JP6975543B2 - A method for manufacturing an electrode for an organic electroluminescence element, an organic electroluminescence element, an organic electroluminescence display device, and an electrode for an organic electroluminescence element. - Google Patents

Description

The present invention relates to an electrode for an organic electroluminescence element, an organic electroluminescence element, an organic electroluminescence display device, and a method for manufacturing an electrode for an organic electroluminescence element.

In recent years, organic electroluminescence elements (hereinafter referred to as organic EL elements) have been used in various fields, and in particular, they have been used in applications such as display displays for smartphones, display devices such as flat-screen televisions, and lighting equipment.

Organic EL panels used in display devices and lighting devices using organic EL elements are roughly classified into two types, top emission type and bottom emission type, depending on the difference in the light extraction direction.
In the top emission type, a TFT (Thin Film Transistor) layer is formed on a substrate, and each layer such as an electrode and an organic EL layer is laminated on the TFT (Thin Film Transistor) layer. The top emission type extracts light from the opposite side of the substrate, that is, to the opposite side of the TFT circuit. On the other hand, the bottom emission type extracts light from the substrate side, that is, from a region other than the TFT circuit.

Compared to bottom emission type organic EL elements, top emission type organic EL elements are suitable for high brightness and high definition because they can secure a high aperture ratio without being restricted by light-shielding objects such as TFTs and wiring. ..
In the top emission type organic EL panel, it was conventionally necessary to install a circularly polarizing plate on the panel surface to prevent external light reflection of the TFT and the electrode for the organic EL element, but it is not necessary to stack multiple circularly polarizing films. It was difficult to create a flexible organic EL panel because it should not be used.

In order to omit the circularly polarizing plate, it is necessary to prevent external light reflection of the TFT and the organic EL element. External light reflection from the TFT array can be prevented by a black matrix, but for the anode of the organic EL element, a material having low reflectance, conductivity, and a deep work function is required for the anode of the organic EL element. Further, when the reflective electrode side is used as a cathode, a material having a shallow work function is required.

Patent Document 1 relates to a technique for preventing mirroring of an EL light emitting device without using a circularly polarizing film, and describes an anode or cathode made of an oxide conductive film and an EL light emitting element provided with a light shielding film. ing.

Patent Document 2 relates to an organic EL display element using molybdenum or chromium oxide as an antireflection layer, and molybdenum or chromium oxide may be used as an antireflection layer in order to prevent reflection of external light by a metal electrode. Have been described.

Patent Document 3 relates to an organic light emitting device that suppresses ambient light reflection from a cathode, and describes that an n-type semiconductor such as zinc oxide or calcium hexaborochloride is used as a reflection suppressing layer.

Patent Document 4 relates to an EL color filter constituting an EL display device, and describes that a light-absorbing oxide such as molybdenum oxide is used as a material for an antireflection layer of the EL color filter. ..

Japanese Unexamined Patent Publication No. 2002-033185 Japanese Unexamined Patent Publication No. 2004-303481 Japanese Unexamined Patent Publication No. 2001-332391 Japanese Unexamined Patent Publication No. 2003-017263

In Patent Documents 1 to 4, a light-shielding film and an antireflection layer are provided in order to prevent external reflection in the organic EL element, but the work is performed while having low reflectance in the visible light region and good conductivity. Electrode configurations with adjustable functions have not been realized.
In addition, an electrode configuration that has low reflectance in the visible light region and good conductivity, has a work function that can be adjusted, and can be etched all at once has not been realized.

The present invention has been made in view of the above problems, and an object of the present invention is to suppress external reflection by reducing the reflectance in the visible light region, and it is possible to arbitrarily adjust the work function. The present invention provides a method for manufacturing an electrode for an organic EL element, which can be applied to both an anode and a cathode of the organic EL element, and an electrode for an organic EL element.
Another object of the present invention is an electrode for an organic EL element and an electrode for an organic EL element, which have low reflectance in the visible light region and good conductivity, and whose work function can be adjusted, and which can be collectively etched. The purpose is to provide a manufacturing method.

The problem is that according to the electrode for an organic electroluminescence element of the present invention, a conductive layer containing a metal or an alloy as a main component and black having a reflectance of 40% or less in a visible light region provided on the conductive layer. A work function adjusting layer made of a transparent conductive oxide having a predetermined work function provided on the blackened layer is included, and the conductive layer contains Al, Cu, Ag, Mo, and Cr. A metal or alloy containing one or more metals as a main component selected from the group containing the blackened layer, which is a lower oxide, a lower nitride, or a lower acid nitride containing Mo or Zn as a main component. It is a physical vapor deposition film, and the work function adjusting layer is a transparent conductive oxide based on _{In 2} O ₃ or Zn O, has a reflectance in the visible light region of 10% or less, and a sheet resistance of 1 Ω / sq or less. Is solved by.
With the above configuration, since the blackening layer and the work function adjusting layer are provided on the conductive layer, external reflection is suppressed by reducing the reflectance in the visible light region, and the sheet resistance value is small, so that the work function can be achieved. It is possible to provide an electrode for an organic EL element that can be arbitrarily adjusted. Therefore, it is possible to form a flexible organic EL panel without a polarizing plate.
Further, by using these metals or alloys, the conductive layer can be laminated by a simple process such as a sputtering method, and low sheet resistance can be realized.
Further, by using a conductive substance having high absorbance in the visible light region as the blackening layer, it is possible to realize reflectance and good conductivity in the low visible light region.
Further, by using a transparent conductive oxide which can be doped with various metals and whose work function can be adjusted according to the amount of dopant added, the work function adjusting layer can be used as both an anode and a cathode. At the same time, it is possible to provide an electrode having a low reflectance in the visible light region.
In addition, since the conductive layer, blackening layer, and work function adjusting layer are formed of appropriate materials, they are collectively wet-etched using a phosphoric acid-based etching solution (phosphoric acid, nitric acid, acetic acid mixture). Since it can be etched, it is easy to manufacture the electrode.

At this time, it is preferable that the electrode for the organic electroluminescence element is composed of three layers including the conductive layer, the blackening layer, and the work function adjusting layer.
As described above, it has a low reflectance in the visible light region, sufficient conductivity, and has an advantage that it can be used as both an anode and a cathode, but it is composed of a small number of layers of three. Therefore, the electrode can be easily manufactured and the electrode can be made thin.

At this time, it is preferable that the blackened layer is made of a lower oxide, a lower nitride, or a lower oxynitride containing Mo as a main component.

At this time, the work function adjusting layer is made of a transparent conductive oxide based on _{In 2} O ₃ , and is selected from the group containing Ga, Ce, Zn, Sn, Si, W, and Ti in _{In 2} O _3. It is preferable that it is composed of a transparent conductive oxide to which one or more is added, or a transparent conductive oxide to which one or more selected from the group containing Al or Ga in ZnO is added .

At this time, the work function adjusting layer has a work function of 4.6 eV or less and is used as a cathode of the organic electroluminescence element, or has a work function of 4.7 eV or more and is used as an anode of the organic electroluminescence element. Is suitable.
As described above, since the work function of the work function adjusting layer is adjusted according to the type and amount of the dopant added to the base transparent conductive oxide, it can be used as both an anode and a cathode of the organic EL element. Is possible.

The problem is solved by an organic electroluminescence element provided with an electrode for an organic electroluminescence element of the present invention, and an organic electroluminescence display device provided with the organic electroluminescence element and not provided with a polarizing plate.
As described above, since the electrode for the organic electroluminescence element of the present invention has a reduced reflectance in the visible light region, external reflection can be suppressed when used as an electrode of an organic EL element and an organic EL display device. It is possible to provide an organic EL display device without a polarizing plate.

The problem is that according to the method for manufacturing an electrode for an organic electroluminescence element of the present invention, conductivity containing one or more metals selected from the group containing Al, Cu, Ag, Mo, and Cr on a substrate as a main component. The reflectance of the visible light region composed of a lower oxide, a lower nitride, or a lower oxynitride containing Mo or Zn as a main component on the conductive layer laminating step of laminating the layers is 40% or less. Work function adjustment having a blackened layer laminating step of laminating the blackened layer by a physical vapor deposition method and a predetermined work function composed of a transparent conductive oxide based _{on In 2} O _{3 or ZnO on the blackened layer.} Wet using a work function adjusting layer laminating step of laminating layers, the laminated conductive layer, the blackening layer, and the work function adjusting layer using a phosphoric acid acetic acid-based etching solution which is a mixed solution of phosphoric acid, nitric acid, and acetic acid. It is solved by performing an etching step of batch etching by etching.

In this way, since the conductive layer, the blackening layer, and the work function adjusting layer are formed of appropriate materials, all at once by wet etching using a phosphoric acid acetic acid-based etching solution (phosphoric acid, nitric acid, acetic acid mixed solution). It is easy to manufacture the electrode because it can be etched.
In addition, since the blackening layer and the work function adjustment layer are provided on the conductive layer, external reflection is suppressed by reducing the reflectance in the visible light region, and the sheet resistance is small, so that the work function can be adjusted arbitrarily. A possible electrode for an organic EL element can be provided.

According to the electrode for electronic devices of the present invention, the subject is a conductive layer containing a metal or an alloy as a main component and a blackening layer having a reflectance of 40% or less in a visible light region provided on the conductive layer. And a work function adjusting layer made of a transparent conductive oxide having a predetermined work function provided on the blackening layer, and the conductive layer is a group containing Al, Cu, Ag, Mo, Cr. A metal or alloy containing one or more metals as a main component, which is selected from the above, and the blackening layer is a physical vapor deposition of a lower oxide, a lower nitride, or a lower acid nitride containing Mo or Zn as a main component. The work function adjusting layer is a film, which is a transparent conductive oxide based on _{In 2} O ₃ or Zn O, has a reflectance in the visible light region of 10% or less, and a sheet resistance of 1 Ω / sq or less. It will be solved by that.
With the above configuration, since the blackening layer and the work function adjusting layer are provided on the conductive layer, external reflection is suppressed by reducing the reflectance in the visible light region, and the sheet resistance value is small, so that the electronic device It is possible to provide electrodes for electronic devices with reduced power consumption.
Further, by using these metals or alloys, the conductive layer can be laminated by a simple process such as a sputtering method, and low sheet resistance can be realized.
Further, by using a conductive substance having high absorbance in the visible light region as the blackening layer, it is possible to realize reflectance and good conductivity in the low visible light region.
Further, by using a transparent conductive oxide which can be doped with various metals and whose work function can be adjusted according to the amount of dopant added, the work function adjusting layer can be used as both an anode and a cathode. At the same time, it is possible to provide an electrode having a low reflectance in the visible light region.
In addition, since the conductive layer, blackening layer, and work function adjusting layer are formed of appropriate materials, they are collectively wet-etched using a phosphoric acid-based etching solution (phosphoric acid, nitric acid, acetic acid mixture). Since it can be etched, it is easy to manufacture the electrode.

In the electrode for an organic EL element of the present invention, the blackened layer is a lower oxide, a lower nitride, or a lower oxynitride whose main component is Mo or Zn having high electrical conductivity and high absorbance in the visible light region. Since it is formed of, the reflectance can be lowered while the sheet resistance value remains low. Further, since the transparent conductive oxide having an appropriate work function is used as the work function adjusting layer, the electrode can be used for both the anode and the cathode. Further, by combining the blackening layer and the work function adjusting layer, the reflectance in the visible light region can be reduced to 10% or less. Therefore, a flexible organic EL panel without a polarizing plate can be formed.

Further, since the conductive layer, the blackening layer, and the work function adjusting layer are collectively selected from the materials that can be etched, the electrode can be easily manufactured.

It is a schematic cross-sectional view which shows the electrode for an organic EL element which concerns on one Embodiment of this invention. It is a flow chart of the manufacturing method of the electrode for an organic EL element which concerns on one Embodiment of this invention. It is a schematic sectional drawing which shows the organic EL element which concerns on one Embodiment of this invention. It is a schematic cross-sectional view which shows the organic EL element which concerns on the modification of one Embodiment of this invention. It is the result of the optical constant measurement of the blackened layer of the reference example 1 and the reference example 2 of this invention, (a) the graph which shows the refractive index, (b) the graph which shows the extinction coefficient. It is a graph which shows the result of the reflectance measurement of the blackened layer of the reference example 1 to 3 of this invention. It is a graph which shows the result of the reflectance measurement of the work function adjustment layer of the reference example 4 to 8 of this invention. It is a graph which shows the result of the reflectance measurement of the electrode for an organic EL element of Example 1 and Comparative Example 1 of this invention. It is a graph which shows the result of the reflectance measurement of the electrode for an organic EL element of Examples 2 to 6 and Comparative Example 2 of this invention. It is an SEM cross-sectional photograph of the sample which etched the electrode for an organic EL element of Example 2. FIG. It is a graph which shows the result of the reflectance measurement of the conductive film of Example 7 of this invention.

Hereinafter, an electrode for an organic EL element according to an embodiment of the present invention, a method for manufacturing the electrode for the organic EL element, an organic EL element provided with the electrode for the organic EL element, and an organic EL display device using the organic EL element will be described. explain.

<Electrodes for organic EL elements>
As shown in FIG. 1, the electrode 20 for an organic EL element of the present embodiment has a conductive layer 1, a blackening layer 2 formed on the conductive layer 1, and a work formed on the blackening layer 2. The function adjustment layer 3 is laminated. Hereinafter, each layer constituting the electrode 20 for the organic EL element will be described in detail.

(Conductive layer)
The conductive layer 1 is selected from the group containing Al, Cu, Ag, and Mo, and is selected from the group containing one or more of the main components of a metal or APC (alloy of silver, palladium, and copper), AlNd, AlSi, AlCu, and AlSiCu. The alloy of choice.
Here, the main component is a case where the conductive layer contains 50% by weight or more by weight.
The metal constituting the conductive layer 1 may be any metal having sufficient conductivity and used for the organic EL element. For example, Al, Cu, Ag, Mo and the like can be mentioned, but the present invention is not limited thereto.
The alloy constituting the conductive layer 1 may be any alloy having sufficient conductivity and used for the organic EL element. Examples thereof include alloys containing Al, Cu, Ag, Mo and the like as main components, or alloys selected from the group containing APC (alloy of silver, palladium and copper), AlNd, AlSi, AlCu and AlSiCu. Not limited to.
The thickness of the conductive layer 1 is preferably 10 nm or more and 1000 nm or less, more preferably 20 nm or more and 800 nm or less, more preferably 30 nm or more and 700 nm or less, still more preferably 40 nm or more and 600 nm or less, still more preferably 50 nm or more and 500 nm or less. It would be nice to have one. If the thickness of the conductive layer 1 becomes too thin, the conductivity will decrease. On the other hand, if the conductive layer 1 is too thick, the thickness of the organic EL element increases, and the processability and manufacturability of etching deteriorate.

(Blackened layer)
The blackening layer 2 is a layer containing Mo or Zn as a main component and having a reflectance of 40% or less in a visible light region composed of a lower oxide, a lower nitride, or a lower oxynitride.
Here, the main component is a case where Mo or Zn contained in the blackened layer contains 50 atomic% or more in terms of the atomic number ratio of metal atoms.
The lower oxide, lower nitride, or lower oxynitride constituting the blackening layer 2 may be any as long as it can sufficiently absorb light in the visible light region and has sufficient conductivity. Examples thereof include, but are not limited to, lower oxides, lower nitrides, lower oxynitrides and the like containing Mo or Zn as a main component.

The lower oxide containing Mo as the main component is MoO _x (x = stoichiometric ratio, 2≤x <3), and the lower nitride containing Mo as the main component is MoN _y (y = stoichiometric ratio). ), The lower oxynitride containing Mo as a main component is MoO _x N _y (x, y = stoichiometric ratio).

The lower oxides containing Zn as the main component are ZnO _x (x = chemical ratio), and the lower nitrides containing Zn as the main component are ZnN _y (y = chemical ratio) and Zn as the main components. The lower oxynitride to be referred to is ZnO _x N _y (x, y = chemical quantity theory ratio).

In the blackening layer 2, a dopant metal may be added to a metal other than Mo or Zn, which is the main component.
The dopant metal is preferably a transition metal, and is, for example, Nb, W, Al, Ni, Cu, Cr, Ti, Ag, Ga, Zn, In, and Ta, but is not limited thereto.

The content ratio of the dopant metal to the lower oxide, the lower nitride, or the lower oxynitride containing Mo or Zn as a main component is preferably 20 atomic% or less. When the content ratio of the dopant metal (Nb, Ta, etc.) is within the above range, good conductivity and light absorption in the visible light region can be realized.

The reflectance of the visible light region of the blackening layer 2 is preferably 50% or less, more preferably 40% or less. According to the definition of JIS Z8120, the lower limit of the wavelength of the electromagnetic wave corresponding to visible light is about 360 to 400 nm, and the upper limit is about 760 to 830 nm. Say the area.
When the visible light transmittance of the blackening layer 2 is low, the visible light reflected from the electrode 20 for the organic EL element is reduced, and it can be suitably used for a flexible organic EL display device without a polarizing plate.

The thickness of the blackening layer 2 is preferably 5 nm or more and 200 nm or less, more preferably 10 nm or more and 150 nm or less, more preferably 20 nm or more and 100 nm or less, still more preferably 30 nm or more and 75 nm or less, still more preferably 40 nm or more and 60 nm or less. It should be. If the thickness of the blackening layer 2 becomes too thin, the absorption of light in the visible light region becomes insufficient and the film formation becomes difficult. On the other hand, if the blackening layer 2 is too thick, the processability and manufacturability of etching are deteriorated.

(Work function adjustment layer)
The work function adjusting layer 3 is a layer made of a transparent conductive oxide having a predetermined work function.
The transparent conductive oxide constituting the work function adjusting layer 3 may be any transparent conductive oxide having sufficient conductivity and whose work function can be adjusted by adding various metals. Examples of such transparent conductive oxides include, but are not limited to _{, In 2} O ₃ , ZnO, Ga ₂ O ₃ , SnO ₂ , TiO _{2, CdO, and composite oxides thereof.} No.
In the present embodiment, it is preferable to use a transparent conductive oxide based on _{In 2} O ₃ or Zn O as the material constituting the work function adjusting layer 3.

The In ₂ O ₃ as a transparent conductive oxide based, Ga to _In 2 _{O 3} of the main component, Ce, Zn, Sn, Si , W, is at least one metallic element selected from the group comprising Ti is added A transparent conductive oxide can be used.

Among such _{transparent conductive oxides based on In 2} O ₃ , IGO (gallium-doped indium oxide) to which Ga is added, IZO (indium tin oxide) to which Zn is added, and ITO (ITO) to which Sn is added. Indium tin oxide), ICO (indium cerium oxide) to which Ce, Sn and Ti are added, and IWZO (tungsten-zinc-doped indium oxide) to which W and Zn are added can be preferably used.

Further, _{the content ratio of the metal element added to In 2} O ₃ is preferably 50% by weight or less in terms of weight ratio. If it is contained in a large amount exceeding the above range, high resistance will occur, which is not preferable.
In addition to Ga, Ce, Zn, Sn, Si, W, and Ti, other elements in the transparent conductive oxide based on _{In 2} O _{3 have the performance of the electrode for the organic EL element of this embodiment.} It may be included as long as it does not impair.

As the transparent conductive oxide based on ZnO, a transparent conductive oxide obtained by adding one or more metal elements selected from the group containing Al or Ga to ZnO as the main component can be used.

Examples of such ZnO-based transparent conductive oxides include AZO (aluminum-doped zinc oxide) to which Al is added, GZO (gallium-doped zinc oxide) to which Ga is added, and GAZO (GAZO) to which Al and Ga are added. (Gallium / aluminum-doped zinc oxide) can be preferably used.

Further, the content ratio of the metal element added to ZnO is preferably 10% by weight or less in terms of weight ratio. If it is contained in a large amount exceeding the above range, high resistance will occur, which is not preferable.
In addition to Al or Ga, the transparent conductive oxide based on ZnO may contain other elements as long as the performance of the electrode for the organic EL element of the present embodiment is not impaired.

When the electrode 20 for an organic EL element is used as a cathode, for example, the transparent conductive oxide may be selected so that the work function of the work function adjusting layer 3 is 4.6 eV or less.
On the other hand, when the electrode 20 for an organic EL element is used as an anode, for example, the transparent conductive oxide may be selected so that the work function of the work function adjusting layer is 4.7 eV or more.

In the present embodiment, various metals are added to the work function adjusting layer 3 to obtain a predetermined work function, but the addition of various metals is a crystal of _{In 2 O 3} or Zn O as a base. Causes sexual deterioration. Therefore, the addition of the metal lowers the crystallinity of the work function adjusting layer 3 and amorphizes it, so that etching can be performed using a predetermined etching solution.

The thickness of the work function adjusting layer 3 is preferably 5 nm or more and 150 nm or less, more preferably 10 nm or more and 100 nm or less, more preferably 20 nm or more and 80 nm or less, still more preferably 30 nm or more and 60 nm or less, still more preferably 40 nm or more and 50 nm. It should be as follows. If the thickness of the work function adjusting layer 3 becomes too thin, the absorption of light in the visible light region becomes insufficient, the work function becomes unstable, and film formation becomes difficult. On the other hand, if the work function adjusting layer 3 is too thick, the processability and manufacturability of etching are deteriorated.

(Physical characteristics of electrodes for organic EL elements)
The electrode 20 for an organic EL element according to the present embodiment has a low reflectance in a visible light region and sufficient conductivity that can be used in a polarizing plate-less organic EL display device by having the above configuration. It is characterized by being.

The reflectance of the electrode 20 for an organic EL element in the visible light region (400 nm to 700 nm) is 10% or less.

The sheet resistance of the electrode 20 for an organic EL element is 1 Ω / sq or less, more preferably 0.75 Ω / sq or less, still more preferably 0.5 Ω / sq or less, and particularly preferably 0.25 Ω / sq or less.
The work function of the electrode 20 for the organic EL element is determined by the work function of the work function adjusting layer 3, but when the electrode 20 for the organic EL element is used as a cathode, it is 4.6 eV or less, while the electrode for the organic EL element. When 20 is used as an anode, it is 4.7 eV or more.

The electrode 20 for an organic EL element is composed of a small number of layers, that is, a conductive layer 1, a blackening layer 2, and a work function adjusting layer 3, which is a small number of layers. It has sufficient conductivity and has an advantage that it can be used as both an anode and a cathode of an organic EL element by appropriately selecting a material to be used for the work function adjusting layer.

The thickness of the electrode 20 for an organic EL element is preferably 20 nm or more and 1500 nm or less, more preferably 100 nm or more and 1000 nm or less, more preferably 200 nm or more and 800 nm or less, still more preferably 300 nm or more and 600 nm or less, still more preferably 350 nm or more. It is preferably 500 nm or less. If the electrode 20 for an organic EL element is too thick, the processability and manufacturability of etching will deteriorate.

<Manufacturing method of electrodes for organic EL elements>
As shown in FIG. 2, the electrode 20 for an organic EL element of the present embodiment is conductive with one or more metals selected from the group containing Al, Cu, Ag, Mo, and Cr on the substrate as a main component. The reflectance of the visible light region composed of a conductive layer laminating step of laminating layers and a lower oxide, a lower nitride, or a lower oxynitride having Mo or Zn as a main component on the conductive layer is 40% or less. A work function adjusting layer having a predetermined work function made of a transparent conductive oxide based _{on In 2} O ₃ or Zn O is laminated on the blackened layer laminating step of laminating the blackened layer. A method for manufacturing an electrode for an organic EL element, which comprises performing a work function adjusting layer laminating step and an etching step of collectively etching the laminated conductive layer, the blackening layer, and the work function adjusting layer. Manufactured by.
Hereinafter, each step will be described in detail with reference to FIG.

(Conductive layer laminating process)
In the conductive layer laminating step (step S1), the conductive layer 1 containing one or more metals selected from the group containing Al, Cu, Ag, Mo, and Cr as a main component is laminated on the base material 10. As a method for forming the conductive layer 1 on the base material 10, a physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, or an ion plating method can be used, but the method is not limited thereto.

(Blackening layer laminating process)
In the blackening layer laminating step (step S2), a lower oxide, a lower nitride, or a lower acid containing Mo or Zn as a main component on the conductive layer 1 laminated on the base material 10 in the conductive layer laminating step. The blackening layer 2 having a reflectance of 40% or less in the visible light region made of nitride is laminated. As a method for forming the blackening layer 2 on the conductive layer 1, a physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, or an ion plating method can be used, but the method is not limited thereto.

In the blackening layer laminating step, in order to obtain a lower oxide, a lower nitride, or a lower oxynitride containing Mo or Zn as a main component, Mo and ZnO are used as targets, and the oxygen flow rate is 5 to 50 sccm. do.

(Work function adjustment layer laminating process)
In the work function adjusting layer laminating step (step S3), a predetermined transparent conductive oxide based _{on In 2} O ₃ or Zn O is formed on the blackening layer 2 laminated on the conductive layer 1 in the blackening layer laminating step. The work function adjustment layer 3 having a work function is laminated. As a method for forming the work function adjusting layer 3 on the blackening layer 2, a physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, or an ion plating method can be used, but the method is not limited thereto.

In the work function adjusting layer laminating step, in _{order to obtain a transparent conductive oxide based on In 2} O ₃ or Zn O, ITO and GZO are used as targets, and the oxygen flow rate is set to 5 sccm.

If the method for forming the conductive layer 1, the blackening layer 2, and the work function adjusting layer 3 is, for example, a vacuum vapor deposition method and / or a sputtering method, the organic layer is continuously and continuously formed on the substrate 10 in a dry process. The electrode 20 for an EL element can be formed.

(Etching process)
In the etching step (step S4), the conductive layer 1, the blackening layer 2, and the work function adjusting layer 3 laminated on the base material 10 are collectively etched. For example, a photoresist is applied on a conductive layer 1, a blackening layer 2, and a work function adjusting layer 3 laminated on a substrate 10 by a photolithography technique, and exposure and development are performed to transfer a mask pattern to the resist. Are performed in order, and further, the portion other than the portion that should be left as an electrode is removed by etching. After that, when the resist is removed, the remaining portion is obtained as the electrode 20 for the organic EL element.

As the etching method, wet etching with an etching solution or dry etching such as reactive gas etching, reactive ion etching, reactive ion beam etching, ion beam etching, and reactive laser beam etching can be used.
In this embodiment, since the conductive layer 1, the blackening layer 2, and the work function adjusting layer 3 are formed of the above-mentioned materials, a phosphoric acid acetic acid-based etching solution (a mixed solution of phosphoric acid, nitric acid, and acetic acid) was used. It is possible to etch all at once by wet etching.

<Organic light emitting element>
As shown in FIG. 3, the top-emission type organic EL element 100 including the organic EL element electrode 20 of the present embodiment as an anode (anode) includes a base material 10, an organic EL element electrode 20, and hole transport. The layer 30, the organic light emitting layer 40, the electron transport layer 50, and the transparent electrode 60 are sequentially laminated and formed, and the light emitting L is taken out from the opposite side of the base material 10.
The electrode 20 for an organic EL element of the present embodiment has an advantage that it is not necessary to use a polarizing plate because the reflectance in the visible light region is 10% or less and the reflection of external light is suppressed.
Hereinafter, each component of the organic EL element 100 will be described in detail.

(Base material)
The base material 10 constituting the organic EL element 100 of the present invention may be any material that does not change when forming the electrode and the organic material layer, for example, glass, plastic, polymer film, silicon substrate, or a laminated material thereof. Can be used.

(Hole transport layer)
Materials constituting the hole transport layer 30 include polyvinylcarbazole or its derivatives, polysilanes or derivatives thereof, polysiloxane derivatives having aromatic amines in their side chains or main chains, pyrazoline derivatives, arylamine derivatives, stylben derivatives, and triphenyls. Diamine derivative, polyaniline or its derivative, polythiophene or its derivative, polyarylamine or its derivative, polypyrrole or its derivative, poly (p-phenylenebinylene) or its derivative, or poly (2,5-thienylenebinylene) or its derivative. And so on.

The method for forming the hole transport layer 30 is not particularly limited, but examples of the low molecular weight hole transport material include a method of forming a film from a mixed solution with a polymer binder, and polymer hole transport can be mentioned. Examples of the material include a method of forming a film from a solution.

The optimum film thickness of the hole transport layer 30 differs depending on the material, and it may be selected so that the drive voltage and the luminous efficiency are appropriate values, but at least the thickness must be such that pinholes do not occur. be. If the film thickness is too thick, the driving voltage of the organic EL element 100 becomes high. Therefore, the film thickness of the hole transport layer 30 is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm. It should be ~ 200 nm.

(Organic light emitting layer)
The organic light emitting layer 40 contains an organic substance (small molecule compound and high molecular compound) that emits fluorescence or phosphorescence. In addition, a dopant material may be further contained. Examples of the material for forming the organic light emitting layer 40 that can be used in the present embodiment include, but are not limited to, a dye-based material, a metal complex-based material, and a polymer-based material.
It is also possible to add a dopant to the organic light emitting layer 40 for the purpose of improving the light emitting efficiency and changing the light emitting wavelength.
The method for forming the organic light emitting layer 40 is not particularly limited, but a method of applying a solution containing a light emitting material on or above a substrate, a vacuum vapor deposition method, a transfer method, or the like can be used.
The thickness of the organic light emitting layer 40 is usually 20 to 2000 Å.

(Electron transport layer)
Known materials can be used as the material constituting the electron transport layer 50, and oxadiazole derivatives, anthracinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthracinos. Dimethane or its derivatives, fluorenone derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinolin or its derivatives, polyquinoxalin or its derivatives, polyfluorene or its derivatives and the like. Be done.

The method for forming the electron transport layer 50 is not particularly limited, and examples of the low molecular weight electron transport material include a vacuum vapor deposition method from powder and a method by forming a film from a solution or a molten state. Examples of the electron transport material include a method of forming a film from a solution or a molten state.

The optimum value of the film thickness of the electron transport layer 50 differs depending on the material, and it may be selected so that the drive voltage and the luminous efficiency are appropriate values, but at least the thickness must be such that pinholes do not occur. .. If the film thickness is too thick, the driving voltage of the organic EL element 100 becomes high. Therefore, the film thickness of the electron transport layer 50 is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to. It is preferably 200 nm.

(Transparent electrode)
Since the organic EL element 100 according to the present embodiment emits light through the transparent electrode 60, it is necessary to use a transparent or translucent electrode for the transparent electrode 60.

When the electrode 20 for an organic EL element is used as an anode in the organic EL element 100 according to the present embodiment, the material constituting the transparent electrode 60 as a cathode has a small work function and the electron transport layer 50 and the organic light emitting layer 40. A material that facilitates electron injection into is preferred. For example, a conductive metal oxide, a conductive organic substance, or the like can be used. Specifically, indium oxide, zinc oxide, tin oxide, and composites thereof ITO and IZO can be used as the conductive metal oxide, but the present invention is not limited thereto. As the conductive organic substance, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof can be used, but the present invention is not limited thereto.

(Modification example of organic light emitting element)
FIG. 3 shows a top-emission type organic EL element 100 provided with the organic EL element electrode 20 of the present embodiment as an anode (anode), but the organic EL element electrode 20 of the present embodiment is a cathode (cathode). It can also be used as.
As a modification of this embodiment, FIG. 4 shows an organic EL element 100'using an organic EL element electrode 20'as a cathode. In the organic EL element 100', the base material 10, the electrode 20' for the organic EL element, the electron transport layer 50, the organic light emitting layer 40, the hole transport layer 30, and the transparent electrode 60' are laminated in this order. Since the electrode 20'for the organic EL element is used as a cathode, the positions of the electron transport layer 50 and the hole transport layer 30 are different.

Here, in the organic EL element 100'according to the modification of the present embodiment, the electrode 20' for the organic EL element is used as a cathode, and the work function is used as a material constituting the transparent electrode 60'which is an anode. A material that is large and easy to inject holes into the hole transport layer 30 and the organic light emitting layer 40 is preferable. As the transparent electrode or the translucent electrode, a metal oxide having high electrical conductivity, a metal sulfide, or a thin film of metal can be used. As the transparent electrode, indium oxide, zinc oxide, tin oxide, and their composites, ITO and IZO, are preferable, but the transparent electrode is not limited thereto.

(Organic light emitting device)
Since the organic EL elements 100 and 100'of this embodiment have low reflectance in the visible light region and suppress external reflection, it is possible to manufacture a polarizing plate-less organic EL display device without using a polarizing plate. It is possible.
Examples of the organic EL display device include, but are not limited to, a display of a mobile terminal such as a smartphone or a tablet terminal, a display of a flat-screen TV or the like.
If a base material made of a flexible material such as a plastic film is selected as the base material 10, a flexible organic EL display device can be obtained.

In the present embodiment, a method for manufacturing an electrode for an organic EL element, an organic EL element, an organic EL display device, and an electrode for an organic EL element according to the present invention has been mainly described.
However, the above embodiment is merely an example for facilitating the understanding of the present invention, and does not limit the present invention. The present invention can be modified and improved without departing from the spirit thereof, and it goes without saying that the present invention includes an equivalent thereof.

Hereinafter, specific examples of the electrode for an organic EL device of the present invention will be described, but the present invention is not limited thereto.
<A. Formation of Electrodes for Organic EL Devices According to Examples and Comparative Examples>
(A-1. Conductive layer forming step)
Under the following conditions, the conductive layers according to Examples 1 to 6 and Comparative Examples 1 and 2 were laminated on the base material.
Sputtering equipment: Carousel type batch type sputtering equipment Target: 5 "x 25", thickness 6 mm, 100% aluminum (Al)
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Reaching vacuum: 5 × 10 ^-4 Pa
Base material temperature: 25 ° C (room temperature)
Spatter power: 6kW
Film thickness of conductive layer: 300 ± 10 nm
Ar flow rate: 250 sccm
Base material used: Glass base material (1.1 mm thick)

(A-2. Blackening layer laminating process)
_{Under the following conditions, MoNbO x} (x = stoichiometric ratio) as a blackening layer was laminated on the conductive layer according to Example 1 and Comparative Example 1, and the conductivity according to Examples 2 to 6 and Comparative Example 2 was laminated. _{MoO x} (x = stoichiometric ratio) as a blackening layer was laminated on the layer.
Sputtering equipment: Carousel type batch type sputtering equipment Target:
(Example 1) 5 "x 25", thickness 6 mm, Mo90 atomic%, Nb10 atomic%
(Comparative Example 1) 5 "x 25", thickness 6 mm, Mo90 atomic%, Nb10 atomic%
(Examples 2 to 6) 5 "x 25", thickness 6 mm, Mo100 atomic%
(Comparative Example 2) 5 "x 25", thickness 6 mm, Mo100 atomic%
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Reaching vacuum degree: 5 × 10 ^-4 Pa
Base material temperature: 25 ° C (room temperature)
Spatter power: 3kW
Film thickness of blackened layer: 50 ± 5 nm
Ar flow rate: 250 sccm
Oxygen flow rate: 50 sccm

(A-3. Work function adjustment layer laminating process)
Under the following conditions, IGO (gallium-doped indium oxide) as a work function adjusting layer was laminated on the blackened layer according to Examples 1 to 6. On the other hand, the work function adjusting layer was not laminated on the blackened layers according to Comparative Examples 1 and 2.
Sputtering equipment: Carousel type batch type sputtering equipment Target:
(Example 1) 5 "x 25", thickness 6 mm, In ₂ O ₃ 60% by weight, Ga ₂ O ₃ 40% by weight
(Example 2) 5 "x 25", thickness 6 mm, In ₂ O ₃ 60% by weight, Ga ₂ O ₃ 40% by weight
(Example 3) 5 "x 25", thickness 6 mm, In ₂ O ₃ 90% by weight, Sn ₂ O ₃ 10% by weight
(Example 4) 5 "x 25", thickness 6 mm, In ₂ O ₃ 90% by weight, ZnO 10% by weight
(Example 5) 5 "x 25", thickness 6 mm, In ₂ O ₃ 86.5% by weight, CeO ₂ 10% by weight, SnO ₂ 3.2% by weight, TiO ₂ 0.3% by weight.
(Example 6) 5 "x 25", thickness 6 mm, In ₂ O ₃ 96.5% by weight, WO ₃ 3.0% by weight, ZnO 0.5% by weight.
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Reaching vacuum degree: 5 × 10 ^-4 Pa
Base material temperature: 25 ° C (room temperature)
Spatter power: 2kW
Work function adjustment layer film thickness: 35 ± 5 nm
Ar flow rate: 100 sccm
Oxygen flow rate: 5 sccm

<B. Formation of blackening layer or work function adjustment layer according to the reference example>
(B-1. Blackening layer laminating process)
Under the following conditions, the blackening layer according to Reference Examples 1 to 3 was laminated on the base material.
Sputtering equipment: Carousel type batch type sputtering equipment Target:
(Reference example 1) 5 "x 25", thickness 6 mm, Mo100 atomic%
(Reference example 2) 5 "x 25", thickness 6 mm, Mo90 atomic%, Nb10 atomic%
(Reference Example 3) 5 "x 25", thickness 6 mm, Mo90 atomic%, Nb7 atomic%, Ta3 atomic%
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Reaching vacuum degree: 5 × 10 ^-4 Pa
Base material temperature: 25 ° C (room temperature)
Spatter power: 3kW
Film thickness of blackened layer: 50 ± 5 nm
Ar flow rate: 250 sccm
Oxygen flow rate: 50 sccm

(B-2. Work function adjustment layer laminating process)
Under the following conditions, the work function adjusting layer according to Reference Examples 4 to 8 was laminated on the base material.
Sputtering equipment: Carousel type batch type sputtering equipment Target:
(Reference Example 4) 5 "x 25", thickness 6 mm, In ₂ O ₃ 60% by weight, Ga ₂ O ₃ 40% by weight
(Reference Example 5) 5 "x 25", thickness 6 mm, In ₂ O ₃ 90% by weight, Sn ₂ O ₃ 10% by weight
(Reference Example 6) 5 "x 25", thickness 6 mm, In ₂ O ₃ 90% by weight, ZnO 10% by weight
(Reference Example 7) 5 "x 25", thickness 6 mm, In ₂ O ₃ 86.5% by weight, CeO ₂ 10% by weight, SnO ₂ 3.2% by weight, TiO ₂ 0.3% by weight
(Reference Example 8) 5 "x 25", thickness 6 mm, In ₂ O ₃ 96.5% by weight, WO ₃ 3.0% by weight, ZnO 0.5% by weight
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Reaching vacuum degree: 5 × 10 ^-4 Pa
Base material temperature: 25 ° C (room temperature)
Spatter power: 2kW
Work function adjustment layer film thickness: 35 ± 5 nm
Ar flow rate: 100 sccm
Oxygen flow rate: 5 sccm

<C. Various tests>
(Reference test 1: Measurement of optical constants of the blackened layer)
The optical constants of the blackened layers of Reference Example 1 and Reference Example 2 were measured. The optical constant was measured using a spectroscopic ellipsometer (M-220, manufactured by JASCO Corporation).
The results are shown in FIG. FIG. 5A is a graph showing the refractive index, and FIG. 5B is a graph showing the extinction coefficient.
Table 1 shows the refractive index n and the extinction coefficient k at 550 nm.

(Reference test 2: Reflectance measurement of the blackened layer)
The reflectance of the blackened layer of Reference Examples 1 to 3 was measured. The reflectance was measured in the wavelength range of 350 nm to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
The results are shown in FIG.
The reflectance of the blackened layers of Reference Examples 1 to 3 is about 25% or more and 40% or less, and the reflectance in the visible light region cannot be reduced to 10% or less only by laminating the blackened layers. I understood.

(Reference test 3: Reflectance measurement of work function adjustment layer)
The reflectance of the work function adjusting layer of Reference Examples 4 to 8 was measured. The reflectance was measured in the wavelength range of 350 nm to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
The results are shown in FIG.
It was found that the reflectance of the work function adjustment layer of Reference Examples 4 to 8 is larger than 10%, and the reflectance in the visible light region cannot be reduced to 10% or less only by stacking the work function adjustment layers. rice field.

(Reference test 4: Work function measurement of work function adjustment layer)
The work function of the work function adjustment layer of Reference Examples 4 to 8 was measured.
The work function was calculated using an atmospheric photoelectron spectrometer (manufactured by RIKEN Keiki Co., Ltd., model name AC-2).
The results are shown in Table 2 below.

(Test 1: Measurement of reflectance of electrodes for organic EL elements)
The reflectances of the electrodes of Examples (Examples 1 to 6) and Comparative Examples (Comparative Example 1 and Comparative Example 2) were measured. The reflectance was measured in the wavelength range of 350 nm to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
The results are shown in FIGS. 8 and 9.
In FIG. 8, the reflectance of Comparative Example 1 shown by the broken line was 10% or more. On the other hand, the reflectance of Example 1 shown by the solid line was 7.4% (535 nm) at the maximum, and showed a low value of 10% or less in the entire visible light region of 400 nm to 700 nm.
In FIG. 9, the reflectance of Comparative Example 2 shown by the dotted line was 10% or more. On the other hand, the reflectances of Examples 2 to 6 showed a low value of 10% or less in the entire visible light region of 400 nm to 700 nm.
From these results, the reflectance in the visible light region cannot be reduced to 10% or less simply by laminating the blackening layer on the conductive layer, and the three layers consisting of the conductive layer, the blackening layer, and the work function adjusting layer. It was found that the reflectance in the visible light region can be reduced to 10% or less by adopting the configuration.

(Test 2: Measurement of sheet resistance and work function of electrodes for organic EL elements)
The sheet resistance of the electrodes of Example 1 and Comparative Example 1 was measured by a four-terminal method using a resistivity meter (manufactured by Mitsubishi Chemical Analytec Co., Ltd., model name MCP-T610).
Further, the work functions of the electrodes of Examples 1 to 6 and Comparative Examples 1 and 2 were calculated using an atmospheric photoelectron spectroscope (manufactured by RIKEN KEIKI Co., Ltd., model name AC-2).
The results are shown in Table 3 below.

From the above, it was found that the sheet resistance value of the electrode of Example 1 was 0.11 Ω / sq, which was a sufficiently small value, and could be used as an electrode for an organic EL element. Further, the electrode of Example 1 shows the same value as the sheet resistance value of Comparative Example 1 having no work function adjusting layer, and the work function adjusting layer does not affect the sheet resistance value in the visible light region. It was found that the reflectance can be reduced to 10% or less.
Further, since the work function of the work function adjusting layer can be set to an arbitrary value according to the type of dopant added to the base transparent conductive oxide, it can be used as both an anode and a cathode of an organic EL element. It turned out to be.

(Test 3: Etching evaluation)
Etching evaluation was performed on the electrodes of Example 2.
The conductive film of Example 2 was coated with a photoresist (OFPR-800LB manufactured by Tokyo Ohka Co., Ltd.), and a patterned mask original plate was used to irradiate the photoresist with ultraviolet rays to print a pattern on the photoresist. Using a developing solution (TMAH (tetramethylammonium hydroxide) aqueous solution), the uncured photoresist is removed to develop the pattern of the original plate, and the unnecessary part of the conductive film from which the photoresist has been removed is etched. It was removed by etching with (a mixed solution of phosphoric acid, nitrate and acetic acid). Then, the photoresist remaining on the conductive film was peeled off and washed to obtain an etching sample of Example 2.
Then, the etching sample of Example 2 was subjected to SEM cross-sectional analysis (S-4300 manufactured by Hitachi High-Tech Fielding).
An SEM cross-sectional photograph of the etching sample of Example 2 is shown in FIG. As shown in FIG. 10, the etching surface was observed as a clear boundary, and it was found that good etching was performed.

(Example 7: Al-Nd / nitriding Mo-Nb / IGO conductive film)
An Al—Nd alloy layer (thickness 330 nm), a Mo-Nb alloy nitride layer (thickness 40 nm), and an IGO layer (thickness 30 nm) were prepared on a glass substrate by the following procedure, and the conductivity of Example 7 was prepared. It was made into a film.
An Al—Nd alloy layer having a film thickness of 330 nm was formed on a glass substrate by a DC magnetron sputtering method.

Next, the target, the film thickness, the sputtering power, and the introduced gas were changed as follows to form a Mo-Nb alloy nitride layer on the Al—Nd alloy layer.
-Target: Thickness 9 mm, Mo-Nb target-Spattering power: 1.5 W / cm ²
-Film thickness: 40 nm
・ Ar flow rate: 500 sccm
・ N ₂ flow rate: 88 sccm

Next, the target, the film thickness, the sputtering power, and the introduced gas were changed as follows to form an IGO layer on the nitrided layer of the Mo—Nb alloy.
・ Target: IGO 6t 5 ”x 62” Target ・ Spatter power: 2.5W / cm ²
-Film thickness: 30 nm
・ Ar flow rate: 500 sccm
・ O ₂ flow rate: 12 sccm
From the above, the conductive film of Example 7 was obtained.

〇Characteristics of the conductive film The characteristics of the conductive film of Example 7 formed as described above were measured.
Resistance value and reflectance of the conductive film of Example 7 For the conductive film of Example 7, the reflectance in the visible light range from a wavelength of 400 nm to 700 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.). It was measured. Further, the resistivity value was measured using a resistivity meter (Rollester GP manufactured by Mitsubishi Chemical Corporation), and the reflectance was measured using a film thickness meter (DEKTAKXT manufactured by ULVAC). The measurement results of the reflectance are shown in FIG. 11, and the measurement results of the resistance value and the film thickness are shown in Table 4.

The reflectance of the conductive film of Example 7 shown by the solid line in FIG. 10 was as low as 10% or less in the entire visible light region of 400 nm to 700 nm.
Further, the value of the sheet resistance of the conductive film of Example 7 was 0.16 Ω / sq, which was a sufficiently small value, and it was found that the conductive film could be used as a conductive film.

As described above, as a specific example of the electrode of the present invention, an electrode for an organic EL element has been described as an example. However, the electrode of the present invention has a low resistance and a low reflectance of about 10% or less in the visible light region. Therefore, the application is not limited to the electrode for the organic EL element, and it can also be used as an electrode for an electronic device and an electrode for an optical device.

As an example of such an electronic device, a capacitive input device having a touch panel can be mentioned. Here, the touch panel refers to a touch sensor integrated display device that integrally includes a touch sensor and a display device. The touch panel may be a touch panel manufactured by adhering a touch sensor substrate having a pattern formed of a transparent conductive film on a transparent substrate on the visible side of a display device such as a liquid crystal device as a detection electrode, or a touch panel of a display device. There is a device that forms a touch sensor electrode pattern to form a touch sensor integrated display device.

In electronic devices such as touch panels where a substrate with electrodes is placed in front of the display element, it is a necessary condition that the visibility of the display is not obstructed. Therefore, the electrodes are subject to shielding, scattering, stray light, reflection, etc. It is required to be as small as possible.
According to the electrode of the present invention, since the reflectance in the visible light region is 10% or less, glare is suppressed even when used as an electrode of a capacitive touch panel type input device, and the contrast ratio of the display is increased. Since the decrease is suppressed and the seat resistance is as small as 1 Ω / sq or less, the power consumption of electronic devices such as capacitance type input devices can be reduced.

1 Conductive layer 2 Blackening layer 3 Work function adjustment layer 10 Base material 20, 20'Electrode for organic EL element 30 Hole transport layer 40 Organic light emitting layer 50 Electron transport layer 60, 60'Transparent electrode 100, 100'Organic EL element L emission

Claims (13)

A conductive layer whose main component is metal or alloy,
A blackening layer having a reflectance of 40% or less in the visible light region provided on the conductive layer, and a blackening layer.
A work function adjusting layer made of a transparent conductive oxide having a predetermined work function provided on the blackening layer is included.
The conductive layer is a metal or alloy containing one or more metals selected from the group containing Al, Cu, Ag, Mo, and Cr as a main component.
The blackened layer is a physically vapor-deposited film of a lower oxide, a lower nitride, or a lower oxynitride containing Mo or Zn as a main component.
The work function adjusting layer is a transparent conductive oxide based on _{In 2} O _{3 or Zn O.}
The reflectance in the visible light region is 10% or less,
An electrode for an organic electroluminescence device characterized by a sheet resistance of 1 Ω / sq or less. The organic electroluminescence according to claim 1, wherein the electrode for an organic electroluminescence element is composed of three layers including the conductive layer, the blackening layer, and the work function adjusting layer. Electrode for element. The electrode for an organic electroluminescence element according to claim 1 or 2, wherein the etching can be performed collectively by wet etching using a phosphoric acid acetic acid-based etching solution which is a mixed solution of phosphoric acid, nitric acid and acetic acid. The blackening layer is composed mainly of M o, lower oxides, organic electroluminescent element of any one of claims 1 to 3, characterized by comprising a lower nitride, or a lower oxynitride Electrode. The work function adjustment layer, an organic electroluminescence element electrode according to any one of claims 1 to 4, characterized in that a transparent conductive oxide based on In ₂ O _3. The work function adjusting layer is made of a transparent conductive oxide obtained by adding one or more selected from the group containing Ga, Ce, Zn, Sn, Si, W, and Ti to _{In 2} O _3. Item 1. The electrode for an organic electroluminescence element according to Item 1. The electrode for an organic electroluminescence element according to claim 1 , wherein the work function adjusting layer is made of a transparent conductive oxide in which one or more selected from the group containing Al or Ga is added to ZnO. The electrode for an organic electroluminescence element according to any one of claims 1 to 7, wherein the work function adjusting layer has a work function of 4.6 eV or less and is used as a cathode of the organic electroluminescence element. The electrode for an organic electroluminescence element according to any one of claims 1 to 7, wherein the work function adjusting layer has a work function of 4.7 eV or more and is used as an anode of the organic electroluminescence element. An organic electroluminescence device comprising the electrode for the organic electroluminescence device according to any one of claims 1 to 9. The organic electroluminescence display device provided with the organic electroluminescence element according to claim 10 and not provided with a polarizing plate. A conductive layer laminating step of laminating a conductive layer containing one or more metals selected from the group containing Al, Cu, Ag, Mo, and Cr on a base material as a main component.
A blackened layer having a reflectance of 40% or less in the visible light region, which is composed of a lower oxide, a lower nitride, or a lower oxynitride, containing Mo or Zn as a main component, is laminated on the conductive layer by a physical vapor deposition method. Blackening layer laminating process and
A work function adjusting layer laminating step of laminating a work function adjusting layer having a predetermined work function made of a transparent conductive oxide based _{on In 2} O ₃ or Zn O on the blackened layer.
An etching step in which the laminated conductive layer, the blackening layer, and the work function adjusting layer are collectively etched by wet etching using a phosphoric acid, nitric acid, and acetic acid mixed solution of phosphoric acid, nitric acid, and acetic acid.
A method for manufacturing an electrode for an organic electroluminescence device, which comprises the above. A conductive layer whose main component is metal or alloy,
A blackening layer having a reflectance of 40% or less in the visible light region provided on the conductive layer, and a blackening layer.
A work function adjusting layer made of a transparent conductive oxide having a predetermined work function provided on the blackening layer is included.
The conductive layer is a metal or alloy containing one or more metals selected from the group containing Al, Cu, Ag, Mo, and Cr as a main component.
The blackened layer is a physically vapor-deposited film of a lower oxide, a lower nitride, or a lower oxynitride containing Mo or Zn as a main component.
The work function adjusting layer is a transparent conductive oxide based on _{In 2} O _{3 or Zn O.}
The reflectance in the visible light region is 10% or less,
An electrode for electronic devices characterized by a sheet resistance of 1 Ω / sq or less.

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