better, but if the content is too large, the reflectance may be lowered. For this reason, the content is preferably 1.5 atom% or less, more preferably 1.3 atom% or less, still more preferably 1.1 atom% or less. Among these The preferred element is Zn.

As a component of the preferable second layer (Ag alloy film) containing the alloy elements of the above (2-A) to (2-D) group, Ag-0.3Bi-0.5Nd is exemplified.

(Formation method of the first layer (Al alloy film))

Examples of the method for forming the first layer (Al alloy film) contained in the laminated film of the constituent electrode of the present invention include a sputtering method and a vacuum vapor deposition method. In the present invention, it is possible to form a first layer (Al) by using a sputtering target in a sputtering method from the viewpoint of thinning and homogenization of alloy components in a film, and easy control of the amount of added elements. An alloy film) is preferred.

When the first layer (Al alloy film) is formed by a sputtering method, an element corresponding to (1-A) to (1-C) constituting the first layer (Al alloy film) is used. Al alloy sputtering targets are useful. Specifically, at least one selected from the group consisting of [(1-A) such that the rare earth element is 0.05 to 1.0 at%, and (1-B) is composed of Si, Cu, and Ge is 0.5 to 1.5 at%. (1-C) Al alloy sputtering of at least one selected from the group consisting of at least one selected from the group consisting of Ti, Ta, W, and Nb of 0.05 to 0.7 atomic %] The target is preferred.

Basically, as long as an Ag alloy sputtering target having the same composition as the desired Al alloy film is used, an Al alloy film having a desired composition can be formed without a composition variation.

However, there is no need for a sputtering target to contain all alloys with Al. The element corresponding to the composition of the film. Simultaneous sputtering (co-sputtering) of a sputtering target containing a predetermined amount of elements is also useful for the formation of an Al alloy film of a desired composition.

Examples of the method for producing the Al alloy sputtering target include a vacuum melting method and a powder sintering method, but from the viewpoint of ensuring the composition and the uniformity of the structure in the surface of the target, in particular, by vacuum melting. Better production.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar, nitrogen, etc.

‧In the film formation (Ar) pressure: 1.0~5.0mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

(Method of forming the second layer (Ag alloy film))

A method of forming the second layer (Ag alloy film) constituting the reflective electrode may be the same as the above-described first layer (Al alloy film). However, for the same reason as the first layer (Al alloy film), the second layer (Ag alloy film) is preferably formed by using a sputtering target in the sputtering method.

When the second layer (Ag alloy film) is formed by sputtering, it is useful to use an Ag alloy sputtering target containing any of the above-mentioned (2-A) to (2-D) elements.

Specifically, the use of [(2-A) makes the rare earth element 0.05 to 1.0 atom%, (2-B) makes Cu 0.05 to 1.0 atom%, and/or makes Bi 0.25 to 5.0 atom%, ( 2-C) consisting of at least one selected from the group consisting of Pd, Pt, and Au being 0.1 to 1.5 at%, and (2-D) having Zn and/or In being 0.1 to 1.5 at%] At least one of the Ag alloy sputtering targets selected in the group may be used.

Basically, an Ag alloy sputtering target having the same composition as that of the desired second layer (Ag alloy film) can be used to form an Ag alloy film having a desired composition without any compositional variation. However, since Bi is an element which is easily splashed during the film formation process and is easily concentrated near the surface of the film, it is preferable to include Bi which is about 5 times the amount of Bi in the Ag alloy film in the sputtering target. The content of Bi is preferably 0.25 atom% or more, more preferably 0.35 atom% or more, still more preferably 0.5 atom% or more, and more preferably 5.0 atom% or less, more preferably less than the content of Bi in the film. 3.5 atom% or less, more preferably 2.5 atom% or less.

However, it is not necessary for one sputtering target to contain all the elements corresponding to the composition of the Ag alloy film. Simultaneous sputtering (co-sputtering) of a sputtering target containing a predetermined amount of elements is also useful for the formation of an Ag alloy film of a desired composition.

Although the above various methods are mentioned in the manufacturing method of the Ag alloy sputtering target, the vacuum melting method is preferable similarly to the above-mentioned Al alloy sputtering target.

The second layer (Ag alloy film) can also be formed by sputtering One layer (Al alloy film) is then formed by sputtering.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar, nitrogen, etc.

‧In the film formation (Ar) pressure: 1~5mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

Further, the shape of the Al alloy sputtering target and the Ag alloy sputtering target include the shape of the sputtering apparatus and the processing into an arbitrary shape depending on the structure (square plate shape, disk shape, doughnut plate shape). Wait).

The first layer (Al alloy film) and the second layer (Ag alloy film) of the laminated film which is a characteristic part of the present invention have been described above. In the following, the electrode used in the display device and the input device using the laminated film including the first layer (Al alloy film) and the second layer (Ag alloy film) is used as an organic EL element as a reflective electrode of an organic EL. Construction is explained.

However, the present invention is not limited to the above structure, and may be applied to electrodes such as a gate electrode, a source drain (source, drain), and the like in addition to the reflective electrode.

An organic EL device including an electrode comprising a laminate film of a first layer (Al alloy film) and a second layer (Ag alloy film) of the present invention as a reflective electrode will be described using an organic EL display shown in FIG. 1 as an example. . In the following, although this organic EL element is applied to In the case of the EL display, the organic EL element is not limited to be applied to an organic EL display, and may be applied to organic EL illumination or the like. In addition, FIG. 1 is an example of an organic EL display. The present invention is characterized in that the reflective electrode is composed of a laminated film including the first layer (Al alloy film) and the second layer (Ag alloy film), and the reflective electrode, the first layer, and the second layer are appropriately controlled. The thickness of each film and the structure of the first layer. The configuration other than the configuration shown in FIG. 1 is not limited, and a known configuration generally used in the field of organic EL displays can be employed. Furthermore, the reflective electrode of the present invention is not limited to the reflective anode described above, and may be used for other reflective electrodes.

First, as shown in FIG. 1, on the substrate 1, a TFT 2 and a passivation film 3 are formed, and further, a planarization layer 4 is formed thereon. On the TFT 2, a contact hole 5 is formed. The source drain (not shown) of the TFT 2 is electrically connected to the first layer (Al alloy film) 6 constituting the reflective electrode of the present invention through the contact hole 5.

Further, a second layer (Ag alloy film) 7 is formed directly above the first layer (Al alloy film) 6. The formation of the first layer (Al alloy film) 6 and the second layer (Ag alloy film) 7 can be carried out by the above method.

Next, an organic layer 9 is formed on the second layer (Ag alloy film) 7. The organic layer 9 may include, for example, a hole transport layer, an electron transport layer, and the like in addition to the organic light-emitting layer. Further, a cathode 10 is formed on the organic layer 9. In the case of FIG. 1, the material constituting the cathode 10 is not particularly limited, and it can be constituted by a material used in the past.

In the above organic EL display, since it is from the organic layer 9 The light emitted by the organic light-emitting layer is efficiently reflected by the reflective anode (particularly the second layer (Ag alloy film) 7) of the present invention, so that excellent light-emitting luminance can be achieved. Further, the higher the reflectance of the reflective electrode (the first layer (Al alloy film) 6 + the second layer (Ag alloy film) 7), the higher the value can be obtained, generally 90% or more, preferably 92% or more. Reflectivity.

Further, the higher the hole injection characteristics of the reflective anode to the organic layer 9, the better.

The reflective electrode including the electrode of the present invention and the organic EL device having the electrode have been described above.

The electrodes of the display device of the present invention described above can be used as electrodes of various display devices (including input devices). Examples of applicable electrodes include a gate for a thin film transistor in a liquid crystal display (LDC) illustrated in FIG. 2, a source drain (source, drain), and an organic body such as illustrated in FIG. A gate electrode for a thin film transistor in an EL display (OELD), a source drain, such as a cathode in a field emission display (FED) illustrated in FIG. 4, and a gate, such as the fluorescent vacuum tube (VFD) illustrated in FIG. The anode in the middle, for example, an address electrode in a plasma display (PDP) illustrated in Fig. 6, for example, a back electrode in an inorganic EL display exemplified in Fig. 7.

In FIG. 2, the transparent electrode is connected to the liquid crystal. In FIG. 2, a semiconductor germanium, a gate insulating film, and a gate electrode which are in contact with a source and a drain which will be described later are formed on the glass substrate via an insulating film. Then, the source and the drain are disposed via the insulating protective film, and the transparent electrode in contact with the drain is further disposed via the insulating protective film.

In Figure 3, the anode is attached to an organic layer. In FIG. 3, a semiconductor germanium, a gate insulating film, and a gate electrode which are in contact with a source and a drain which will be described later are formed on the glass substrate via an insulating film. Then, the source and the drain are disposed via the insulating protective film, and the anode in contact with the drain is further disposed via the insulating protective film.

In FIG. 4, a cathode and a resistance layer are laminated on a glass substrate. Then, in the sealing by the sealing layer, the emitters separated by the insulating layer and the gate of the laminated layer are disposed. On top of this, a phosphor layer, a transparent electrode, and a glass substrate separated by a black matrix are further laminated.

In FIG. 5, an insulating film is laminated on a glass substrate. Then, the anode wiring, the anode, and the phosphor are further laminated while being sealed by the sealing layer. A gate electrode is disposed on the anode, and a filament is disposed thereon, and a transparent electrode and a surface glass substrate are further laminated.

In FIG. 6, on the back glass substrate, an address electrode and a dielectric layer are formed. A plurality of phosphor layers separated by a partition wall are formed on the dielectric layer, and a dielectric layer, a display electrode, and a surface glass substrate are laminated thereon.

In FIG. 7, a back surface electrode, an insulating layer, a phosphor layer, a transparent electrode, and a surface glass substrate are laminated on the back glass substrate.

Further, the electrode of the present invention can also be applied to an input device. The input device includes an input device such as a touch panel having an input means on the display device, and an input device not having a display device such as a touch panel. Specifically, the electrode of the present invention can also be used in combination with the above various display devices and position input means, by pressing and pressing on the screen. An input device for operating the device and an electrode (for example, the above-described various electrodes) of the input device of the display device that is separately provided corresponding to the input position on the position input means. Further, as the position input means, various known operational principles can be employed: a matrix switch, a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, a capacitive method, and the like.

When the electrode of the present invention is used as an electrode of such a display device or an input device, the above-described predetermined effects can be obtained and confirmed by experiments.

[First Embodiment]

In the following, the first invention is more specifically described by way of examples, but the present invention is not limited to the following examples, and it is of course possible to carry out appropriate modifications and modifications in the scope that can be adapted to the scope of the prior and the following description, and the like. It is within the technical scope of the present invention.

(film formation)

A sputtering target (a disc type having a diameter of 4 Å) having the same composition as that of the first layer (Al alloy film: residual portion being Al and unavoidable impurities) having the composition shown in Tables 1 to 3 was prepared. Using this sputtering target, a first layer was formed on a glass substrate (an alkali-free glass, a plate thickness of 0.7 mm, and a diameter of 4 Å) by a DC magnetron sputtering apparatus according to the following sputtering conditions. Subsequently, a sputtering target (a disc shape having a diameter of 4 Å) having the same composition as that of the second layer (Ag alloy film: residual portion being Ag and unavoidable impurities) having the composition shown in Tables 1 to 3 was used. In the first layer of the following sputtering conditions The second layer of the film was formed on the top to prepare a sample. Further, the first layer of No. 21 in Table 2 used a pure Al sputtering target, and the second layer of No. 51 in Table 3 used a pure Ag sputtering target. In addition, the Bi content in the target is made five times larger than the Bi content in the second layer (Ag alloy film). For example, in No. 21 of Table 2, a second layer (Ag alloy film) of Ag-0.1 at% Bi-1.0 at% Zn was formed using a sputtering target of Ag-0.5 at% Bi-1.0 at% Zn.

The composition of the first layer (Al alloy film) and the second layer (Ag alloy film) after film formation was confirmed by Inductively Coupled Plasma (ICP) mass spectrometry. In the table, the content rates in "Layer 1" and "Layer 2" are all atomic %.

(Al alloy sputtering conditions)

‧ substrate temperature: room temperature

‧Ar gas flow: 30sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 260W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

(Ag alloy sputtering conditions)

‧ substrate temperature: room temperature

‧Ar gas flow: 30sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 130W

‧ Ultimate vacuum: 3 × 10 ^-6 Torr:

(Method for measuring film thickness)

The film thickness of each of the first layer (Al alloy film) and the second layer (Ag alloy film) was measured by a probe surface profiler (manufactured by KLATencor, Alpha-step). The film thickness of the total of three points was measured from the center of the film at a distance of 5 mm in the radial direction, and the average value was referred to as "thickness of the film" (nm). In addition, the film thickness of the first layer (Al alloy film) and the film thickness of the second layer (Ag alloy film) are collectively used as the film thickness of the laminated film (in the table, "total").

(Processability evaluation)

A photoresist pattern having a line gap of 10 μm in width was formed on the sample (layer film) produced as described above to evaluate etching workability. Specifically, the laminated film was immersed in a mixed acid etching solution (phosphoric acid: nitric acid: acetic acid: water = 50:0.2:30:19.8) while heating to 40 ° C, and was performed during the etching end time + 20 seconds (percause time). Etching. The size of the wiring pattern after etching was observed with an optical microscope (magnification: 1000 times), and the wiring size was measured to evaluate the side etching. In the present example, evaluation was performed according to the following criteria: ◎ or ○ was judged to be acceptable (good etching property), and × was judged as unacceptable ("micromachining property" in the table).

◎: 9μm or more

○: 8 μm or more, less than 9 μm

×: less than 8 μm

(Measurement of reflectance)

According to JIS R 3106, the visible light reflectance was measured by a spectrophotometer (manufactured by JASCO Corporation: visible light ‧ ultraviolet spectrophotometer "V-570") using light having a wavelength of 380 to 780 nm under a D65 light source. Specifically, the reflectance is obtained as follows from the reflected light intensity (measured value) of the sample prepared as described above with respect to the intensity of the reflected light of the reference mirror.

[Reflectance] (= [Reflected light intensity of sample / reflected light intensity of reference mirror] × 100%)

Then, in the present embodiment, the reflectance of the sample in λ = 450 nm was evaluated based on the following criteria, ○ was judged as pass, and × was judged as unacceptable.

○: 90% or more

×: less than 90%

(resistivity)

The resistivity was measured using a sample in which a 10 μm wide line gap pattern was formed for the laminated film. Specifically, the specific resistance was measured by a four-terminal method generally used. Therefore, in the present embodiment, the evaluation was performed based on the following criteria, ○ was judged as pass, and × was judged as unacceptable.

○: 7 μΩcm or less

×: Super 7μΩcm

The above test results are shown in Tables 1-3.

Table 1 is a result of investigating the influence of the composition of the first layer (Al alloy film) and the second layer (Ag alloy film) on the reflectance and the micro-workability only when the film thickness is changed. The following can be seen from Table 1.

The total film thickness of No. 1 and No. 2 was 100 nm, but the film thickness of the second layer (Ag alloy film) was reduced to No. 1 (50 nm). From this, it is understood that a desired reflectance can be obtained as long as the second layer (Ag alloy film) is at least 60 nm or more.

Further, when only the reflectance is focused on, the film thickness of the second layer (Ag alloy film) is 60 nm or more, and the reflectance (No. 2 to 12) is good.

No. 12 is the upper limit (480 nm or less) of the film thickness of the second layer (Ag alloy film) in the range of the total film thickness (800 nm or less) defined in the present invention, and the second layer (Ag alloy film). The film thickness ratio is high. In the case of this example, since the film thickness ratio of the first layer (Al alloy film) is less than 30% (the ratio of the second layer (Ag alloy film) is high), the etching rate cannot be appropriately controlled by the Al alloy film. Therefore, the micro workability is deteriorated.

In addition, No. 5 and No. 9 satisfy the total film thickness prescribed by the present invention and the film thickness of the second layer (Ag alloy film), but the film thickness ratio of the second layer (Ag alloy film) is high. example of. In the same manner as in No. 12, since the film thickness ratio of the first layer (Al alloy film) is less than 30% (the ratio of the second layer (Ag alloy film) is high), the etching rate cannot be appropriately controlled. Micro workability is deteriorated.

In addition, when the film thickness of the first layer (Al alloy) is thicker than that of the second layer (Ag alloy film) (first film thickness > second film thickness), more precise etching can be performed. Processing ("Micromachinity" is ◎) (No. 3, 4, 7, 8).

According to the above results, it is understood that if the reflectance and the micro-workability are to be satisfied, it is necessary to control not only the film thickness of the second layer (Ag alloy film) (No. 1, No. 12) but also the total film thickness of the laminated film. And the film thickness ratio of the Ag alloy is controlled within a predetermined range (No. 5, 9, 12).

In the case where the composition of the second layer (Ag alloy film), the film thickness, and the film thickness ratio of the Ag alloy are fixed, and the composition of the first layer (Al alloy) is appropriately changed, the reflectance and the micro-machining are investigated. The result of the effects of sex and electrical resistivity. The following can be seen from Table 2.

No. 21 is an example in which pure Al containing no alloying element component is used as the first layer. In this case, both resistivity and micro-machining properties are good, but the reflectance is low. On the other hand, a predetermined reflectance can be obtained as long as it contains at least an alloying element of the lower limit level specified in the present invention (No. 22, 27, 30, and 33). Therefore, it was learned that it is effective to contain an alloying element in the first layer (Al alloy film).

No. 22 to 25 are examples in which the content of the alloying element in the first layer (Al alloy film) is changed. In these cases, as long as the content of the alloying element is within a predetermined range, good results (No. 22 to 24) can be obtained simultaneously with the reflectance, the micro-workability, and the electrical resistivity. However, if the content of the alloying element is excessive, Then, the reflectance and the resistivity are deteriorated (No. 25). The same results are also shown in Nos. 27 to 29 and 30 to 32. It is learned that if the content of the alloying element contained in the first layer (Al alloy film) is excessive, the reflectance and the electrical resistivity are adversely affected.

Further, it is understood that as long as the alloying elements of the first layer (Al alloy film) are within a predetermined range, even if a plurality of alloying elements (No. 38) are combined, the above-described desired effects can be exhibited.

In the case where the composition of the first layer (Al alloy film), the film thickness, and the film thickness ratio of the Ag alloy are fixed, and the composition of the Ag alloy is appropriately changed, the reflectance, the micro-workability, and the specific resistance are investigated. The result of the impact. The following can be seen from Table 3.

No. 51 is an example in which pure Ag containing no alloying element component is used as the second layer. In this example, both the resistivity and the micro-machining property were good, but the reflectance was low. On the other hand, a predetermined reflectance can be obtained as long as it contains at least an alloying element of the lower limit level specified by the present invention (No. 52, 57, 61, 67, etc.). Therefore, it was found that it is effective to contain an alloying element in the second layer (Ag alloy film).

No. 52 to 55 are examples in which the content of the alloying element (Nd) in the second layer (Ag alloy film) is changed. In these cases, as long as the content of the alloying element is within a predetermined range, good results (No. 52 to 54) can be obtained simultaneously with the reflectance, the micro-workability, and the electrical resistivity. However, if the content of the alloying element is excessive, Then, the reflectance and the resistivity are deteriorated (No. 55). The same results are also shown in No. 57-60, 61-64, 67-70, and 71-74. It is learned that if the content of alloying elements contained in the second layer (Ag alloy film) is too large, the reflectance is Resistivity has an adverse effect.

Further, the alloy element of the second layer (Ag alloy film) can exhibit the above-described desired effects even when a plurality of alloy elements (No. 75 to 82) are combined within a predetermined range.

[Second invention]

Hereinafter, the second invention will be described in detail.

The present inventors have further intensively studied in order to solve the above problems. As a result, the inventors of the present invention have found that the electrode for use in a display device or an input device includes a first layer made of an Al alloy from the substrate side, and an Ag alloy formed thereon. a second layer composed of an oxide or a nitride, and a laminated film of a third layer made of an Ag alloy formed on the second layer (the first layer, the second layer, and the third layer may be in direct contact with each other) Alternatively, the film thickness of the electrode and the film thickness of each layer constituting the electrode may be appropriately controlled.

The reason for achieving the second invention is as follows. First, the problem of the conventional Ag alloy film (single layer), that is, the problem of poorly etching precision microfabrication when the photoresist is patterned by wet etching of the mask, is known to use an Al film. The laminated structure with the Ag alloy film can be solved by adjusting the etching rate (Patent Document 1). This is because the etching rate of the Al film is slower than the etching rate of the Ag alloy film, and the Al film exhibits an etching rate control function. According to this technique, if the electrode is a laminated structure of the Ag alloy film and the Al film, the etching rate can be adjusted, and excessive etching of the Ag alloy film can be suppressed, and the size can be processed with high precision.

However, in recent years, the electrodes of the display device require the refinement of the wiring and the suppression of the opposite characteristics of the wiring resistance. Further, the reflective electrode used in an organic EL display or the like requires high reflectance in addition to miniaturization of wiring and suppression of wiring resistance. In the prior art as disclosed in Patent Document 1, although the etching process can be performed with high precision for the wiring, since the Ag alloy film of the target anode is as thin as 50 to 80 nm, It is also difficult to ensure a stable high reflectance. Further, although the Al film has the above-described etching rate control function, it is difficult to ensure high reflectance because it does not have sufficient reflectance.

As a result of review by the present inventors, it was found that, in order to ensure good micro-machining properties while considering the reflectance, pure Al (or Al oxide and Al intermetallic compound) is formed on the first layer on the substrate side. In the case where it is difficult to form the first layer using an Al alloy film, it is useful.

As a result of further review, it was learned that the process of manufacturing a thin film transistor and an organic EL element due to the formation of a transparent oxide conductive film such as ITO or an insulating film in the case where only an Al alloy film and an Ag alloy film are laminated. In the thermal history of high temperature (for example, 300 ° C grade), Al diffuses from the Al alloy film to the Ag alloy film, and the reflectance of the Ag alloy film decreases.

As a result of reviewing the constitution of the problem, the present inventors have learned that the first layer (Al alloy film) and the third layer (Ag alloy film) are provided as an intermediate layer as described above. Two layers (an oxide film or a nitride film of an Al alloy) are effective. In other words, it is understood that the second layer (the oxide film or the nitride film of the Al alloy) provided as the intermediate layer functions as an Al diffusion preventing layer and prevents Al from being formed from the first layer (Al alloy film). The diffusion to the third layer (Ag alloy film) suppresses the decrease in the reflectance of the third layer (Ag alloy film).

On the other hand, it is learned that oxides and nitridation are generated when the second layer (the oxide film or the nitride film of the Al alloy) is interposed. In the case of the insulating layer of the material, there is a problem that the contact resistance becomes high. However, by appropriately controlling the film thickness of the second layer, it is possible to obtain a good contact resistance and exhibit the above-described diffusion preventing effect, and have a low wiring resistance.

The present inventors made the first layer (Al alloy film), the second layer (the oxide film or the nitride film of the Al alloy), and the third layer (the Ag alloy film) in accordance with the effect of the formation of the intermediate layer. The reflective electrode (layered film) laminated in this order was examined for reflectance, micromachinability (dimension accuracy during patterning, presence or absence of residual stains), and contact resistance. As a result, the following findings were obtained from Table 4 of the examples described later.

First, it is understood that when the second layer (the oxide film or the nitride film of the Al alloy) is not provided as in No. 101 of Table 4, diffusion of Al cannot be prevented, and the reflectance of the reflective electrode is deteriorated.

On the other hand, when the second layer (the oxide film or the nitride film of the Al alloy) is provided to exhibit the diffusion preventing effect, the reflectance is improved (No. 102 to 104), but if the film thickness is too thick, the display is exhibited. Micromachineability and tendency to deteriorate contact resistance (No. 105).

According to the above results, it has been found that it is effective to appropriately control the film thickness of the second layer (the oxide film or the nitride film of the Al alloy) in order to ensure good reflectance, micro workability, and contact resistance.

Further, regarding the third layer (Ag alloy film), it was found from the comparison of Nos. 106, 107, 112, and 113 that if the film thickness is reduced, the reflectance is lowered. This is thought to be caused by the fact that the thickness of the third layer (Ag alloy film) is thinner and the light of the third layer (Ag alloy film) is increased, and the reflectance of the third layer (Ag alloy film) is lowered. At the same time relative to the transmitted light The first layer (Al alloy film) and the second layer (the oxide film or the nitride film of the Al alloy) have a low reflectance.

In addition, although it is not described in Table 4, it is understood that the thickness of the third layer (Ag alloy film) is increased, and the reflectance of the reflective electrode is increased. However, the etching rate control function of the first layer (Al alloy) cannot be used. Fully effective, high-precision micromachining becomes difficult.

As a result of further experiments, it was found that the relationship between the film thickness ratio of the first layer (Al alloy film) and the third layer (Ag alloy film) affects the micro workability. In other words, when the film thickness ratio of the third layer (Ag alloy film) exceeds 70%, the third layer (Ag alloy film) to be etched is increased, so that the micro workability is deteriorated. This tendency is irrelevant to the film thickness of the third layer (Ag alloy film) and occurs when the ratio of the film thickness to the electrode (layer film) exceeds 70%.

From these results, it is learned that if a good contact resistance, micromachinability, and reflectance are to be ensured, it is not necessary to laminate the first layer (Al alloy film), the second layer (the oxide film or the nitride film of the Al alloy), In the third layer (Ag alloy film), it is necessary to appropriately control the ratio of the film thickness of the third layer (Ag alloy film) to the total film thickness of the laminated film within a predetermined film thickness range. The present inventors have found that the present invention can be achieved by appropriately controlling the film thickness in such a manner that even if the electrode is thickened (for example, at a level of 800 nm) in order to obtain good wiring resistance, the above characteristics can be ensured.

Next, the present inventors have directed the first layer (Al alloy film) and the second layer (the oxide film or nitride of the Al alloy) constituting the electrode. The composition of the film) and the third layer (Ag alloy film) was examined for the effects of reflectance, micromachinability, and contact resistance.

First, when various alloying elements are added to the first layer (Al alloy film) and the relationship with the above characteristics is investigated, it is learned that among the alloying elements, especially rare earth elements, Ti, Ta, W, and Nb are suitable for reflectance and micro Improvement in workability and contact resistance (refer to Table 5).

Further, in the case where these alloying elements are added, there is a preferable content in terms of reflectance and electrical resistivity. That is, the pure Al film (No. 121 in Table 5) which does not contain an alloying element has good micromachinability and contact resistance, but cannot satisfy the reflectance required for the reflective electrode. In addition, it is understood that even if the content of the alloy element is too large, the alloy layer is left as a residue in the first layer (Al alloy film) after etching, and the micro-workability is deteriorated (No. 125, 129 of Table 5). , 132).

In addition, as long as the other requirements are satisfied and the second layer has a suitable film thickness, the oxide film of the Al alloy (No. 122 to 124, No. 126 to 128 in Table 5) and the nitride film of the Al alloy (Table) Any of No. 130, 131, and 133) of 5 can obtain a desired reflectance, micro workability, and contact resistance.

Furthermore, the present inventors investigated the relationship with the above characteristics by adding various alloying elements to the third layer (Ag alloy film). As a result, it was found that among the alloying elements, particularly rare earth elements, Bi, Cu, Pd, Pt, Au, In, and Zn are suitable for improvement in reflectance and contact resistance (refer to Tables 6A and 6B).

In addition, in the case of adding these alloying elements, according to the reflection The ratio is related to the resistivity, and there is a preferable content. That is, the pure Ag film (No. 201, No. 233 of Table 6A) to which no alloying element is added has a low reflectance, and the reflectance required for the reflective electrode cannot be satisfied. Further, it has been found that even when the alloy element is added, if the content is too large, the reflectance tends to decrease (for example, No. 202 to No. 205 in Table 6A).

From the experimental results shown in Tables 4, 5, 6A, and 6B, it was found that the reflectance and the micro-workability can be improved by appropriately controlling the alloying elements and film thicknesses of the Al alloy film and the Ag alloy film. In addition, it is learned that the second layer (the oxide film or the nitride film of the Al alloy) is improved in reflectance, but if the second layer (the oxide film or the nitride film of the Al alloy) is excessively thickened, Then, the contact resistance and the micro-workability are deteriorated, and the desired wiring resistance and workability cannot be obtained. Then, in the present invention, based on such a result, the alloying elements and their contents are specified as described later.

Hereinafter, an electrode for a display device or an input device of the present invention will be described.

(composition of electrodes)

The electrode for a display device or an input device of the present invention comprises a laminate film comprising: a first layer made of an Al alloy formed on the substrate side, and an oxide or nitride of an Ag alloy formed thereon. The second layer formed and the third layer formed of an Ag alloy formed above the second layer.

In the laminated film of the present invention, it is preferable that the first layer (Al alloy film) and the second layer (oxygen of the Al alloy) are sequentially arranged from the substrate side. The compound film or the nitride film) and the third layer (Ag alloy film) have a three-layer structure in which the layers are laminated in this order.

Further, the laminated film of the present invention is not limited thereto, and may include any layer (fourth layer). Therefore, in the first layer (Al alloy film) and the second layer (the oxide film or nitride film of the Al alloy), the second layer (the oxide film or the nitride film of the Al alloy), and the third layer (the Ag alloy) An arbitrary fourth layer (a film of any constituent component) may be formed between the films. As the fourth layer, a known adhesiveness-promoting film or the like which contributes to an improvement in adhesion is exemplified.

(film thickness of the electrode)

In the present invention, in order to exhibit good wiring resistance, reflectance, and micro-workability, it is necessary to make the thickness of the electrode (layered film) in the range of 100 to 800 nm. When the film thickness is less than 100 nm, there is a problem that the wiring resistance increases and the stable reflectance cannot be obtained. On the other hand, when it exceeds 800 nm, the deterioration of the micro-workability and the coverage of the upper film (passivation film or the like) are deteriorated to cause a problem such as a fracture. The film preferably has a film thickness of 120 nm or more, more preferably 150 nm or more, more preferably 700 nm or less, still more preferably 500 nm or less.

(film thickness of the first layer (Al alloy film))

The first layer (Al alloy film) reflects the light transmitted through the second layer (the oxide film or the nitride film of the Al alloy) and the third layer (the Ag alloy film), and at the same time controls the etching rate at the time of wet etching. The layer of the layer's role. 1st The film thickness of the layer (Al alloy film) is appropriately adjusted to the film thickness of the electrode in accordance with the relationship between the second layer (the oxide film or the nitride film of the Al alloy) and the third layer (the Ag alloy film). can. The film thickness of the first layer (Al alloy film) is preferably 29 nm or more, more preferably 35 nm or more, still more preferably 44 nm or more. On the other hand, when the film thickness of the first layer (Al alloy film) is too thick, the film thickness of the third layer (Ag alloy film) is too small and the reflectance is lowered in accordance with the film thickness of the electrode. Also, the effect of the second layer (the oxide film or the nitride film of the Al alloy) cannot be sufficiently obtained. Therefore, the film thickness of the first layer (Al alloy film) is preferably 729 nm or less, more preferably 629 nm or less, still more preferably 449 nm or less.

(film thickness of the second layer (the oxide film or the nitride film of the Al alloy))

The second layer (the oxide film or the nitride film of the Al alloy) functions as a diffusion preventing layer of Al from the first layer (Al alloy film) to the third layer (Ag alloy film). From the viewpoint of ensuring sufficient diffusion barrier properties, the film thickness needs to be 1 nm or more, preferably 2 nm or more, and more preferably 3 nm or more. On the other hand, when the film thickness of the second layer (the oxide film or the nitride film of the Al alloy) is too thick, the ratio of the second layer having a high specific resistance to the entire wiring increases, so that the first layer to the first layer The contact resistance between the three layers rises, and etching residues are generated to deteriorate the micro workability. From this, it is understood that the thickness of the second layer needs to be 10 nm or less, preferably 8 nm or less, and more preferably 6 nm or less.

(film thickness of the third layer (Ag alloy film))

The third layer (Ag alloy film) particularly acts as a reflective film in the reflective electrode character of. In order to secure high reflectance, the film thickness of the third layer needs to be 70 nm or more, preferably 90 nm or more, and more preferably 100 nm or more. On the other hand, when the film thickness of the third layer (Ag alloy film) is too large, the amount of etching during wet etching increases, and a desired wiring width cannot be obtained, and micro workability is deteriorated. Therefore, the film thickness of the third layer needs to be 480 nm or less, preferably 400 nm or less, more preferably 300 nm or less.

(film thickness ratio of the third layer (Ag alloy film))

The third layer (Ag alloy film) accounts for 10 to 70% of the film thickness (100 to 800 nm) of the electrode (laminated film) of the present invention. When the film thickness ratio of the third layer (Ag alloy film) is lowered, a desired reflectance cannot be obtained. Therefore, the film thickness ratio of the third layer (Ag alloy film) needs to be 10% or more, preferably 15% or more. More preferably, it is more than 20%. On the other hand, when the ratio of the third layer (Ag alloy film) is too high, the above-described etching rate control effect by the first layer (Al alloy film) cannot be sufficiently obtained, and the etching amount at the time of wet etching is increased and the precision is high. Micromachining becomes difficult. Therefore, the film thickness ratio of the third layer (Ag alloy film) needs to be 70% or less, preferably 50% or less, more preferably 40% or less, still more preferably 30% or less.

Further, in order to find the effect of controlling the etching rate of the first layer (Al alloy film), the film thickness ratio of the first layer (Al alloy film) is preferably 29% or more, more preferably 40% or more, and still more preferably It is 45% or more.

(component of the first layer (Al alloy film))

In the present invention, the composition of the first layer (Al alloy film) is not special. The composition of the conventionally used Al alloy film can be used without limitation. However, in order to exhibit a good reflectance, wiring resistance, and micro-workability while thickening the electrode, it is preferable that the alloy element containing the following is within a predetermined range.

The alloying element added to the first layer (Al alloy) preferably contains from 0.05 to 1.0 atom% of the rare earth element from [(1-A), and/or (1-B) from Ti, Ta, W, and Nb. At least one selected from the group consisting of at least one selected from the group consisting of 0.05 to 0.7 atom%. These elements may be added singly or in combination of any two or more. That is, any one of the (1-A) group and the (1-B) group may be used alone, or all (two groups) may be used in combination. Further, the elements constituting each group may be used alone or in combination of two or more kinds. The same is true for the sputtering target described later.

Further, the content of each group is a single content when it is separately contained, and is a total amount when a plurality of elements are included. The second layer (the oxide film or the nitride film of the Al alloy) and the third layer (the Ag alloy film) are also the same.

In the relationship with the above effects, the Al alloy is preferably adjusted so that Al is preferably 90 atom% or more, and more preferably 95 atom% or more is Al.

The Al alloy constituting the first layer preferably contains the above elements, and the residual portion is Al and unavoidable impurities.

(1-A) makes the rare earth element 0.05~1.0 atom%

The rare earth element is an element which suppresses the coarsening of the structure of the Al alloy and contributes to the suppression of the decrease in reflectance. In order to exert such an effect, the content of the rare earth element is preferably 0.05 atom% or more, more preferably 0.1 atom% or more, still more preferably 0.15 atom% or more. From the viewpoint of suppression of coarsening of the structure, the higher the content of the rare earth element, the better, but if the content is too large, the rare earth element becomes a residue after etching, and the leakage current increases, and the transmittance of the glass substrate decreases. The situation. For this reason, the content is preferably 1.0 atom% or less, more preferably 0.8 atom% or less, still more preferably 0.6 atom% or less.

The above rare earth element means a lanthanoid element (a total of 15 elements of Lu of atomic sequence 57 to Lu of atomic sequence 71 in the periodic table) plus an element group of Sc (钪) and Y (钇). A preferred rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce (better rare earth elements are Nd, La).

(1-B) making at least one selected from the group consisting of Ti, Ta, W, and Nb 0.05 to 0.7 at%

Ti, Ta, W, and Nb are the same as the above-described rare earth element, and are elements which suppress the coarsening of the structure and contribute to the suppression of the decrease in reflectance. In order to exert such an effect, the content of at least one selected from the group consisting of Ti, Ta, W, and Nb is preferably 0.05 atom% or more, more preferably 0.1 atom% or more, and still more preferably 0.15 atom% or more. From the viewpoint of the above-described roughening suppression, the content of Ti, Ta, W, and Nb is preferably as high as possible, but if it is too large, residual particles may be generated in the same manner as the rare earth element, and leakage current may increase. The case of a decrease in transmittance. For this reason, the content is preferably 0.7 atom% or less, more preferably 0.5 atom% or less, still more preferably 0.4 atom% or less. The preferred elements among these are Ti and Ta.

The composition of the preferred first layer (Al alloy film) containing the alloy elements of the above (1-A) and (1-B) groups is exemplified by Al-0.2 at% Nd and Al-0.2 at% Nd-0.3. Atomic % Ta.

(component of the second layer (the oxide film or the nitride film of the Al alloy))

The alloying element added to the second layer (the oxide film or the nitride film of the Al alloy) is not particularly limited, and the constituent components of the conventionally used Al alloy film can be used. Further, the composition of the second layer and the first layer (Al alloy) may be the same or different. However, in order to exhibit a good reflectance, contact resistance, and micro-workability while thickening the electrode, it is preferable that the second layer contains the same alloying element as the first layer (Al alloy) within a predetermined range.

That is, the alloying element added to the second layer (Al alloy) preferably contains from 0.05 to 1.0 atom% of the rare earth element from [(1-A), and/or (1-B) from Ti, Ta, At least one selected from the group consisting of W and Nb is at least one selected from the group consisting of 0.05 to 0.7 atom%. The preferred range of the content of each alloying element is also the same as that of the first layer (Al alloy film). Any one of the groups (1-A) and (1-B) as described above may be used alone, or two groups may be used in combination, and the elements constituting each group may be used singly or in combination of two or more kinds. Splash after The same is true for plating targets. The composition ratio of the alloying elements of the second layer (the oxide film or the nitride film of the Al alloy) may be the same as that of the first layer (Al alloy film) or may be different. However, from the viewpoint of easiness of film formation and production cost, the composition ratio of the second layer is preferably the same as that of the first layer (Al alloy film). Further, the second layer (the oxide film or the nitride film of the Al alloy) may exhibit the diffusion preventing effect of Al, and depending on the film thickness, all the Al alloys of the second layer may not be oxidized or nitrided. . Preferably, the second layer is preferably an oxide of a first layer of an Al alloy (for example, an Al oxide, and/or an oxide of an added alloy) or a nitride (for example, an Al nitride, and/or an alloy-added nitride). ) constitutes.

In a more preferred embodiment, when the total of Al and the alloying elements is 100%, it is preferably 90% by atom or more, and more preferably 95% by atom or more of Al. Make adjustments.

The metal element constituting the oxide or nitride of the second layer is preferably the above-mentioned additive element, and the residual portion is Al and an unavoidable impurity.

(component of the third layer (Ag alloy film))

In the present invention, the composition of the third layer (Ag alloy film) is not particularly limited, and a constituent component of a conventionally used Ag alloy film can be used. However, in order to exhibit a good reflectance, wiring resistance, and micro-workability while thickening the electrode, it is preferable that the alloy element containing the following is within a predetermined range.

The alloying element preferably contains 0.05 to 1.0 at% of the rare earth element from [(2-A), (2-B) such that Bi and/or Cu is 0.05 to 1.0 at%, and (2-C) is derived from Pd, Selecting at least one selected from the group consisting of Pt and Au is 0.1 to 1.5 at%, and (2-D) is such that Zn and/or In is 0.1 to 1.5 at%. At least one. Any one of the above-mentioned (2-A) to (2-D) groups may be used alone, or a plurality of groups (arbitrary two or more groups) may be used in combination. In addition, the elements constituting each group may be used singly or in combination of two or more kinds thereof, and the content of each group is a single content or a total amount as described above. The same is true for the sputtering target described later.

In a more preferable embodiment, the Ag alloy is adjusted so that 98 atom% or more of the Ag alloy and 99.98 atom% or less are Ag in accordance with the above-described effects (especially, reflectance).

The Ag alloy constituting the third layer preferably contains the above elements, and the residual portion is Ag and unavoidable impurities.

(2-A) making the rare earth element 0.05~1.0 atom%

The rare earth element suppresses the element which suppresses the decrease of the reflectance according to the growth of the Ag crystal grain in the thermal history and contributes to the aggregation inhibition (halogen resistance) by the halogen ion. In order to exert such an effect, the content of the rare earth element is preferably 0.05 atom% or more, more preferably 0.1 atom% or more, still more preferably 0.15 atom% or more. From the viewpoint of the above-mentioned effects improvement, the content of the rare earth element is preferably as large as possible, but if the amount is too large, the reflectance may be lowered. For this reason, the content is preferably 1.0 atom% or less, more preferably 0.7 atom% or less, more preferably 0.5 atom% or less.

The rare earth element is the same as the first layer, and means a lanthanoid element, Sc, and Y. A preferred rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce (better The rare earth elements are Nd, La).

(2-B) making Bi and/or Cu 0.05 to 1.0 atom%

Bi and Cu are the same as the above-mentioned rare earth elements, and are elements which contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance. In order to exert such an effect, the content of mBi and/or Cu is preferably 0.05 atom% or more, more preferably 0.07 atom% or more, still more preferably 0.1 atom% or more. From the viewpoint of the improvement of the above effects, the content of Bi and Cu is preferably as large as possible, but if the amount is too large, the reflectance may be lowered. The content of Bi and/or Cu is preferably 1.0 atom% or less, more preferably 0.7 atom% or less, still more preferably 0.5 atom% or less. The preferred element among these is Bi.

(2-C) making at least one selected from the group consisting of Pd, Pt, and Au 0.1 to 1.5 atom%

Pd, Pt, and Au are the same as the above-mentioned rare earth elements, Bi and Cu, and contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance. In order to exert such an effect, the content of at least one selected from the group consisting of Pd, Pt, and Au is preferably 0.1 atom% or more, more preferably 0.15 atom% or more, still more preferably 0.2 atom. %the above. From the point of view of the above effects, the content of Pd, Pt, and Au is as high as possible, but Once there is too much, there will be a case where the reflectance is lowered. For this reason, the content is preferably 1.5 atom% or less, more preferably 1.0 atom% or less, still more preferably 0.8 atom% or less. The preferred elements among these are Pd, Pt.

(2-D) making Zn and/or In 0.1 to 1.5 atom%

Zn and In are the same as the above-mentioned elements, and contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance while contributing to the improvement of oxidation resistance and sulfur resistance. In order to exert such an effect, the content of Zn and/or In is preferably 0.1 atom% or more, more preferably 0.3 atom% or more, still more preferably 0.5 atom% or more. From the viewpoint of the above-mentioned effects improvement, the content of Zn and In is preferably as large as possible, but if the amount is too large, the reflectance may be lowered. For this reason, the content is preferably 1.5 atom% or less, more preferably 1.3 atom% or less, still more preferably 1.1 atom% or less. The preferred element among these is Zn.

As a component of the preferable third layer (Ag alloy film) containing the alloy element of the above (2-A) to (2-D) group, Ag-0.3 at% Bi-0.5 at% Nd is exemplified.

(Formation method of the first layer (Al alloy film))

Examples of the method for forming the first layer (Al alloy film) contained in the laminated film of the constituent electrode of the present invention include a sputtering method and a vacuum vapor deposition method. In the present invention, it is possible to form a first layer (Al) by using a sputtering target in a sputtering method from the viewpoint of thinning and homogenization of alloy components in a film, and easy control of the amount of added elements. An alloy film) is preferred.

When the first layer (Al alloy film) is formed by a sputtering method, an element corresponding to (1-A) and (1-B) constituting the first layer (Al alloy film) is used. Al alloy sputtering targets are useful. Specifically, at least one selected from the group consisting of Ti, Ta, W, and Nb containing [(1-A) such that the rare earth element is 0.05 to 1.0 atomic %, and/or (1-B) An Al alloy sputtering target of 0.05 to 0.7 at%] is preferred.

Basically, as long as an Ag alloy sputtering target containing these elements and having the same composition as the desired first layer (Al alloy film) is used, the first layer of the desired composition can be formed without composition variation. Al alloy film).

However, it is not necessary for one sputtering target to contain all the elements corresponding to the constituents of the first layer (Al alloy film). Simultaneous sputtering (co-sputtering) of a sputtering target containing a predetermined amount of elements is also useful for forming a first layer (Al alloy film) of a desired composition.

In the method for producing the above-described Al alloy sputtering target, a vacuum melting method and a powder sintering method are exemplified, but the composition and the uniformity of the structure in the surface of the target can be ensured by the production of the vacuum melting method. Preferably.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar

‧In the film formation (Ar) pressure: 1.0~5.0mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

(Second layer (formation method of oxide film or nitride film of Al alloy))

The method of forming the second layer (the oxide film or the nitride film of the Al alloy film) constituting the electrode may be, for example, an oxygen (or nitrogen) addition sputtering method or an inertness of Ar (other than nitrogen). After the Al alloy film is formed by a sputtering method in a gas atmosphere, an oxide film (or a nitride film) is formed by plasma treatment with oxygen (or nitrogen).

Further, the composition of the Al alloy constituting the second layer (the oxide film or the nitride film of the Al alloy) is not particularly limited, and may be the same as or different from the first layer (Al alloy film). For example, it may be an Al alloy sputtering target containing an element corresponding to the above (1-A) and (1-B). From the viewpoint of reduction in manufacturing cost, it is preferable to form the first layer (Al alloy film) by sputtering, and then use the Al alloy sputtering target used for film formation of the first layer (Al alloy film) to form the first 2 layer. In this case, when the sputtering method is added by oxygen (or nitrogen), the atmosphere may be sputtered by an atmosphere containing oxygen (or nitrogen) (for example, an inert gas such as argon or the like is added with oxygen or nitrogen at a level of 10%). A second layer (an oxide film or a nitride film of an Al alloy) is formed. In addition, in the case of plasma treatment, after the Al alloy film is formed, high-frequency plasma is applied in an oxygen (or nitrogen) atmosphere to oxidize (or nitride) the surface of the Al alloy film to form a second A layer (an oxide film or a nitride film of an Al alloy). As such a plasma Various known methods can be employed.

The film formation conditions in the oxygen (or nitrogen) addition sputtering method are also not particularly limited. However, in order to form an oxide film or a nitride film of an Al alloy exhibiting the above effects, for example, the following conditions are preferably employed.

(oxygen addition sputtering conditions)

‧ substrate temperature: room temperature ~ 150 ° C

‧ atmosphere gas: inert gas such as Ar, oxygen gas such as O ₂

‧Air flow ratio: oxygen-containing gas such as O ₂ / (oxygen gas such as inert gas such as Ar + O ₂ ) = 0.05~0.5

‧Air pressure at film formation: 1.0~5.0mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

(nitrogen addition sputtering conditions)

‧ substrate temperature: room temperature ~ 150 ° C

‧ atmosphere gas: inert gas such as Ar, nitrogen gas such as N ₂

‧Air flow ratio: N ₂ or other nitrogen-containing gas / (Inert gas such as Ar + N _{2 ,} etc.) = 0.05~0.5

‧Air pressure at film formation: 1.0~5.0mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

(Method of forming the third layer (Ag alloy film))

A method of forming the third layer (Ag alloy film) constituting the electrode may be the same as the above-described first layer (Al alloy film). Of course Further, for the same reason as the first layer (Al alloy film), the third layer (Ag alloy film) is preferably formed by using a sputtering target in the sputtering method.

When the third layer (Ag alloy film) is formed by sputtering, it is useful to use an Ag alloy sputtering target containing any of the above-mentioned (2-A) to (2-D) elements.

Specifically, the use of [(2-A) makes the rare earth element 0.05 to 1.0 atom%, (2-B) makes Cu 0.05 to 1.0 atom%, and/or makes Bi 0.25 to 5.0 atom%, ( 2-C) wherein at least one selected from the group consisting of Pd, Pt, and Au is 0.1 to 1.5 atom%, and (2-D) is Zn and/or In is 0.1 to 1.5 atom%] The Ag alloy sputtering target of at least one selected from the group consisting of may be used.

Basically, as long as an Ag alloy sputtering target containing these elements and having the same composition as the desired third layer (Ag alloy film) is used, the third layer (the desired composition) can be formed without compositional deviation. Ag alloy film). However, since Bi is an element which is easily splashed during the film formation process and is easily concentrated near the surface of the film, it is preferable to make Bi which is about 5 times the amount of Bi in the third layer (Ag alloy film). Plated in the target. The content of Bi is preferably 0.25 atom% or more, more preferably 0.35 atom% or more, still more preferably 0.5 atom% or more, and more preferably 5.0 atom% or less, more preferably less than the content of Bi in the film. 3.5 atom% or less, more preferably 2.5 atom% or less.

It is not necessary for one sputtering target to contain all the elements corresponding to the composition of the third layer (Ag alloy film). Sputtering targets containing a predetermined amount of elements are simultaneously sputtered (co-sputtered) for the desired composition The formation of the third layer (Ag alloy film) is also useful.

Although the above various methods are mentioned in the manufacturing method of the Ag alloy sputtering target, the vacuum melting method is preferable similarly to the above-mentioned Al alloy sputtering target.

In the case where the second layer (the oxide film or the nitride film of the Al alloy) is formed by the sputtering method, the third layer (Ag alloy film) may be formed by sputtering.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar, nitrogen, etc.

‧In the film formation (Ar) pressure: 1~5mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

Further, the shape of the Al alloy sputtering target and the Ag alloy sputtering target include the shape of the sputtering apparatus and the processing into an arbitrary shape depending on the structure (square plate shape, disk shape, doughnut plate shape). , cylindrical, etc.).

As described above, the first layer (Al alloy film), the second layer (the oxide film of the Al alloy or the nitride film), and the third layer (Ag alloy film) of the laminated film which is a characteristic part of the present invention are used. The explanation. Hereinafter, a display device and an input device using a laminated film including the first layer (Al alloy film), the second layer (the oxide film of the Al alloy or the nitride film), and the third layer (Ag alloy film) are used. Electrode used in the device The structure of the organic EL element as the reflective anode of the organic EL will be described.

However, the present invention is not limited to the above structure, and may be applied to electrodes such as a gate electrode, a source drain (source, drain), and the like in addition to the reflective electrode.

An organic EL display shown in FIG. 8 will be described as an example of a first layer (Al alloy film), a second layer (an oxide film or a nitride film of an Al alloy), and a third layer (Ag alloy film). The electrode formed of the laminated film is used as an organic EL element of a reflective electrode. In the following, the case where this organic EL element is applied to an organic EL display will be described. However, the application of the organic EL element is not limited to the organic EL display, and various known configurations such as organic EL illumination can be employed. Furthermore, the reflective electrode of the present invention is not limited to the reflective anode described above, and may be used for other reflective electrodes.

First, as shown in FIG. 8, on the substrate 21, a TFT 22 and a passivation film 23 are formed, and further, a planarization layer 24 is formed thereon. On the TFT 22, a contact hole 25 is formed. The source drain (not shown) of the TFT 22 is electrically connected to the first layer (Al alloy film) 26 constituting the reflective electrode of the present invention through the contact hole 25.

Further, a second layer (an oxide film or a nitride film of an Al alloy) 27 is formed directly above the first layer (Al alloy film) 26, and a third layer (Ag alloy film) 28 is formed directly above it. . The formation of the first layer (Al alloy film) 26, the second layer (the oxide film or nitride film of the Al alloy) 27, and the third layer (Ag alloy film) 28 can be carried out by the above method. Row.

Next, an organic layer 29 is formed on the third layer (Ag alloy film) 28. The organic layer 29 may include, for example, a hole transport layer, an electron transport layer, and the like in addition to the organic light-emitting layer. Further, a cathode 30 is formed on the organic layer 29. In the case of FIG. 8, the material constituting the cathode 30 is not particularly limited, and it can be constituted by a material that has been conventionally used.

In the above organic EL display, since the light emitted from the organic light-emitting layer in the organic layer 29 is efficiently reflected in the reflective anodes 26 to 28 (especially the third layer (Ag alloy film) 28) of the present invention, Achieve excellent brightness. Further, the higher the reflectance of the reflective electrode (the first layer (Al alloy film) 26, the second layer (the oxide film of the Al alloy or the nitride film) 27, and the third layer (the Ag alloy film) 28) The higher the higher the reflectance is 90% or more, preferably 93% or more.

Further, the higher the hole injection characteristics of the reflective anode to the organic layer 9, the better.

The reflective anode including the electrode of the present invention and the organic EL device including the electrode have been described above.

The electrodes of the display device of the present invention described above can be used as electrodes of various display devices (including input devices). Examples of the electrode that can be used include a gate electrode, a source drain (source, and a drain) for a thin film transistor in a liquid crystal display (LDC) illustrated in FIG. 2 described in the first invention. For example, the gate electrode and the source drain of the thin film transistor in the organic EL display (OELD) illustrated in FIG. 3, such as the cathode in the field emission display (FED) illustrated in FIG. 4, and the gate, for example, FIG. Illustration An anode in a fluorescent vacuum tube (VFD), such as an address electrode in a plasma display (PDP) illustrated in Fig. 6, for example, a back electrode in an inorganic EL display exemplified in Fig. 7.

Further, the electrode of the present invention can also be applied to an input device. The input device includes an input device such as a touch panel having an input means on the display device, and an input device not having a display device such as a touch panel. Specifically, the electrode of the present invention may be used in combination with the above various display devices and position input means, and the input device for operating the device by pressing the display on the screen, and the operation and the input position on the position input means are additionally provided. The electrodes of the input device of the display device (such as the various electrodes described above). Further, as the position input means, various known operational principles can be employed: a matrix switch, a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, a capacitive method, and the like.

When the electrode of the present invention is used as an electrode of such a display device or an input device, the above-described predetermined effects can be obtained and confirmed by experiments.

[Second Embodiment]

In the following, the second invention will be more specifically described by way of examples, but the present invention is not limited to the following examples, and it is of course possible to carry out the appropriate modifications in the scope that can be adapted to the purpose of the preceding and the following description, and the like. It is within the technical scope of the present invention.

(film formation)

A sputtering target having the same composition as that of the first layer (Al alloy film: residual portion is Al and unavoidable impurities) having the composition shown in Tables 4 to 6B (all of which are contained in atomic percentage of the alloy component) is prepared. (disc type with a diameter of 4 inches). Then, using the sputtering target, a first layer was formed on a glass substrate (an alkali-free glass, a plate thickness of 0.7 mm, and a diameter of 4 Å) by a DC magnetron sputtering apparatus according to the following sputtering conditions. Subsequently, the sputtering target used for the formation of the first layer (Al alloy film) is directly used to form the second layer directly on the first layer (Al alloy film) under the following sputtering conditions (Al alloy Oxide film or nitride film).

Then, in the second layer (the oxide film or the nitride film of the Al alloy), the third layer having the composition shown in Tables 4 to 6B is used (the Ag alloy film: the residual portion is Ag and cannot be avoided). Impurity) A sputtering target of the same composition (a disc shape having a diameter of 4 Å) was formed into a film under the following sputtering conditions to prepare a sample.

Further, No. 101 of Table 4 does not form the second layer (the oxide film of the Al alloy film or the nitride film). Further, in the first layer of No. 121 of Table 5, a pure Al sputtering target was used, and in the third layer of No. 201 and No. 233 of Table 6, a pure Ag sputtering target was used. The amount of Bi contained in the sputtering target in the case where Bi is contained in the third layer (Ag alloy film) is 5 times the amount of Bi in the third layer (Ag alloy film). For example, in the case of No. 121 of Table 5, a third layer (Ag alloy film) of Ag-0.1 at% Bi-1.0 at% Zn is formed using a sputtering target of Ag-0.5 at% Bi-1.0 at% Zn.

The first layer (Al alloy film) and the third layer after film formation The composition of the (Ag alloy film) was confirmed by Inductively Coupled Plasma (ICP) mass spectrometry. In the table, the content rates in "Layer 1" and "Layer 3" are all atomic %. Further, since the composition of the second layer (the oxide film or the nitride film of the Al alloy) is the same as that of the first layer, the first layer (Al alloy film) is the same as the first layer (Al alloy film), and is not shown in the table. Further, it was analyzed by X-ray spectroscopy (X-ray spectroscopy) whether or not the second layer was formed of an oxide film or a nitride film of an Al alloy. In the table, the "oxide film" means an oxide film of an Al alloy having the same composition as that of the Al alloy of the first layer, and the "nitride film" means the nitrogen of an Al alloy having the same composition as the Al alloy of the first layer. Chemical film.

(Layer 1: Al alloy sputtering conditions)

‧ substrate temperature: room temperature

‧Ar gas flow: 30sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 260W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

(Layer 2: Oxygen addition sputtering conditions)

‧ substrate temperature: room temperature

‧Ar gas flow: 27sccm

‧O ₂ gas flow: 3sccm

‧Ar pressure: 2mTorr

‧ ultimate vacuum: 3 × 10 ^-6 Torr

‧ Sputtering power: 260W

(Layer 2: Nitrogen addition sputtering conditions)

‧ substrate temperature: room temperature

‧Ar gas flow: 27sccm

‧N ₂ gas flow: 3sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 260W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

(Layer 3: Ag alloy sputtering conditions)

‧ substrate temperature: room temperature

‧Ar gas flow: 30sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 130W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

(Method for measuring film thickness)

The first layer (Al alloy film), the second layer (oxide film or nitride film of the Al alloy), and the third layer (Ag alloy) were measured by a probe surface profiler (manufactured by KLA-Tencor, Alpha-step). Each film thickness of the film). The film thickness of the total of three points was measured from the center of the film at a distance of 5 mm in the radial direction, and the average value was referred to as "thickness of the film" (nm). In addition, total The film thickness of the first layer (Al alloy film), the second layer (the oxide film or the nitride film of the Al alloy), and the third layer (the Ag alloy film) as the thickness of the laminated film (in the table, "total") ). The film thickness ratio of the third layer ("Ag alloy film thickness ratio" in the table) was calculated from the total film thickness.

(Processability evaluation)

A photoresist pattern having a line gap of 10 μm in width was formed on the sample (layer film) produced as described above to evaluate etching workability. Specifically, the laminated film was immersed in a mixed acid etching solution (phosphoric acid: nitric acid: acetic acid: water = 50:0.2:30:19.8) while heating to 40 ° C, and was performed during the etching end time + 20 seconds (percause time). Etching. The size of the wiring pattern after the etching was observed with an optical microscope (magnification: 1000 times), and the size of the wiring was measured, and the presence or absence of the residue was visually confirmed to evaluate the side etching. In the present example, evaluation was performed according to the following criteria: ◎ or ○ was judged to be acceptable (good etching property), and × was judged as unacceptable ("micromachining property" in the table).

◎: 9μm or more, and no residue

○: 8 μm or more, less than 9 μm, and no residue

×: less than 8 μm, or there are residual stains

(Measurement of reflectance after heat treatment)

After the heat treatment was performed at 300 ° C for 60 minutes on the sample prepared above, a spectrophotometer (manufactured by JASCO Corporation: visible ‧ ultraviolet spectrophotometry) was used according to JIS R 3106 by light having a wavelength of 380 to 780 nm under a D65 light source. The visible light reflectance was measured by "V-570". Specifically, the reflectance is obtained as follows from the reflected light intensity (measured value) of the sample prepared as described above with respect to the intensity of the reflected light of the reference mirror.

[Reflectance] (=[Reflected light intensity of sample/Reflected light intensity of reference mirror]×100%)

Then, in the present embodiment, the reflectance of the sample in λ = 450 nm was evaluated based on the following criteria, and ○ and Δ were judged as pass, and × was judged as unacceptable.

○: 93% or more

△: 90% or more, less than 93%

×: less than 90%

(Contact resistance)

It is easy to form a laminated film wiring of a first layer (Al alloy film) having a width of 10 μm and a second layer (an oxide film or a nitride film of an Al alloy) and a single layer wiring of a third layer (Ag alloy film). The Kelvin pattern was measured for contact resistance. Therefore, in the present example, evaluation was performed based on the following criteria, ◎, ○, and △ were acceptable, and × was judged as unacceptable.

◎: 10kΩ or less

○: More than 10kΩ~1MΩ

△: More than 1 MΩ to 100 MΩ or less

×: more than 100MΩ

Tables 4 to 6B show the results of the above tests.

Table 4 investigates the reflection of the first layer (Al alloy film), the second layer (the oxide film or nitride film of the Al alloy), and the third layer (Ag alloy film). The result of the effects of rate, micromachining, and contact resistance. The following can be seen from Table 4.

No. 101 is an example in which the second layer (the oxide film or the nitride film of the Al alloy) is not formed, and the reflectance is low.

In No. 105, since the film thickness of the second layer (the oxide film or the nitride film of the Al alloy) was too thick, the desired micro workability and contact resistance could not be obtained.

No. 102 and No. 109, No. 103 and No. 110, No. 104 and No. 111, No. 106 and No. 112, No. 107 and No. 113, No. 108 and No. 114 are layers. The film thickness is the same, and the structure of the second layer is an oxide film or a nitride film of an Al alloy. Good reflectance, micromachinability, and contact resistance were obtained in either case.

In particular, No. 106, 112 (30 nm) and No. 107 and 113 (200 nm) are examples in which the film thickness of the first layer (Al alloy film) is changed, and both exhibit good reflectance and micromachinability. Contact resistance.

From the above results, it was found that it is effective to increase the film thickness of the second layer (the oxide film or the nitride film of the Al alloy) and the thickness of the third layer (the Ag alloy film) in order to increase the reflectance.

In Table 5, the composition of the second layer (the oxide film or the nitride film of the Al alloy) and the third layer (the Ag alloy film), the film thickness, and the film thickness ratio are fixed, and the first layer (Al alloy) is appropriately changed. In the case of the composition, the results of such effects on reflectance, micromachinability, and contact resistance were investigated. The following can be seen from Table 5.

No. 121 is an example in which pure Al is used as the first layer. In this case, although the contact resistance and the micro-machining property are good, the reflectance is low.

No. 122 to 124, 126 to 128, 130, 131, and 133 are examples in which the preferable alloying elements of the present invention are added in an appropriate amount, and the reflectance, the micro-workability, and the contact resistance are good.

In particular, No. 133 is an example in which a plurality of preferable alloying elements of the present invention are added in an appropriate amount, and the reflectance, the micro-workability, and the contact resistance are good.

No. 125, 129, and 132 are examples in which the content of the alloying element is excessive, and the residue of the alloy component is confirmed in the first layer (Al alloy film) after the etching, and the micro-machining property is not good.

Tables 6A and 6B are the results of investigating the effects on the reflectance, the micro-workability, and the contact resistance in the case where the composition of the third layer (Ag alloy film) is appropriately changed. The following can be seen from Tables 6A and 6B.

No. 201 and No. 233 are examples in which pure Ag is the third layer. In these examples, the micro-workability and the contact resistance are good, but the reflectance is low.

No. 202 to 204 are examples in which a preferred alloying element of the present invention is added in an appropriate amount. As long as the content of the alloying element is within a predetermined range, desired results can be obtained simultaneously with reflectance, micromachinability, and contact resistance (No. 202 to 204). However, when the content of the alloying element is increased, the reflectance tends to be lowered (the reflectance in the case where the Nd content is 0.2 atom% is good (○), but it is ok when 1.0 atom% is ( △)).

No. 205 is an example in which the content of the alloying element is excessive, and the reflectance is lowered (not (x)).

The same tendency is also exhibited in No. 207 to No. 210 (No. 210 is an example in which the Bi content is poor in reflectance), and No. 211 to No. 214 (No. 214 is a Pd content having a large reflectance. Example), No. 217 to No. 220 (No. 220 is an example in which the Zn content is insufficient in reflectance), and No. 221 to No. 224 (No. 224 is an example in which the In content is insufficient in reflectance) No. 237 to No. 237 to No. 237 of Table 6B (No. 237 is an example in which the Nd content is insufficient in reflectance), and No. 239 to No. 242 (No. 242 is a case where the Bi content is large and the reflectance is poor. Example), No. 243 to No. 246 (No. 246 is Pd) Examples in which the amount of reflectance is not good), No. 249 to No. 252 (No. 252 is an example in which the Zn content is insufficient in reflectance), and No. 253 to No. 256 (No. 256 is in a large amount of In) Examples of poor reflectance). Accordingly, it has been found that when the content of the alloying element contained in the third layer (Ag alloy film) is too large, the reflectance is adversely affected.

Further, all of Nos. 206, 215, 216, 247, and 248 are examples in which the preferable alloying elements of the present invention are added in an appropriate amount, and all of the reflectance, the micro-workability, and the contact resistance are good.

Nos. 225 to 232 and Nos. 257 to 264 are examples in which a plurality of preferred alloying elements of the present invention are added in an appropriate amount, and reflectance, micromachinability, and contact resistance are good.

[Third invention]

Hereinafter, the third invention will be described in detail.

The present inventors have made intensive studies in order to solve the above problems. As a result, the present inventors have found that the present invention has been completed in that the electrode for a display device or an input device includes a first layer composed of an Al alloy from the substrate side, and (a) formed thereon. At least one selected from the group consisting of Mo, Mo alloy, Ti, Ti alloy, Ta, W, and Nb, and/or (b) a conductive oxide containing In oxide and/or Zn oxide The second layer formed and the third layer of the Ag alloy formed on the upper side of the second layer (the first layer, the second layer, and the third layer may be directly contacted or not in direct contact) ), appropriately controlling the film thickness of the electrode and constituting the layers of the electrode The film thickness can be.

The reason for achieving the third invention is as follows. In order to achieve a low wiring resistance, the film thickness of the Ag alloy film may be increased, but the problem that the amount of Ag used is increased and the manufacturing cost is increased. In addition, the increase in film thickness alone does not improve the adhesion. Then, a laminated film having a property of Al having excellent conductivity and excellent adhesion to a base layer (for example, a substrate, an insulating film, a planarizing layer, etc.) has been proposed (Patent Document 1). It is believed that by using such a laminated film, wiring resistance and adhesion can be improved without increasing the amount of Ag used.

However, a reflective electrode used for an organic EL display or the like requires high reflectance in addition to suppression of wiring resistance. For this reason, in the prior art as disclosed in Patent Document 1, since the thickness of the target anode is as thin as 100 to 300 nm, not only the wiring resistance is insufficient, but also the Ag alloy film is as thin as 50 to 80 nm, so that stability is ensured. The high reflectivity is also difficult. Further, the Al film is useful for improving the adhesion to the underlayer (for example, a substrate, an insulating film, a planarization layer, etc.), but it is difficult to ensure high reflectance because it does not have sufficient reflectance.

As a result of review by the present inventors, it was learned that while ensuring good adhesion, even if the electrode is thickened, a good wiring resistance and high reflectance are ensured, and pure Al (or Al oxide and Al intermetallic compound) are formed. In the case of the first layer on the substrate side, it is difficult to use an Al alloy film.

As a result of further review, it was learned that in the case of simply laminating an Al alloy film and an Ag alloy film, transparent oxygen such as ITO The thermal history of high temperature (for example, 300 ° C grade) in the process of forming a thin film transistor and an organic EL device, etc., formation of a conductive film and an insulating film, and diffusion of Al from the Al alloy film to the Ag alloy film, reflectance and wiring The resistance will deteriorate.

As a result of reviewing the constitution of such a problem, the present inventors have learned that the first layer (Al alloy film) and the third layer (Ag alloy film) are provided as an intermediate layer as described above. 2 layers (at least one selected from the group consisting of (a) from Mo, Mo alloy, Ti, Ti alloy, Ta, W, and Nb, and/or (b) containing In oxide, and/or Zn A film composed of a conductive oxide of an oxide; hereinafter, referred to as a "anti-diffusion film" is effective. In other words, it is understood that the second layer (anti-diffusion film) provided as an intermediate layer functions as an Al diffusion preventing layer, and prevents Al from diffusing from the first layer (Al alloy film) to the third layer (Ag). The alloy film) can suppress the decrease in the reflectance of the third layer (Ag alloy film).

On the other hand, it is understood that when the second layer (anti-diffusion film) is interposed, there is a problem in that the wiring resistance is increased when the second layer is thickened in order to increase the diffusion preventing effect, but it is appropriate to use it. By controlling the film thickness of the second layer, it is possible to obtain a good wiring resistance while exhibiting the above-described diffusion preventing effect.

The inventors of the present invention have produced a reflective electrode in which the first layer (Al alloy film), the second layer (anti-diffusion film), and the third layer (Ag alloy film) are laminated in this order in view of the effect of the formation of the intermediate layer. (Laminated film). Then, review the reflectivity and wiring resistance As a result, the following findings were obtained from Table 7 of the examples described later.

First, it is understood that when the second layer (anti-diffusion film) is not provided as in No. 301 of Table 7, diffusion of Al cannot be prevented, and the reflectance of the reflective electrode and the wiring resistance are deteriorated.

On the other hand, in the case of No. 302 to 304, when the film thickness of the second layer (anti-diffusion film) is appropriately controlled, a sufficient diffusion preventing effect is exhibited, and a good reflectance and wiring resistance are obtained.

However, as in No. 305, if the film thickness of the second layer (anti-diffusion film) is too thick, the wiring resistance is deteriorated.

Further, such a tendency is also the same when the composition of the second layer (anti-diffusion film) is different (No. 309 to 328).

The composition of the second layer (anti-diffusion film) of No. 329 to 331 is outside the specifications of the present invention, so that the reflectance and the wiring resistance are not good.

According to the above results, it has been found that in order to secure a good reflectance and wiring resistance, it is effective to appropriately control the composition and film thickness of the second layer (anti-diffusion film).

Further, although the following results are not shown in Table 7, it is understood that when the thickness of the third layer (Ag alloy film) is reduced, the reflectance is lowered. It is conceivable that the film thickness of the third layer (Ag alloy film) is inadvertently increased, and the light of the third layer (Ag alloy film) is increased, and the reflectance of the third layer (Ag alloy film) is lowered. At the same time, the reflectance of the first layer (Al alloy film) and the second layer (anti-diffusion film) with respect to the transmitted light is lower than that of the third layer (Ag alloy film).

In addition, I learned that if you want to have good adhesion on one side When ensuring the desired wiring resistance and reflectance, it is necessary to laminate not only the first layer (Al alloy film), the second layer (anti-diffusion film), and the third layer (Ag alloy film), but also a predetermined film thickness. Within the range, the ratio of the film thickness of the third layer (Ag alloy film) with respect to the total film thickness of the laminated film was appropriately controlled.

According to the above experimental results, it has been found that the present invention can be achieved by appropriately controlling the configuration of the electrodes, the constituent components of the respective layers, and the film thickness of each layer, and thickening the electrode (to, for example, 800 nm level) in order to obtain good wiring resistance. , still can ensure good above characteristics.

Next, the inventors of the present invention reviewed the influence of the composition of the first layer (Al alloy film) constituting the electrode on the reflectance and the wiring resistance (see Table 8).

First, when various alloying elements are added to the first layer (Al alloy film) and the relationship with the above characteristics is investigated, it is learned that among the alloying elements, especially rare earth elements, Ti, Ta, W, and Nb are suitable for improvement of reflectance. . Further, it has been found that when these alloying elements are added, there is a preferable content in terms of reflectance and wiring resistance.

No. 351 of Table 8 is an example of a pure Al film. In the case of this example, although the wiring resistance is good, the reflectance required for the reflective electrode cannot be satisfied.

On the other hand, No. 352 to 354 are examples in which an alloying element is added. In such an example, when the alloy element of the first layer (Al alloy film) is appropriately controlled, good reflectance and wiring resistance are obtained.

Further, No. 355 is an example in which the content of the alloy element is excessive. In the case of this example, the alloy of the first layer (Al alloy film) Since the content of the element is excessive, the wiring resistance is deteriorated.

In addition, as shown in No. 351 to 355, even if the composition of the second layer (anti-diffusion film) is different (Mo, Ti, ITO), the same is true (No. 359 to 363, No. 367 to 371). .

Further, although not described in the table, the first layer is not related to the composition, and the adhesion to the substrate is excellent, and there is no peeling.

From the results, it is understood that the first layer (Al alloy film) can exhibit good adhesion and exhibit good adhesion as long as the reflectance of the Al alloy is increased. However, if the content of the alloying element is excessive, the electrical resistivity becomes high and the wiring resistance deteriorates. The situation. For this reason, the amount of the alloying element added is appropriately controlled to be preferable.

In addition, the present inventors investigated the relationship with the above characteristics by adding various alloying elements to the third layer (Ag alloy film) in the same manner as the first layer (Al alloy film). As a result, it was found that among the alloying elements, especially rare earth elements, Bi, Cu, Pd, Pt, Au, In, and Zn are added to the third layer, which is suitable for improvement in reflectance and wiring resistance (refer to Tables 9A and 9B, 9C). Further, when these alloying elements are added, there is a preferable content in terms of the relationship between the reflectance and the wiring resistance.

No. 401 of Table 9A is an example of a pure Ag film. In the case of this example, the reflectance is low and the reflectance required for the reflective electrode cannot be satisfied.

On the other hand, Nos. 402 to 404 are examples in which alloying elements are added. In such an example, if the alloying element of the third layer (Ag alloy film) is appropriately controlled, good reflectance and wiring resistance are obtained.

In addition, No. 405 is an excessive amount of alloying elements. example. When the content of the alloying element of the third layer (Ag alloy film) is excessive as in the case, the reflectance is lowered.

In addition, as shown in No. 401 to 405, when the types of alloying elements in the third layer are different (No. 407 to 410, etc.) and the composition of the second layer (diffusion preventing layer) are different, The same is true (Table 9B, Table 9C).

From the experimental results shown in Tables 7, 8, 9A, 9B, and 9C, it is learned that if a good reflectance and wiring resistance are to be obtained, it is necessary to provide the second layer of a predetermined composition with a predetermined film thickness (diffusion prevention). At the same time, it is necessary to appropriately control the composition and film thickness of the first layer (Al alloy film) and the third layer (Ag alloy film). Then, in the present invention, according to such a result, the film composition is specified for the appropriate composition and the content thereof as described later.

Hereinafter, an electrode for a display device or an input device of the present invention will be described.

(composition of electrodes)

The electrode for a display device or an input device of the present invention comprises a laminate film comprising: a first layer made of an Al alloy formed on a substrate side, and (a) a Mo and Mo alloy formed thereon. At least one selected from the group consisting of Ti, a Ti alloy, Ta, W, and Nb, and/or (b) a second oxide consisting of a conductive oxide containing an In oxide and/or a Zn oxide The layer and the third layer formed of an Ag alloy formed on the upper side of the second layer.

In the laminated film of the present invention, the first layer (Al alloy film), the second layer (diffusion film), and the third layer (Ag alloy film) are sequentially laminated in this order from the substrate side. Construction is also a preferred embodiment.

Further, the laminated film of the present invention is not limited thereto, and may include any layer (fourth layer). Therefore, an arbitrary fourth layer (arbitrary) may be formed between the first layer (Al alloy film) and the second layer (diffusion prevention film), the second layer (diffusion prevention film), and the third layer (Ag alloy film). a component of the film). As the fourth layer, a known adhesiveness-promoting film or the like which contributes to an improvement in adhesion is exemplified.

(film thickness of the electrode)

In the present invention, the thickness of the electrode (layered film) is set to 100 to 800 nm. When the film thickness is less than 100 nm, there is a problem in that the wiring resistance is increased and a stable reflectance or the like is not obtained. On the other hand, when the film thickness exceeds 800 nm, the coverage of the upper layer film (passivation film or the like) is deteriorated to cause a problem such as a fracture. The film preferably has a film thickness of 120 nm or more, more preferably 150 nm or more, more preferably 700 nm or less, still more preferably 500 nm or less.

(film thickness of the first layer (Al alloy film))

The first layer (Al alloy film) reflects light passing through the second layer (anti-diffusion film) and the third layer (Ag alloy film), and serves as a layer that promotes adhesion to the underlying layer. Al alloy film has a base layer and Ag Since the adhesiveness of the two layers is excellent, the peeling resistance of the electrode composed of the laminated film of the present invention is improved.

The film thickness of the first layer (Al alloy film) may be appropriately adjusted to the film thickness of the electrode in accordance with the relationship between the second layer (anti-diffusion film) and the third layer (Ag alloy film). The film thickness of the first layer (Al alloy film) is preferably 27 nm or more, more preferably 33 nm or more, still more preferably 42 nm or more. On the other hand, when the film thickness of the first layer (Al alloy film) is too thick, the film thickness of the third layer (Ag alloy film) is too thin and the reflectance is lowered in accordance with the film thickness of the electrode. In addition, the effect of the second layer (anti-diffusion film) sufficient is not obtained. Therefore, the film thickness of the first layer (Al alloy film) is preferably 717 nm or less, more preferably 627 nm or less, still more preferably 447 nm or less.

(film thickness of the second layer (anti-diffusion film))

The second layer (anti-diffusion film) plays the role of a diffusion preventing layer of Al from the first layer (Al alloy film) to the third layer (Ag alloy film). From the viewpoint of ensuring sufficient diffusion barrier properties, the film thickness needs to be 3 nm or more, preferably 4 nm or more, and more preferably 5 nm or more. On the other hand, when the film thickness of the second layer (anti-diffusion film) is too thick, the ratio of the second layer having a high specific resistance to the entire wiring increases, and the wiring resistance increases. From this, it is understood that the film thickness of the second layer needs to be 50 nm or less, preferably 30 nm or less, and more preferably 20 nm or less.

(film thickness of the third layer (Ag alloy film))

The third layer (Ag alloy film) particularly plays the role of a reflective film in the reflective electrode. In order to secure high reflectance, the film thickness of the third layer needs to be 60 nm or more, preferably 90 nm or more, and more preferably 100 nm or more. On the other hand, from the viewpoint of the improvement of the reflectance and the wiring resistance, the upper limit is not limited, but even if the thickness of the third layer (Ag alloy film) is too thick, the surface damage is increased, so that the effect of improving the reflectance is saturated. At the same time, with the increase in the amount of Ag used, the manufacturing cost will also increase. Therefore, the film thickness of the third layer needs to be 480 nm or less, preferably 400 nm or less, more preferably 300 nm or less.

(film thickness ratio of the third layer)

The third layer (Ag alloy film) accounts for 10 to 70% of the film thickness (100 to 800 nm) of the electrode (laminated film) of the present invention. When the film thickness ratio of the third layer (Ag alloy film) is lowered, a desired reflectance cannot be obtained. Therefore, the film thickness ratio of the third layer (Ag alloy film) needs to be 10% or more, preferably 15% or more. More preferably, it is more than 20%. On the other hand, when the ratio of the third layer (Ag alloy film) is too high, the effect of improving the reflectance is saturated, and the amount of use of Ag increases, and the manufacturing cost also increases. Therefore, the film thickness ratio of the third layer (Ag alloy film) needs to be 70% or less, preferably 50% or less, more preferably 40% or less, still more preferably 30% or less.

(component of the first layer (Al alloy film))

In the present invention, the composition of the first layer (Al alloy film) is not In particular, the composition of the conventionally used Al alloy film can be used. However, in order to exhibit good adhesion, reflectance, and wiring resistance, it is preferred that the following alloy elements are within a predetermined range.

The alloying element added to the first layer (Al alloy) preferably contains [(1-A) such that the rare earth element is 0.05 to 1.0 atomic %, and/or (1-B) is made from Ti, Ta, W, and Nb. At least one selected from the group consisting of 0.05 to 0.7 atom%]. These elements can be added individually or in combination of any two. That is, any one of the (1-A) group and the (1-B) group may be used alone, or all (two groups) may be used in combination. Further, the elements constituting each group may be used alone or in combination of two or more kinds. The same is true for the sputtering target described later.

Further, the content of each group is a single content when it is separately contained, and is a total amount when a plurality of elements are included. The second layer (anti-diffusion film) and the third layer (Ag alloy film) are also the same.

The Al alloy is preferably adjusted so as to have an Al content of preferably 90 atom% or more, more preferably 95 atom% or more, in terms of the above effect.

The Al alloy constituting the first layer preferably contains the above elements, and the residual portion is Al and unavoidable impurities.

(1-A) makes the rare earth element 0.05~1.0 atom%

The rare earth element is an element which suppresses the coarsening of the structure of the Al alloy and contributes to the suppression of the decrease in reflectance. In order to exert such an effect, the content of the rare earth element is preferably 0.05 atom% or more, more preferably 0.1 atom%. Further, it is more preferably 0.15 atom% or more. From the viewpoint of suppressing the coarsening of the structure, the content of the rare earth element is preferably as large as possible, but if the amount is too large, the reflectance is lowered and the resistivity is cracked. For this reason, the content is preferably 1.0 atom% or less, more preferably 0.8 atom% or less, still more preferably 0.6 atom% or less.

The above rare earth element means a lanthanoid element (a total of 15 elements of Lu of atomic sequence 57 to Lu of atomic sequence 71 in the periodic table) plus an element group of Sc (钪) and Y (钇). A preferred rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce (better rare earth elements are Nd, La).

(1-B) making at least one selected from the group consisting of Ti, Ta, W, and Nb 0.05 to 0.7 at%

Ti, Ta, W, and Nb are the same as the above-described rare earth element, and are elements which suppress the coarsening of the structure and contribute to the suppression of the decrease in reflectance. In order to exert such an effect, the content of at least one selected from the group consisting of Ti, Ta, W, and Nb is preferably 0.05 atom% or more, more preferably 0.1 atom% or more, and still more preferably 0.15 atom% or more. From the viewpoint of the above-described roughening suppression, the content of Ti, Ta, W, and Nb is preferably as large as possible, but if it is too large, the reflectance is lowered and the electrical resistivity is deteriorated. For this reason, the content is preferably 0.7 atom% or less, more preferably 0.5 atom% or less, still more preferably 0.4 atom% or less. The preferred elements among these are Ti and Ta.

As a constituent component of a preferred first layer (Al alloy film) containing the alloy elements of the above (1-A) and (1-B) groups, Al-0.2 is exemplified. Atomic % Nd, Al - 0.2 Atomic % Nd - 0.3 Atomic % Ta.

(component of layer 2 (anti-diffusion film))

The second layer (anti-diffusion film) prevents Al from diffusing from the first layer (Al alloy) to the third layer (Ag alloy), and is intended to exhibit a good reflectance and a wiring resistance. It needs to be composed of the following components.

That is, the constituent component constituting the second layer is at least one selected from the group consisting of [(a) from Mo, Mo alloy, Ti, Ti alloy, Ta, W, and Nb, and (b) inclusion. At least one selected from the group consisting of In oxides and/or conductive oxides of Zn oxides. Any one of the group (a) and the group (b) may be used alone, or two groups may be used in combination, and the elements constituting each group may be used singly or in combination of two or more kinds. The same is true for the sputtering target described later.

These components have a diffusion preventing effect of Al, contributing to an improvement in reflectance and a reduction in wiring resistance.

As a component of the preferred second layer, Mo is exemplified. In addition, as a preferable alloy component of the Mo alloy and the Ti alloy constituting the second layer, a Mo-Nb alloy, a Mo-Ta alloy, a Mo-Ti alloy, or the like is exemplified.

Further, the conductive oxide constituting the second layer contains In oxide and/or Zn oxide, preferably ITO (indium tin oxide) or IZO (indium zinc oxide).

The metal element constituting the second layer is preferably the above element, and the remaining portion is an unavoidable impurity.

(component of the third layer (Ag alloy film))

In the present invention, the composition of the third layer (Ag alloy film) is not particularly limited, and a constituent component of a conventionally used Ag alloy film can be used. However, in order to exhibit good reflectance and electrical resistivity, it is preferred that the following alloy elements are within a predetermined range.

It is preferable to contain from 0.05 to 1.0 atom% of [(2-A) rare earth element, (2-B) to make Bi and/or Cu 0.05 to 1.0 atom%, and (2-C) to make Pd, Pt, And at least one selected from the group consisting of: 0.1 to 1.5 atomic %, and (2-D) Zn and/or In is 0.1 to 1.5 atom%. As an alloying element. Any one of the above-mentioned (2-A) to (2-D) groups may be used alone, or a plurality of groups (arbitrary two or more groups) may be used in combination. In addition, the elements constituting each group may be used singly or in combination of two or more kinds. Further, the content of each group is a single content or a total amount as described above. The same is true for the sputtering target described later.

In a more preferable embodiment, the Ag alloy is adjusted so that 98 atom% or more of the Ag alloy and 99.98 atom% or less are Ag in accordance with the above-described effects (especially, reflectance).

The Ag alloy constituting the third layer preferably contains the above elements, and the residual portion is Ag and unavoidable impurities.

(2-A) making the rare earth element 0.05~1.0 atom%

Rare earth element inhibits the growth of Ag crystal grains according to thermal history An element which reduces the reflectance and contributes to aggregation inhibition (halogen resistance) caused by halide ions. In order to exert such an effect, the content of the rare earth element is preferably 0.05 atom% or more, more preferably 0.1 atom% or more, still more preferably 0.15 atom% or more. From the viewpoint of the above-mentioned effects improvement, although the content of the rare earth element is preferably a large amount, if the amount is too large, the reflectance may be lowered. For this reason, the content is preferably 1.0 atom% or less, more preferably 0.7 atom% or less, still more preferably 0.5 atom% or less.

The rare earth element is the same as the above first layer, and means a lanthanoid element, Sc, and Y. A preferred rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce (better rare earth elements are Nd, La).

(2-B) making Bi and/or Cu 0.05 to 1.0 atom%

Bi and Cu are the same as the above-mentioned rare earth elements, and are elements which contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance. In order to exert such an effect, the content of Bi and/or Cu is preferably 0.05 atom% or more, more preferably 0.07 atom% or more, still more preferably 0.1 atom% or more. From the viewpoint of the above-described effects, the content of Bi and Cu is preferably a large amount, but if the amount is too large, the reflectance may be lowered. The content of Bi and/or Cu is preferably 1.0% by atom or less, more preferably 0.7% by atom or less, still more preferably 0.5% by atom or less. The preferred element among these is Bi.

(2-C) making at least one selected from the group consisting of Pd, Pt, and Au 0.1 to 1.5 atom%

Pd, Pt, and Au are the same as the above-mentioned rare earth elements, Bi and Cu, and contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance. In order to exert such an effect, the content of at least one selected from the group consisting of Pd, Pt, and Au is preferably 0.1 atom% or more, more preferably 0.15 atom% or more, still more preferably 0.2 atom. %the above. From the viewpoint of the above-mentioned effects, the content of Pd, Pt, and Au is preferably a large amount, but if the amount is too large, the reflectance may be lowered. For this reason, the content is preferably 1.5 atom% or less, more preferably 1.0 atom% or less, still more preferably 0.8 atom% or less. The preferred elements among these are Pd, Pt.

(2-D) making Zn and/or In 0.1 to 1.5 atom%

Zn and In are the same as the above-mentioned elements, and contribute to the growth inhibition of Ag crystal grains and the improvement of halogen resistance while contributing to the improvement of oxidation resistance and sulfur resistance. In order to exert such an effect, the content of Zn and/or In is preferably 0.1 atom% or more, more preferably 0.3 atom% or more, still more preferably 0.5 atom% or more. From the viewpoint of the improvement of the above-mentioned effects, although the content of Zn and In is preferable, the reflectance may be lowered if it is excessive, and therefore the content is preferably 1.5 atom% or less, more preferably 1.3 atom. % or less, more preferably 1.1 atom% or less. A preferred element is Zn.

As a component of the preferable third layer (Ag alloy film) containing the alloy element of the above (2-A) to (2-D) group, Ag-0.3 at% Bi-0.5 at% Nd is exemplified.

(Formation method of the first layer (Al alloy film))

Examples of the method for forming the first layer (Al alloy film) contained in the laminated film of the constituent electrode of the present invention include a sputtering method and a vacuum vapor deposition method. In the present invention, it is possible to form a first layer (Al) by using a sputtering target in a sputtering method from the viewpoint of thinning and homogenization of alloy components in a film, and easy control of the amount of added elements. An alloy film) is preferred.

When the first layer (Al alloy film) is formed by a sputtering method, an element corresponding to (1-A) and (1-B) constituting the first layer (Al alloy film) is used. Al alloy sputtering targets are useful. Specifically, at least one selected from the group consisting of Ti, Ta, W, and Nb containing [(1-A) such that the rare earth element is 0.05 to 1.0 atomic %, and/or (1-B) An Al alloy sputtering target of 0.05 to 0.7 at%] is preferred.

Basically, as long as an Ag alloy sputtering target containing these elements and having the same composition as the desired first layer (Al alloy film) is used, the first layer of the desired composition can be formed without composition variation. Al alloy film).

However, the sputtering target is not required to contain all the elements corresponding to the composition of the first layer (Al alloy film) in one sputtering target. Simultaneous sputtering (co-sputtering) of a sputtering target containing a predetermined amount of elements is also useful for forming a first layer (Al alloy film) of a desired composition.

Examples of the method for producing the Al alloy sputtering target include a vacuum melting method and a powder sintering method, but from the viewpoint of ensuring the composition and the uniformity of the structure in the surface of the target, in particular, by vacuum melting. system Better.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar, nitrogen, etc.

‧In the film formation (Ar) pressure: 1.0~5.0mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

(Method of forming the second layer (anti-diffusion film))

The method for forming the second layer (anti-diffusion film) contained in the laminated film of the constituent electrode of the present invention is not particularly limited, and a sputtering method or the like can be used similarly to the first layer (Al alloy film).

For the same reason as the first layer (Al alloy film) described above, it is preferable to form a second layer (anti-diffusion film) by using a sputtering target in the sputtering method.

When a second layer (anti-diffusion film) is formed, if a sputtering target having the composition components corresponding to the above (a) and (b) of the second layer (diffusion prevention film) is used, there is no composition variation or the like.虞, a second layer (anti-diffusion film) of a desired composition can be formed. Specifically, at least one selected from the group consisting of [(a) from Mo, Mo alloy, Ti, Ti alloy, Ta, W, and Nb, and/or (b) contains In oxide, and A sputtering target composed of a conductive oxide of Zn oxide is suitable. Of course, similar to the first layer (Al alloy film) described above, Sputtering (co-sputtering) is also a useful film forming method.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar, nitrogen, etc.

‧In the film formation (Ar) pressure: 1.0~5.0mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

(Method of forming the third layer (Ag alloy film))

A method of forming the third layer (Ag alloy film) constituting the electrode may be the same as the above-described first layer (Al alloy film). However, for the same reason as the first layer (Al alloy film), the third layer (Ag alloy film) is preferably formed by using a sputtering target in the sputtering method.

When the third layer (Ag alloy film) is formed by sputtering, it is useful to use an Ag alloy sputtering target containing any of the above-mentioned (2-A) to (2-D) elements.

Specifically, the use of [(2-A) makes the rare earth element 0.05 to 1.0 atom%, (2-B) makes Cu 0.05 to 1.0 atom%, and/or makes Bi 0.25 to 5.0 atom%, ( 2-C) wherein at least one selected from the group consisting of Pd, Pt, and Au is 0.1 to 1.5 atom%, and (2-D) is Zn and/or In is 0.1 to 1.5 atom%] The Ag alloy sputtering target of at least one selected from the group consisting of may be used.

Basically, by using an Ag alloy sputtering target having the same composition as the desired third layer (Ag alloy film), the third layer (Ag alloy film) having a desired composition can be formed without a composition variation. However, Bi is an element which is easily splashed during the film formation process and is easily concentrated near the surface of the film. For this reason, it is preferable that Bi which is about 5 times the amount of Bi in the third layer (Ag alloy film) is contained in the sputtering target. The Bi content is preferably 0.25 atom% or more, more preferably 0.35 atom% or more, still more preferably 0.5 atom% or more, more preferably 5.0 atom% or less, still more preferably 3.5 atom%, in terms of the Bi content in the film. Hereinafter, it is more preferably 2.5 atom% or less.

Of course, in the same manner as the first layer (Al alloy film) described above, simultaneous sputtering (co-sputtering) is also useful for forming a third layer (Ag alloy film) of a desired composition.

Although the above various methods are mentioned in the manufacturing method of the Ag alloy sputtering target, the vacuum melting method is preferable similarly to the above-mentioned Al alloy sputtering target.

The film formation conditions in the sputtering method are not particularly limited, and it is preferred to employ, for example, the following conditions.

‧ substrate temperature: room temperature ~ 150 ° C

‧Atmosphere gas: inert gas such as Ar, nitrogen, etc.

‧In the film formation (Ar) pressure: 1~5mTorr

‧ Sputtering power: 100~2000W

‧ Ultimate vacuum: 1 × 10 ^-5 Torr or less

In addition, the shape of the sputter target used includes sputtering The shape of the device and the shape to be processed according to the structure (square plate shape, disk shape, donut plate shape, cylindrical shape, etc.).

The first layer (Al alloy film), the second layer (anti-diffusion film), and the third layer (Ag alloy film) of the laminated film which is a characteristic part of the present invention have been described above.

In the following, an electrode used in a display device and an input device using a laminated film including the first layer (Al alloy film) second layer (anti-diffusion film) and the third layer (Ag alloy film) is used as The structure of the organic EL element of the reflective electrode of the organic EL will be described.

However, the present invention is not limited to the above structure, and may be applied to electrodes such as a gate electrode, a source drain (source, drain), and the like in addition to the reflective electrode.

An organic EL display shown in FIG. 9 will be described as an example of a laminated film including the first layer (Al alloy film), the second layer (anti-diffusion film), and the third layer (Ag alloy film) of the present invention. The electrode is configured as an organic EL element that reflects the anode. In the following, the organic EL device is applied to an organic EL display. However, the application of the organic EL device is not limited to the organic EL display, and various known configurations such as organic EL illumination can be employed. Furthermore, the reflective electrode of the present invention is not limited to the reflective anode described above, and may be used for other reflective electrodes.

First, as shown in FIG. 9, on the substrate 31, a TFT 32 and a passivation film 33 are formed, and further, a planarization layer 34 is formed thereon. On the TFT 32, a contact hole 35 is formed. Through the contact hole 5, the source drain (not shown) of the TFT 32 and the first layer constituting the reflective electrode of the present invention (Al alloy film) 36 is electrically connected.

Further, a second layer (anti-diffusion film) 37 is formed directly above the first layer (Al alloy film) 36, and a third layer (Ag alloy film) 38 is formed directly above the layer. The formation of the first layer (Al alloy film) 36, the second layer (diffusion prevention film) 37, and the third layer (Ag alloy film) 38 can be carried out by the above method.

Next, an organic layer 39 is formed on the third layer (Ag alloy film) 38. The organic layer 39 may include, for example, a hole transport layer, an electron transport layer, and the like in addition to the organic light-emitting layer. Further, a cathode 40 is formed over the organic layer 39. In the case of FIG. 9, the material constituting the cathode 40 is not particularly limited, and it can be constituted by a material used in the past.

In the above organic EL display, since the light emitted from the organic light-emitting layer in the organic layer 39 is efficiently reflected in the reflective anode 36 to 38 (particularly the third layer (Ag alloy film) 38) of the present invention, Achieve excellent brightness. Further, the higher the reflectance of the reflective electrode (the first layer (Al alloy film) 36, the second layer (diffusion prevention film) 37, and the third layer (Ag alloy film) 38), the higher the value can be obtained. The reflectance is % or more, preferably 93% or more.

In addition, the higher the hole injection characteristics of the reflective anode to the organic layer 39, the better.

The reflective electrode including the electrode of the present invention and the organic EL device including the electrode have been described above.

The electrodes of the display device of the present invention described above can be used as electrodes of various display devices (including input devices). Applicable electrode For example, the gate electrode and the source drain (source, drain) for the thin film transistor in the liquid crystal display (LDC) illustrated in FIG. 2 described in the first invention are exemplified, for example, as illustrated in FIG. 3 . a gate electrode for a thin film transistor in an organic EL display (OELD), a source drain, such as a cathode in a field emission display (FED) illustrated in FIG. 4, and a gate, such as the fluorescent vacuum tube illustrated in FIG. An anode in (VFD), for example, an address electrode in a plasma display (PDP) illustrated in Fig. 6, for example, a back electrode in an inorganic EL display exemplified in Fig. 7.

Further, the electrode of the present invention can also be applied to an input device. The input device includes an input device such as a touch panel having an input means on the display device, and an input device not having a display device such as a touch panel. Specifically, the electrode of the present invention may be used in combination with the above various display devices and position input means, and the input device for operating the device by pressing the display on the screen, and the operation and the input position on the position input means are additionally provided. The electrodes of the input device of the display device (such as the various electrodes described above). Further, as the position input means, various known operational principles can be employed: a matrix switch, a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, a capacitive method, and the like.

When the electrode of the present invention is used as an electrode of such a display device or an input device, the above-described predetermined effects can be obtained and confirmed by experiments.

[Third embodiment]

Hereinafter, the third invention will be described more specifically by way of examples, but the present invention It is to be understood that the invention is not limited by the following examples, and may be carried out by appropriately changing the scope of the present invention, which is suitable for the purpose of the present invention.

(film formation)

A sputtering target having the same composition as that of the first layer (Al alloy film: residual portion is Al and unavoidable impurities) having the composition components shown in Tables 7 to 9C (all of which are contained in the alloy component) is prepared. (disc type with a diameter of 4 inches). Using this sputtering target, a first layer was formed on a glass substrate (an alkali-free glass, a plate thickness of 0.7 mm, and a diameter of 4 Å) by a DC magnetron sputtering apparatus according to the following sputtering conditions.

Then, a sputtering target (a disc type having a diameter of 4 Å) having the same composition as that of the second layer (the diffusion-proof film: an unavoidable impurity other than the predetermined component) shown in Tables 7 to 9C (the diffusion-preventing film) is prepared. Using this sputtering target, a second layer was formed on the first layer (Al alloy film) directly under the sputtering conditions in the same sputtering apparatus as in the first layer.

Subsequently, a sputtering target (a disc shape having a diameter of 4 Å) having the same composition as that of the third layer (Ag alloy film: residual portion being Ag and unavoidable impurities) having the composition shown in Tables 7 to 9C was used. Each of the samples was prepared by forming a third layer directly above the second layer (anti-diffusion film) under the following sputtering conditions.

Further, in the case of No. 301 of Table 7, the second layer (anti-diffusion film) was not formed. In the first layer of No. 351, 359, and 367 of Table 8, a pure Al sputtering target was used, and No. 401 and Table 9B of Table 9A were used. A pure Ag sputtering target was used for the third layer of No. 433 and No. 465 of Table 9C. The amount of Bi contained in the sputtering target in the case where Bi is contained in the third layer (Ag alloy film) is five times the amount of Bi in the third layer (Ag alloy film). For example, in the case of No. 351 of Table 8, a third layer (Ag alloy film) of Ag-0.1 at% Bi-1.0 at% Zn was formed using a sputtering target of Ag-0.5 at% Bi to 1.0 at% Zn.

The composition of the first layer (Al alloy film), the second layer (anti-diffusion film), and the third layer (Ag alloy film) after film formation was confirmed by Inductively Coupled Plasma (ICP) mass spectrometry .

Layer 1: Al alloy sputtering conditions

‧ substrate temperature: room temperature

‧Ar gas flow: 30sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 260W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

Layer 2: Sputtering conditions

(a) Mo, Mo alloy, Ti, Ti alloy, Ta, W, and Nb

‧ substrate temperature: room temperature

‧Ar gas flow: 27sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 260W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

(b) Conductive oxygen containing In oxide and/or Zn oxide Compound

‧ substrate temperature: room temperature

‧Ar+O ₂ gas flow: 19sccm

‧O ₂ ratio = 5%

‧Ar+O ₂ pressure: 2mTorr

‧ Sputtering power: 200W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

Layer 3: Ag alloy sputtering conditions

‧ substrate temperature: room temperature

‧Ar gas flow: 30sccm

‧Ar pressure: 2mTorr

‧ Sputtering power: 130W

‧ ultimate vacuum: 3 × 10 ^-6 Torr

(Method for measuring film thickness)

The film thicknesses of the first layer (Al alloy film), the second layer (diffusion film), and the third layer (Ag alloy film) were measured by a probe surface profiler (manufactured by KLA-Tencor, Alpha-step). The film thickness of the total of three points was measured from the center of the film at a distance of 5 mm in the radial direction, and the average value was referred to as "thickness of the film" (nm). In addition, the film thickness of the first layer (Al alloy film), the film thickness of the second layer (anti-diffusion film), and the third layer (Ag alloy film) are used as the film thickness of the laminated film (in the table, "total") . The film thickness ratio of the third layer was calculated from the total film thickness ("the third layer film thickness ratio" in the table).

(Measurement of reflectance after heat treatment)

After the heat treatment was performed at 300 ° C for 60 minutes on the sample prepared above, a spectrophotometer (manufactured by JASCO Corporation: visible ‧ ultraviolet spectrophotometer) was used according to JIS R 3106 for light having a wavelength of 380 to 780 nm under a D65 light source. "V-570") was measured for visible light reflectance. Specifically, the reflectance is obtained as follows from the reflected light intensity (measured value) of the sample prepared as described above with respect to the intensity of the reflected light of the reference mirror.

[Reflectance] (=[Reflected light intensity of sample/Reflected light intensity of reference mirror]×100%)

Then, in the present embodiment, the reflectance of the sample in λ = 450 nm was evaluated based on the following criteria, ○ was judged as pass, and × was judged as unacceptable.

○: 90% or more

×: less than 90%

(wiring resistance)

After the heat treatment was performed at 300 ° C for 60 minutes on the sample prepared above, the sheet resistance of each sample was measured. Specifically, the sheet resistance was measured by a four-terminal method generally used. The resistivity was calculated from the sheet resistance and the film thickness described above. Therefore, in the present embodiment, compared with the case where the separately prepared Al alloy single layer film (composition: Al-0.2 at % Nd) and the second layer (anti-diffusion film) are not provided (No. 301 of Table 7) Lower wiring resistance is higher If it is × (failed), the wiring resistance is the same or lower, and it is evaluated as ○ (passed).

The above 10 μm wide line gap is first heated to 40 ° C and the mixed film is immersed in a mixed acid etching solution (phosphoric acid: nitric acid: acetic acid: water = 50:0.2:30:19.8) and at the end of the etching time +20 seconds (percause time) During the etching, it is formed.

(adhesiveness)

The presence or absence of peeling of the substrate and the laminated film of each of the samples prepared above was visually confirmed. As a result, peeling of the laminated film was not confirmed for all the samples, and the adhesiveness was good.

Tables 7 to 9 show the results of the above tests.

Table 7 shows the case where the film thickness of the first layer (Al alloy film), the second layer (diffusion film), and the third layer (Ag alloy film) and the composition of the second layer (anti-diffusion film) are changed. Investigate the results of these effects on reflectance and wiring resistance. The following can be seen from Table 7.

No. 301 is an example in which the second layer (anti-diffusion film) is not formed, and the reflectance and wiring resistance are not good.

In Nos. 305, 312, and 324, since the film thickness of the second layer (anti-diffusion film) was too thick, a desired wiring resistance could not be obtained.

No. 329-331 is an example in which the constituent components of the second layer (anti-diffusion film) do not conform to the provisions of the present invention. In these cases, the reflectance and wiring resistance are not good.

On the other hand, No. 302 to 304, 306 to 311, 313 to 323, and 325 to 328 are examples in which the components of the second layer of the present invention and other elements are satisfied, and good wiring resistance and reflectance are obtained.

Table 8 shows the results of investigating the influence of the composition of the first layer on the reflectance and the wiring resistance in the case where the composition of the first layer (Al alloy) was appropriately changed. The following can be seen from Table 8.

No. 351, 359, and 367 are examples in which pure Al is used in the first layer. In these examples, the wiring resistance is good, but the reflectance is low.

No. 355, 363, and 371 are examples in which the content of the alloy element is excessive, and the wiring resistance is deteriorated.

No.352~354, 356~358, 360~362, 364~366, 368~370, 372~374 are examples of the composition of the first layer of the invention and other requirements, and obtain good wiring resistance and reflection. rate.

Tables 9A, 9B, and 9C are the results of investigating the influence on the reflectance and the wiring resistance when the composition of the third layer (Ag alloy film) is appropriately changed. The following can be understood from Tables 9A, 9B, and 9C.

No. 401, 433, and 465 are examples in which a pure Ag film is the third layer. In these examples, the wiring resistance is good, but the reflectance is low.

No. 405, 410, 414, 420, 424, 437, 442, 446, 452, 456, 469, 474, 478, 484, and 488 are examples in which the content of the alloy element is excessive, and the reflectance is lowered.

On the other hand, examples other than the above are examples in which the constituent components of the third layer (Ag alloy film) of the present invention and other elements are satisfied, and good wiring resistance and reflectance are obtained.

Further, Nos. 401 to 432 of Table 9A are examples in which pure Mo is used in the second layer, and Nos. 433 to 464 in Table 9B are examples in which a pure Ti film is used in the second layer, and No. 465 to 496 in Table 9C are An example in which an ITO film is used in the second layer. Further, it has been found that although the composition of the third layer (Ag alloy) is also changed, the desired reflectance and wiring resistance can be obtained even if the constituent components are appropriately used in combination as long as the predetermined requirements of the present invention are satisfied.

In addition, all the embodiments of the present disclosure are illustrative and should not be construed as limiting. The scope of the present invention is defined by the scope of the claims and the scope of the claims This case is based on the Japanese invention patent application filed on November 21, 2012 (Special Wish 2012-255360), 2012 Japanese Patent Application (Japanese Patent Application No. 2012-271802) filed on Dec. 12, and Japanese Patent Application No. 2012-271803 filed on Dec. 12, 2012, the content of which is hereby incorporated herein.

1‧‧‧Substrate

2‧‧‧TFT

3‧‧‧passivation film

4‧‧‧flattening layer

5‧‧‧Contact hole

6‧‧‧1st layer (Al alloy film)

7‧‧‧2nd layer (Ag alloy film)

9‧‧‧Organic layer

10‧‧‧ cathode

Claims (12)

An electrode for use in a display device or an input device, wherein the electrode has a laminated film comprising a first layer containing an Al alloy formed on the substrate side and a second layer containing an Ag alloy formed above the first layer, The film thickness of the electrode is 100 nm or more and 800 nm or less, and the film thickness of the second layer is 60 nm or more and 480 nm or less, and the film thickness ratio of the second layer in the film thickness of the electrode is 10% or more. 70% or less, the film thickness ratio of the first layer in the film thickness of the electrode is 30% or more, and the Al alloy contains at least one selected from the group consisting of: (1) -A) The rare earth element is 0.05 atom% or more and 1.0 atom% or less, and (1-B) at least one selected from the group consisting of Si, Cu, and Ge is 0.5 atom% or more and 1.5 atom%. In the following, (1-C) at least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 atom% or more and 0.7 atom% or less. The electrode according to claim 1, wherein the Ag alloy contains Ag at 98 atom% or more and 99.98 atom% or less. The electrode according to claim 1, wherein the Ag alloy as the alloying element contains at least one selected from the group consisting of: (2-A) having a rare earth element of 0.05 atom% or more and 1.0 atom% Next, (2-B) is such that Bi and/or Cu is 0.05 atom% or more and 1.0 atom% or less, and (2-C) is at least one selected from the group consisting of Pd, Pt, and Au. % or more and 1.5 atom% or less, and (2-D) is Zn and/or In of 0.1 atom% or more and 1.5 atom% or less. The electrode according to claim 3, wherein the rare earth element of the above (1-A) or the aforementioned (2-A) is at least one selected from the group consisting of Nd, La, Gd, and Ce. The electrode according to claim 1, wherein the electrode has a third layer of an oxide containing an Al alloy or a nitride of an Al alloy between the first layer and the second layer, and a film thickness of the third layer It is 1 nm or more and 10 nm or less. The electrode of the fifth aspect of the invention, wherein the third layer of the Al alloy as the alloying element contains at least one selected from the group consisting of: (3-A) having a rare earth element of 0.05 atom% or more, 1.0 atom% or less, or (3-B) at least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 atom% or more and 0.7 atom% or less. The electrode of claim 1, wherein the electrode has a fourth layer containing a conductive oxide between the first layer and the second layer, the conductive oxide comprising: (a) at least one selected from the group consisting of Mo, Mo alloy, Ti, Ti alloy, Ta, W, Nb, or (b) at least one of In oxide and Zn oxide, the aforementioned fourth The film thickness of the layer is 3 nm or more and 50 nm or less. The electrode according to claim 7, wherein the conductive oxide of the fourth layer is ITO (indium tin oxide) or IZO (indium zinc oxide). An Al alloy sputtering target for electrode formation, which is used for forming an electrode as in the first aspect of the patent application, and contains at least one selected from the group consisting of: (1-A) having a rare earth element of 0.05 At least one atom selected from the group consisting of Si, Cu, and Ge is 0.5 atom% or more and 1.5 atom% or less, and (1-C). At least one selected from the group consisting of Ti, Ta, W, and Nb is 0.05 atom% or more and 0.7 atom% or less. The sputtering target according to claim 9, wherein the rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce. An Ag alloy sputtering target for electrode formation, which is used for forming an electrode as in the third item of the patent application, and contains at least one selected from the group consisting of: (2-A) having a rare earth element of 0.05 Atom% or more, 1.0 atom% or less, (2-B) Cu is 0.05 atom% or more and 1.0 atom% or less, and/or Bi is 0.25 atom% or more and 5.0 atomic% or less, and (2-C) is a group consisting of Pd, Pt, and Au. At least one selected is 0.1 atom% or more and 1.5 atom% or less, and (2-D) is Zn and/or In of 0.1 atom% or more and 1.5 atom% or less. The sputtering target according to claim 11, wherein the rare earth element is at least one selected from the group consisting of Nd, La, Gd, and Ce.