KR20190132378A - Electrode for organic electroluminescence element, organic electroluminescence element, organic electroluminescence display device, and method for manufacturing electrode for organic electroluminescence element - Google Patents

Abstract

The present invention can suppress external reflection and reduce the work function arbitrarily by reducing the reflectance in the visible light region, and can be applied to both the anode and the cathode of the organic EL device, and the organic EL device electrode and the organic EL device. It is a problem to provide a method for producing an electrode.
The above object is a transparent conductive oxide having a conductive layer 1 mainly composed of a metal or an alloy, a blackening layer 2 having a reflectance of 40% or less in the visible light region provided on the conductive layer, and a predetermined work function provided on the blackening layer. It is solved by the organic EL element electrode 20 which includes the work function adjustment layer 3 which consists of a metal oxide, and has the reflectance of 10% or less of visible region, and 1 or less ohm / sq.

Description

ELECTRODE FOR ORGANIC ELECTROLUMINESCENCE ELEMENT, ORGANIC ELECTROLUMINESCENCE ELEMENT, ORGANIC ELECTROLUMINESCENCE DISPLAY , AND METHOD FOR MANUFACTURING ELECTRODE FOR ORGANIC ELECTROLUMINESCENCE ELEMENT}

The present invention relates to a method for producing an electrode for an organic electroluminescent device, an organic electroluminescent device, an organic electroluminescent display device, and an electrode for an organic electroluminescent device.

In recent years, organic electroluminescent elements (hereinafter referred to as organic EL elements) are used in various fields, and in particular, they are used for display displays of smartphones, display devices such as thin TVs, and lighting fixtures.

The organic EL panel used for a display device or an illumination device using an organic EL element is classified into two types, a top emission type and a bottom emission type, depending on 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 stacked thereon. The top emission type is to extract light from the opposite side of the substrate, that is, the opposite side to 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 with the bottom emission type organic EL element, the top emission type organic EL element is suitable for high brightness and high definition since it can secure a high aperture ratio without being restricted by light shielding materials such as TFT and wiring.

In the top-emitting organic EL panel, it was necessary to prevent the reflection of external light of the TFT and the electrode for the organic EL element by installing a circular polarizing plate on the surface of the panel. However, the flexible organic EL panel has to overlap several sheets of the circularly polarizing film. The production of was difficult.

In order to omit the circularly polarizing plate, it is necessary to prevent the reflection of external light of the TFT and the organic EL element. The reflection of external light from the TFT array can be prevented with a black matrix, but a material having a low reflectance, a conductivity, and a deep work function is required for the anode of the organic EL element. In addition, when the reflective electrode side is used as the 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 polarized film, and describes an anode or cathode made of an oxide conductive film and an EL light emitting device provided with a light shielding film.

Patent document 2 relates to an organic EL display element using molybdenum or chromium oxide as an antireflection layer, and describes using molybdenum or chromium oxide as an antireflection layer in order to prevent reflection of external light by a metal electrode.

Patent document 3 relates to the organic light emitting device which suppressed the reflection of ambient light from the cathode, and describes using n-type semiconductors, such as zinc oxide, and calcium hexafluoride, as a reflection suppression layer.

PTL 4 relates to a color filter for EL constituting an EL display device, and describes using a light absorbing oxide such as molybdenum oxide as a material of the antireflection layer of the color filter for EL.

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

In Patent Documents 1 to 4, in order to prevent external reflection in the organic EL device, a light shielding film and an antireflection layer are provided. However, an electrode structure in which the work function is adjustable while having a low reflectance in the visible light region and good conductivity is not realized. Did.

Moreover, the electrode structure which can be etched collectively which can adjust the work function while having low reflectance and favorable electroconductivity of the visible region is not realized.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to reduce external reflectance by reducing the reflectance in the visible light region and to adjust the work function arbitrarily. It is providing the manufacturing method of the electrode for organic electroluminescent element, and the electrode for organic electroluminescent element applicable to the side.

Another object of the present invention is to provide a batch-etchable organic EL element electrode and a method for producing an organic EL element electrode, which have a low reflectance in the visible light region and good conductivity, and whose work function can be adjusted.

According to the electrode for an organic electroluminescent device of the present invention, a conductive layer mainly composed of a metal or an alloy, a blackening layer having a reflectance of 40% or less in the visible light region provided on the conductive layer, and a predetermined layer provided on the blackening layer It is solved by including the work function adjustment layer which consists of a transparent conductive oxide which has the work function of, the reflectance of visible region is 10% or less, and sheet resistance is 1 ohm / sq or less.

With the above structure, since the blackening layer and the work function adjustment layer are provided on the conductive layer, by reducing the reflectance in the visible light region, the external reflection is suppressed, the sheet resistance value is small, and the organic function capable of arbitrarily adjusting the work function. An electrode for an EL element can be provided. Therefore, it becomes possible to form the flexible organic EL panel without a polarizing plate.

At this time, it is suitable that the said electrode for organic electroluminescent elements consists of three layers which consist of the said conductive layer, the said blackening layer, and the said work function adjustment layer.

In this way, it has a low reflectance in the visible light region and sufficient conductivity, and has the advantage that it can be used both as an anode and a cathode, and is composed of a small number of layers called three layers. Can be thinned.

At this time, the said conductive layer is suitable if it is a metal or alloy whose main component is at least 1 sort (s) of metal chosen from the group containing Al, Cu, Ag, Mo, Cr.

By using these metals or alloys, conductive layers can be laminated by simple processes such as sputtering, and low sheet resistance can be realized.

At this time, the blackening layer is suitable if it is made of lower oxide, lower nitride or lower oxynitride mainly containing Mo or Zn.

Thus, by using the electroconductive material which has high absorbance in visible region as a blackening layer, the reflectance and favorable electroconductivity of low visible region can be implement | achieved.

In this case, in which the work function adjustment layer is formed of a transparent conductive oxide containing In ₂ O ₃ or ZnO as a base, selected from the group consisting of the In ₂ O ₃ including Ga, Ce, Zn, Sn, Si, W, Ti It is suitable if it consists of the transparent conductive oxide to which 1 or more types were added, or the transparent conductive oxide to which 1 or more types chosen from the group which contains Al or Ga to ZnO is added.

In this manner, by using a transparent conductive oxide capable of doping various metals as the work function adjusting layer and adjusting the work function according to the addition amount of the dopant, the electrode can be used as an anode or a cathode and has a low reflectance in the visible region. Can provide.

In this case, the work function adjusting layer is suitably used when the work function is 4.6 eV or less, used as the cathode of the organic electroluminescent device, or the work function is 4.7 eV or more, used as the anode of the organic electroluminescent device. .

Thus, since the work function of a work function adjustment layer is adjusted according to the kind and addition amount of the dopant added to the transparent conductive oxide used as a base, it can be used also as an anode and an anode of an organic EL element.

The said subject is provided with the organic electroluminescent element provided with the electrode for organic electroluminescent elements of this invention, and the organic electroluminescent display apparatus provided with the said organic electroluminescent element, and without a polarizing plate. Resolved.

Thus, since the reflectance in the visible light region is reduced in the electrode for organic electroluminescent elements of this invention, when used as an electrode of an organic electroluminescent element and an organic electroluminescence display, external reflection can be suppressed, An organic EL display device without a polarizing plate can be provided.

According to the method for producing an electrode for an organic electroluminescent device of the present invention, the above-described problem is to provide a conductive layer containing, as a main component, at least one metal selected from the group consisting of Al, Cu, Ag, Mo, and Cr on a substrate. Conductive layer lamination step of laminating, blackening layer lamination step of laminating blackening layer having reflectance of visible light region composed of lower oxide, lower nitride or lower oxynitride mainly composed of Mo or Zn on the conductive layer of 40% or less, the blackening layer on the work function adjustment layer laminating step, and a laminate of the conductive layer and the blackening layer and the work function of laminating the work function adjustment layer having a predetermined work function made of a transparent conductive oxide containing in ₂ O ₃ or ZnO as a base This is solved by performing an etching step of collectively etching the adjustment layer.

As described above, since the conductive layer, the blackening layer, and the work function adjustment layer are formed of an appropriate material, the electrode can be collectively etched by wet etching using a phosphorus acetic acid-based etching solution (phosphoric acid, nitric acid, acetic acid mixed solution), thereby producing an electrode. Is easy.

In addition, since the blackening layer and the work function adjusting layer are provided on the conductive layer, by reducing the reflectance in the visible light region, external reflection is suppressed, the sheet resistance is small, and the electrode for the organic EL element capable of arbitrarily adjusting the work function. Can be provided.

According to an electrode for an electronic device of the present invention, the above object has a conductive layer composed mainly of a metal or an alloy, a blackening layer having a reflectance of 40% or less in the visible light region provided on the conductive layer, and a predetermined work function provided on the blackening layer. It is solved by including the work function adjustment layer which consists of a transparent conductive oxide, the reflectance of visible region is 10% or less, and sheet resistance is 1 ohm / sq or less.

With the above configuration, since the blackening layer and the work function adjusting layer are provided on the conductive layer, the external reflection is suppressed by reducing the reflectance in the visible light region, and the sheet resistance value is small, so that the power consumption of the electronic device is increased. It is possible to provide a reduced electrode for electronic equipment.

In the electrode for organic EL device of the present invention, since the blackening layer is formed of lower oxide, lower nitride, or lower oxynitride containing Mo or Zn as a main component having high electrical conductivity and high absorbance in the visible light region, the sheet resistance value With this low, the reflectance can be lowered. Moreover, since the transparent conductive oxide which has a suitable work function is used as a work function adjustment layer, it is possible to use an electrode for both an anode and a cathode. In addition, by combining the blackening layer and the work function adjusting layer, the reflectance in the visible light region can be lowered to 10% or less. Therefore, the flexible organic EL panel without a polarizing plate can be formed.

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

1: is a schematic cross section which shows the electrode for organic electroluminescent elements of one Embodiment of this invention.
2 is a flowchart of a method for manufacturing an electrode for an organic EL device according to one embodiment of the present invention.
It is a schematic cross section which shows the organic electroluminescent element of one Embodiment of this invention.
It is a schematic cross section which shows the organic electroluminescent element of the modification of one Embodiment of this invention.
5A is a graph showing refractive indexes as a result of measuring optical constants of the blackening layers of Reference Examples 1 and 2 of the present invention.
5B is a graph showing an extinction coefficient as a result of measuring optical constants of the blackening layers of Reference Examples 1 and 2 of the present invention.
6 is a graph showing the reflectance measurement results of the blackening layer of Reference Examples 1 to 3 of the present invention.
7 is a graph showing the reflectance measurement results of the work function adjustment layer of Reference Examples 4 to 8 of the present invention.
8 is a graph showing the reflectance measurement results of the electrodes for organic EL elements of Example 1 and Comparative Example 1 of the present invention.
9 is a graph showing the reflectance measurement results of the electrodes for organic EL elements of Examples 2 to 6 and Comparative Example 2 of the present invention.
10 is a SEM cross-sectional photograph of a sample of the organic EL element electrode of Example 2 etched.
11 is a graph showing the reflectance measurement results of the conductive film of Example 7 of the present invention.

About the organic electroluminescent element electrode of one Embodiment of this invention, the manufacturing method of the organic electroluminescent element electrode, the organic electroluminescent element provided with this organic electroluminescent element electrode, and the organic electroluminescence display using this organic electroluminescent element. Explain.

<Electrode for organic EL element>

As shown in FIG. 1, the organic EL element electrode 20 of the present embodiment has a work function adjustment formed on the conductive layer 1, the blackening layer 2 formed on the conductive layer 1, and the blackening layer 2. The layers 3 are laminated. Below, each layer which comprises the electrode for organic electroluminescent elements 20 is described in detail.

(Conductor Floor)

The conductive layer 1 is a group containing a metal or APC (silver, palladium, copper alloy), AlNd, AlSi, AlCu, AlSiCu having as a main component one or more selected from the group containing Al, Cu, Ag, and Mo. Alloy selected from.

Here, the main component is a case where 50 wt% or more is included in the weight ratio in the conductive layer.

As a metal which comprises the conductive layer 1, there exists sufficient electroconductivity and what is necessary is just the metal used for the organic electroluminescent element. For example, Al, Cu, Ag, Mo, etc. are mentioned, It is not limited to these.

As an alloy which comprises the conductive layer 1, there exists sufficient electroconductivity and what is necessary is just the alloy used for the organic electroluminescent element. For example, the alloy which has Al, Cu, Ag, Mo, etc. as a main component, or the alloy chosen from the group containing APC (silver, palladium, a copper alloy), AlNd, AlSi, AlCu, AlSiCu, These are mentioned. It is not limited.

The thickness of the conductive layer 1 is preferably 10 nm or more and 1,000 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 or less. It is good to be nm or less, More preferably, it is 50 nm or more and 500 nm or less. When the thickness of the conductive layer 1 becomes too thin, electroconductivity will fall. On the other hand, when the conductive layer 1 is too thick, the thickness of the organic EL element will increase, and the workability and manufacturability of etching will decrease.

(Black layer)

The blackening layer 2 is a layer having a reflectance of 40% or less in the visible light region composed of lower oxide, lower nitride or lower oxynitride mainly containing Mo or Zn.

Here, the main component is a case where Mo or Zn contained in the blackening layer is contained by 50 atomic% or more in the atomic number ratio of the metal atoms.

The lower oxide, lower nitride or lower oxynitride constituting the blackening layer 2 may be sufficiently absorbed in the visible light region and have sufficient conductivity. For example, although lower oxide, lower nitride, or lower oxynitride which has Mo or Zn as a main component is mentioned, it is not limited to these.

Lower oxides containing Mo as the main component are MoO _x (x = stoichiometric ratio, 2≤x <3), and lower nitrides containing Mo as the main component are MoN _y (y = stoichiometric ratio) and lower oxynitride containing Mo as the main component. Is MoO _x N _y (x, y = stoichiometric ratio).

Lower oxides based on Zn are ZnO _x (x = stoichiometric ratio); lower nitrides based on Zn are ZnN _y (y = stoichiometric ratio); lower oxynitrides containing Zn as ZnO _x N _y ( x, y = stoichiometric ratio).

In the blackening layer 2, the dopant metal may be added to metals other than Mo or Zn which are main components.

The dopant metal is preferably a transition metal, for example, but is not limited to, Nb, W, Al, Ni, Cu, Cr, Ti, Ag, Ga, Zn, In, Ta.

It is preferable that the content rate of the dopant metal with respect to the lower oxide, lower nitride, or lower oxynitride which has Mo or Zn as a main component is 20 atomic% or less. Since the content rate of the dopant metal (Nb, Ta, etc.) is in the above range, good conductivity and light absorption in the visible light region can be realized.

It is preferable that the reflectance of the visible light region of the blackening layer 2 is 50% or less, More preferably, it is 40% or less. According to the definition of JIS Z8120, the lower limit of the electromagnetic wave wavelength corresponding to visible light is about 360 to 400 nm and the upper limit is about 760 to 830 nm. In the present embodiment, the visible light region refers to a wavelength region of 400 nm to 700 nm. .

When the visible light transmittance of the blackening layer 2 is low, the visible light reflected from the electrode for organic electroluminescent element 20 is reduced, and can be used suitably for the flexible organic electroluminescence display without a polarizing plate.

It is preferable that the thickness of the blackening layer 2 shall be 5 nm or more and 200 nm or less, More preferably, it is 10 nm or more and 150 nm or less, More preferably, it is 20 nm or more and 100 nm or less, More preferably, it is 30 nm or more 75 It is good to be nm or less, More preferably, it is 40 nm or more and 60 nm or less. If the thickness of the blackening layer 2 becomes too thin, absorption of the light of a visible light region will become inadequate or film-forming will become difficult. On the other hand, when the blackening layer 2 is too thick, the workability and manufacturability of an etching will fall.

(Work function adjustment layer)

The work function adjustment layer 3 is a layer made of a transparent conductive oxide having a predetermined work function.

As a transparent conductive oxide which comprises the work function adjustment layer 3, there exists sufficient electroconductivity, and what is necessary is just a transparent conductive oxide which can adjust a work function by adding various metals. Examples of such a transparent conductive oxide include In ₂ O ₃ , ZnO, Ga ₂ O ₃ , SnO ₂ , TiO ₂ , CdO, composite oxides thereof, and the like, but are not limited thereto.

In the present embodiment, as a material for forming the work function adjustment layer 3, it is preferable to use a transparent conductive oxide for the In ₂ O ₃ or ZnO as a base.

Transparent conductive oxide based on In ₂ O ₃ , wherein transparent conductive oxide is added with at least one metal element selected from the group consisting of Ga, Ce, Zn, Sn, Si, W, and Ti to In ₂ O ₃ as a main component Oxides can be used.

Among these transparent conductive oxides based on In ₂ O ₃ , Ga added IGO (gallium dope indium oxide), Zn added IZO (indium zinc oxide), Sn added ITO (indium tin oxide), Ce, ICO (indium cerium oxide) added with Sn, Ti, and IWZO (tungsten-zinc dope indium oxide) added with W and Zn can be suitably used.

Further, the content of the metal element added to In ₂ O ₃ is preferably not more than 50% by weight. When it contains much more than the said range, since it becomes high resistance, it is unpreferable.

Further, transparent electrically conductive oxide containing In ₂ O ₃ as a base, comprising in the range Ga, Ce, Zn, in addition to Sn, Si, W, Ti, other elements are not detrimental to the performance of an electrode for an organic EL device of the present embodiment It does not matter.

As the transparent conductive oxide based on ZnO, a transparent conductive oxide in which at least one metal element selected from the group containing Al or Ga is added to ZnO as a main component can be used.

Examples of such ZnO-based transparent conductive oxides include AZO (aluminum dope zinc oxide) with Al, GZO (gallium dope zinc oxide) with Ga, and GAZO (gallium / aluminum dope zinc oxide) with Al and Ga added. Can be suitably used.

In addition, it is preferable that the content rate of the metal element added to ZnO is 10 weight% or less by weight ratio. When it contains much more than the said range, since it becomes high resistance, it is unpreferable.

In addition, other elements other than Al or Ga may be contained in the transparent conductive oxide based on ZnO in the range which does not impair the performance of the electrode for organic electroluminescent elements of this embodiment.

When using the electrode for organic electroluminescent element 20 as a cathode, what is necessary is just to select a transparent conductive oxide so that the work function of the work function adjustment layer 3 may be 4.6 eV or less, for example.

On the other hand, when using the electrode for organic electroluminescent element 20 as an anode, what is necessary is just to select a transparent conductive oxide so that the work function of a work function adjustment layer may be 4.7 eV or more, for example.

In the present embodiment, by the addition of various metals in the work function adjustment layer 3, there is adjusted to a predetermined work function, the addition of various metal causes the In ₂ O ₃ or ZnO of crystallinity decreased serving as a base. Therefore, the crystallinity of the work function adjustment layer 3 decreases and becomes amorphous by addition of a metal, and can be etched using a predetermined etching liquid.

The thickness of the work function adjustment 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. 60 nm or less, More preferably, you may be 40 nm or more and 50 nm or less. When the thickness of the work function adjustment layer 3 becomes too thin, absorption of light in the visible light region becomes insufficient, the work function is unstable, or film formation becomes difficult. On the other hand, when the work function adjustment layer 3 is too thick, workability and manufacturability of etching will fall.

(Physical Properties of Electrodes for Organic EL Elements)

The organic electroluminescent element electrode 20 of this embodiment has the reflectance of the low visible light region which can be used for the organic electroluminescence display which does not have a polarizing plate, and has sufficient electroconductivity by setting it as said structure.

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

The sheet resistance of the electrode for organic electroluminescent element 20 is 1 ohm / sq or less, More preferably, it is 0.75 ohm / sq or less, More preferably, it is 0.5 ohm / sq or less, Especially preferably, it is 0.25 ohm / sq or less.

The work function of the organic EL element electrode 20 is determined by the work function of the work function adjustment layer 3, and when the organic EL element electrode 20 is used as a cathode, the organic EL element is 4.6 eV or less. When the electrode 20 is used as an anode, it is 4.7 eV or more.

The organic EL element electrode 20 is composed of a small number of three layers consisting of a conductive layer 1, a blackening layer 2, and a work function adjusting layer 3, and has a low reflectance in the visible region and sufficient conductivity. By suitably selecting the material used for a work function adjustment layer, it has the advantage that it can be used also as an anode and a cathode of an organic EL element.

The thickness of the organic EL element electrode 20 is preferably 20 nm or more and 1,500 nm or less, more preferably 100 nm or more and 1,000 nm or less, more preferably 200 nm or more and 800 nm or less, still more preferably 300 It is good to be nm or more and 600 nm or less, More preferably, 350 nm or more and 500 nm or less. If the electrode 20 for organic EL elements is too thick, the workability and manufacturability of etching will fall.

<Method for Manufacturing Electrode for Organic EL Element>

As shown in FIG. 2, the organic-electrode element electrode 20 of this embodiment has a conductive layer which has as a main component the at least 1 sort (s) of metal chosen from the group containing Al, Cu, Ag, Mo, Cr on a base material. Conductive layer lamination step of laminating, blackening layer lamination step of laminating blackening layer having reflectance of visible light region composed of lower oxide, lower nitride or lower oxynitride mainly composed of Mo or Zn on the conductive layer of 40% or less, the blackening layer on the work function adjustment layer laminating step, and a laminate of the conductive layer and the blackening layer and the work function of laminating the work function adjustment layer having a predetermined work function made of a transparent conductive oxide containing in ₂ O ₃ or ZnO as a base It manufactures by the manufacturing method of the electrode for organic electroluminescent elements characterized by performing the etching process which etches an adjustment layer collectively.

Each process is explained in full detail below with reference to FIG.

(Conductive Layer Lamination Process)

In the conductive layer lamination step (step S1), the conductive layer 1 containing the at least one metal selected from the group containing Al, Cu, Ag, Mo, and Cr as a main component is laminated on the substrate 10. The method of forming the conductive layer 1 on the substrate 10 may be a physical vapor deposition method such as sputtering, vacuum deposition, or ion plating, but is not limited thereto.

(Blackening layer lamination process)

In the blackening layer lamination process (step S2), the visible light region which consists of lower oxide, lower nitride, or lower oxynitride which has Mo or Zn as a main component on the conductive layer 1 laminated | stacked on the base material 10 in the said conductive layer lamination process. The blackening layer 2 whose reflectance is 40% or less is laminated. The method of forming the blackening layer 2 on the conductive layer 1 can use physical vapor deposition methods, such as a sputtering method, a vacuum vapor deposition method, and an ion plating method, but it is not limited to this.

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

(Work function adjustment layer lamination process)

The work function adjustment layer depositing step (step S3) in the predetermined one of made of a transparent conductive oxide containing In ₂ O ₃ or ZnO as a base on the conductive layer 1, a blackening layer (2) laminated on in the blackening layer depositing step A work function adjustment layer 3 having a function is laminated. The method for forming the work function adjustment layer 3 on the blackening layer 2 may be a physical vapor deposition method such as sputtering, vacuum deposition, or ion plating, but is not limited thereto.

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

If the method of forming the conductive layer 1, the blackening layer 2 and the work function adjustment layer 3 is, for example, a vacuum deposition method and / or a sputtering method, the drying process is performed on the substrate 10 continuously and continuously. The electrode 20 for organic electroluminescent elements can be formed.

(Etching process)

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

The etching method may use wet etching with etching liquid or dry etching such as reactive gas etching, reactive ion etching, reactive ion beam etching, ion beam etching, reactive laser beam etching, or the like.

In this embodiment, since the conductive layer 1, the blackening layer 2, and the work function adjustment layer 3 are formed of the above-mentioned material, it is necessary to perform wet etching using a phosphorus acetic acid-based etching solution (phosphoric acid, nitric acid, acetic acid mixed liquid). Collectively etching is possible.

<Organic Light Emitting Device>

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) has a base 10 and an electrode for organic EL element 20. The hole transport layer 30, the organic light emitting layer 40, the electron transport layer 50, and the transparent electrode 60 are stacked in this order, and the light emission L is extracted from the opposite side of the substrate 10.

Since the reflectance of the visible light region is 10% or less and external light reflection is suppressed, the organic electroluminescent element electrode 20 of this embodiment has the advantage that it is not necessary to use a polarizing plate.

Below, each component of the organic electroluminescent element 100 is demonstrated in detail.

(materials)

The base material 10 constituting the organic EL device 100 of the present invention may be any one that does not change when forming the electrode and the organic material layer. For example, glass, plastic, polymer film, silicon substrate, a laminate of these, or the like may be used. Can be.

(Hole transport layer)

Examples of the material constituting the hole transport layer 30 include polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or the main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives and triphenyl. Diamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polyarylamines or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, or poly (2,5-thienylenevinyl) Lene) or derivatives thereof, and the like.

The method of forming the hole transport layer 30 is not particularly limited, but in the case of a low molecular hole transport material, a method is formed by forming a film from a mixed solution with a polymer binder. In the case of a polymer hole transport material, The method by film-forming is mentioned.

The film thickness of the hole transport layer 30 may be selected so that the optimum value is different depending on the material, so that the driving voltage and the luminous efficiency are appropriate, but at least a thickness at which pinholes do not occur is required. If the film thickness is too thick, the driving voltage of the organic EL element 100 becomes high, so that the film thickness of the hole transport layer 30 is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, More preferably, it may be 5 nm to 200 nm.

(Organic Light Emitting Layer)

The organic light emitting layer 40 contains organic materials (low molecular weight compounds and high molecular compounds) that emit fluorescence or phosphorescence. Moreover, the dopant material may be further included. As a material which forms the organic light emitting layer 40 which can be used in this embodiment, a pigment type material, a metal complex system material, and a polymeric material are mentioned, for example, It is not limited to this.

In addition, it is also possible to add a dopant in the organic light emitting layer 40 for the purpose of improving the luminous efficiency or changing the light emission wavelength.

The method of 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 the substrate, a vacuum deposition method, a transfer method, or the like can be used.

The thickness of the organic light emitting layer 40 is 20-2,000 kPa normally.

(Electron transport layer)

As the material constituting the electron transporting layer 50, known materials can be used, and oxadiazole derivatives, anthraquinomethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetra Cyanoanthracinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline Or derivatives thereof, polyfluorene or derivatives thereof, and the like.

The method of forming the electron transport layer 50 is not particularly limited, but in the case of a low molecular electron transport material, there may be mentioned a method of vacuum deposition from powder or a film from a solution or molten state. In the case, the method by film-forming from a solution or a molten state is mentioned.

The film thickness of the electron transporting layer 50 may be selected so that the optimum value is different depending on the material, so that the driving voltage and the luminous efficiency are appropriate, but at least a thickness at which pinholes do not occur is required. If the film thickness is too thick, the driving voltage of the organic EL element 100 becomes high, so that the film thickness of the electron transporting layer 50 is, for example, 1 nm to 1 m, preferably 2 nm to 500 nm, More preferably, 5 nm-200 nm may be sufficient.

(Transparent electrode)

Since the organic electroluminescent element 100 of this embodiment emits light through the transparent electrode 60, it is necessary for the transparent electrode 60 to use a transparent or translucent electrode.

In the organic EL element 100 of the present embodiment, when the electrode 20 for an organic EL element is used as an anode, the material constituting the transparent electrode 60 serving as a cathode has a small work function and has an electron transport layer 50 and an organic layer. A material that is easy to inject electrons into the light emitting layer 40 is preferable. For example, an electroconductive metal oxide, an electroconductive organic substance, etc. can be used. Specifically, indium oxide, zinc oxide, tin oxide, and ITO or IZO which are composites thereof can be used as the conductive metal oxide, but the present invention is not limited thereto. As a conductive organic substance, although organic transparent conductive films, such as polyaniline or its derivative (s), polythiophene or its derivative (s), can be accommodated, it is not limited to this.

(Modified example of organic light emitting element)

Fig. 3 shows a top emission type organic EL element 100 including the organic EL element electrode 20 of the present embodiment as an anode (anode). The organic EL element electrode 20 of the present embodiment is a cathode. It is also possible to use as a (cathode).

As one modification of this embodiment, FIG. 4 shows an organic EL element 100 'using an organic EL element electrode 20' as a cathode. In the case of the organic EL element 100 ', the substrate 10, the electrode for the organic EL element 20', the electron transport layer 50, the organic light emitting layer 40, the hole transport layer 30 and the transparent electrode 60 ' Since the electrode 20 'for organic electroluminescent element is used as a cathode in order to laminate | stack and form, the position of the electron carrying layer 50 and the hole carrying layer 30 differs.

Here, in the organic EL element 100 'of the modification of this embodiment, the electrode for organic EL element 20' is used as a cathode, and the work function is large as a material which comprises the transparent electrode 60 'which is an anode. A material that facilitates hole injection 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, a metal sulfide or a thin film of metal having high electrical conductivity can be used. As the transparent electrode, indium oxide, zinc oxide, tin oxide, and ITO and IZO which are composites thereof are preferable, but not limited thereto.

(Organic Light Emitting Device)

Since the organic EL elements 100 and 100 'of the present embodiment have low reflectance in the visible light region and external reflection is suppressed, it is possible to produce an organic EL display device without a polarizing plate without using a polarizing plate.

Examples of the organic EL display include a display of a mobile terminal such as a smartphone and a tablet terminal, a display of a thin TV, and the like, but is not limited thereto.

If the base material of flexible material, such as a plastic film, is selected as the base material 10, it can be set as a flexible organic electroluminescence display.

In this embodiment, the manufacturing method of the electrode for organic electroluminescent element of this invention, an organic electroluminescent element, an organic electroluminescence display, and an organic electroluminescent element mainly was demonstrated.

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 changed and improved without departing from the spirit thereof, and of course, the equivalents thereof are included in the present invention.

Example

EMBODIMENT OF THE INVENTION Although the specific Example of the electrode for organic electroluminescent elements of this invention is demonstrated below, this invention is not limited to this.

<A. Formation of Electrodes for Organic EL Devices of Examples and Comparative Examples>

(A-1.Conductive Layer Formation Step)

The conductive layers of Examples 1 to 6 and Comparative Examples 1 and 2 were laminated on the substrate under the following conditions.

  Sputtering Device: Carousel Type Sputtering Device

  Target: 5 "x 25", thickness 6mm, aluminum (Al) 100%

  Sputtering method: DC magnetron sputter

  Exhaust System ： Turbo Molecular Pump

Reach vacuum level: 5 x 10 ^-4 kPa

  Base temperature: 25 degrees Celsius (room temperature)

  Sputter power: 6 kW

  Film thickness of the conductive layer: 300 ± 10 nm

  Ar flow rate ： 250 sccm

  Use base material ： Glass base material (1.1mm thickness)

(A-2. Blackening layer lamination process)

MoNbO _x (x = stoichiometric ratio) as a blackening layer was laminated on the conductive layers of Example 1 and Comparative Example 1 under the following conditions, and MoO _x (as a blackening layer on the conductive layers of Examples 2-6 and Comparative Example 2 ( x = stoichiometric ratio) was laminated.

  Sputtering Device: Carousel Type Sputtering Device

  target :

  (Example 1) 5 "x 25", thickness 6mm, Mo 90 atomic%, Nb 10 atomic%

  (Comparative Example 1) 5 "x 25", thickness 6mm, Mo 90 atomic%, Nb 10 atomic%

  (Examples 2 to 6) 5 "x 25", thickness 6mm, Mo 100 atomic%

  (Comparative Example 2) 5 "x 25", thickness 6mm, Mo 100 atomic%

  Sputtering method: DC magnetron sputter

  Exhaust System ： Turbo Molecular Pump

Reach vacuum level: 5 x 10 ^-4 kPa

  Base temperature: 25 degrees Celsius (room temperature)

  Sputter power: 3 kW

  Film thickness of blackening layer: 50 ± 5 nm

  Ar flow rate ： 250 sccm

  Oxygen flow rate ： 50 sccm

(A-3.Work Function Adjustment Layer Lamination Process)

IGO (gallium dope indium oxide) as a work function adjustment layer was laminated on the blackening layer of Examples 1-6 on the following conditions. On the other hand, the work function adjustment layer was not laminated on the blackening layers of Comparative Examples 1 and 2.

  Sputtering Device: Carousel Type Sputtering Device

  target :

(Example 1) 5 "× 25", thickness _{6 ㎜, In 2 O 3 60} % by weight, Ga ₂ O ₃ 40% by weight

(Example 2) 5 "25 ×", 6 ㎜ thickness, 60% by weight of In ₂ O _3, Ga ₂ O ₃ wt% 40

(Example 3) 5 "× 25", thickness 6 ㎜, In ₂ O ₃ 90 wt%, Sn ₂ O ₃ 10% by weight

(Example 4) 5 "× 25", thickness 6 ㎜, In ₂ O ₃ 90 wt%, ZnO 10% by weight

(Example 5) 5 "× 25", thickness _{6 ㎜, In 2 O 3 86.5} % by weight, CeO ₂ 10 wt%, SnO ₂ 3.2% by weight, TiO ₂ 0.3% by weight

(Example 6) 5 "× 25", thickness _{6 ㎜, In 2 O 3 96.5} % by weight, 3.0% by weight of WO _3, ZnO 0.5% by weight

  Sputtering method: DC magnetron sputter

  Exhaust System ： Turbo Molecular Pump

Reach vacuum level: 5 x 10 ^-4 kPa

  Base temperature: 25 degrees Celsius (room temperature)

  Sputter power: 2 kW

  Film thickness of work function adjustment layer: 35 ± 5 nm

  Ar flow rate ： 100 sccm

  Oxygen flow rate ： 5 sccm

<B. Formation of blackening layer or work function adjustment layer of reference example>

(B-1. Blackening layer lamination step)

The blackening layer of Reference Examples 1-3 was laminated | stacked on the base material on condition of the following.

  Sputtering Device: Carousel Type Sputtering Device

  target :

  (Reference Example 1) 5 "x 25", thickness 6mm, Mo 100 atomic%

  (Reference Example 2) 5 "x 25", thickness 6mm, Mo 90 atomic%, Nb 10 atomic%

  (Reference Example 3) 5 "x 25", thickness 6mm, Mo 90 atomic%, Nb 7 atomic%, Ta 3 atomic%

  Sputtering method: DC magnetron sputter

  Exhaust System ： Turbo Molecular Pump

Reach vacuum level: 5 x 10 ^-4 kPa

  Base temperature: 25 degrees Celsius (room temperature)

  Sputter power: 3 kW

  Film thickness of blackening layer: 50 ± 5 nm

  Ar flow rate ： 250 sccm

  Oxygen flow rate ： 50 sccm

(B-2.Work Function Adjustment Layer Lamination Process)

The work function adjustment layer of Reference Examples 4-8 was laminated | stacked on the base material on condition of the following.

  Sputtering Device: Carousel Type Sputtering Device

  target :

(Reference Example 4) 5 "× 25", thickness _{6 ㎜, 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 weight%, Sn ₂ O ₃ 10 weight%

(Reference Example 6) 5 "× 25", thickness 6 ㎜, In ₂ O ₃ 90 wt%, ZnO 10% by weight

(Reference Example 7) 5 "× 25", thickness _{6 ㎜, In 2 O 3 86.5} % by weight, CeO ₂ 10 wt%, SnO ₂ 3.2% by weight, TiO ₂ 0.3% by weight

(Reference Example 8) 5 "× 25", thickness _{6 ㎜, In 2 O 3 96.5} % by weight, 3.0% by weight of WO _3, ZnO 0.5% by weight

  Sputtering method: DC magnetron sputter

  Exhaust System ： Turbo Molecular Pump

Reach vacuum level: 5 x 10 ^-4 kPa

  Base temperature: 25 degrees Celsius (room temperature)

  Sputter power: 2 kW

  Film thickness of work function adjustment layer: 35 ± 5 nm

  Ar flow rate ： 100 sccm

  Oxygen flow rate ： 5 sccm

<C. Various examinations ＞

(Reference test 1: Optical constant measurement of blackening layer)

The optical constants of the blackening layers of Reference Example 1 and Reference Example 2 were measured. The optical constants were measured using a spectroscopic ellipsometer (manufactured by Japan Spectroscopy Co., Ltd., M-220).

The results are shown in FIGS. 5A and 5B. 5A is a graph showing the refractive index, and FIG. 5B is a graph showing the extinction coefficient.

The refractive index n and extinction coefficient k at 550 nm are shown in Table 1.

(Reference test 2: Reflectance measurement of blackening layer)

The reflectances of the blackening layers of Reference Examples 1 to 3 were measured. The reflectance was measured in the wavelength range of 350 nm-800 nm using the spectrophotometer (the Hitachi High-Technologies Corporation make, U-4100).

The results are shown in FIG.

It was found that the reflectance of the blackening layers of Reference Examples 1 to 3 was about 25% or more and 40% or less, and it was impossible to lower the reflectance in the visible light region to 10% or less when only blackening layers were laminated.

(Reference test 3: Reflectance measurement of work function adjustment layer)

The reflectance of the work function adjustment layers of Reference Examples 4 to 8 was measured. The reflectance was measured in the wavelength range of 350 nm-800 nm using the spectrophotometer (the Hitachi High-Technologies Corporation make, U-4100).

The results are shown in FIG.

It was found that the reflectance of the work function adjustment layers of Reference Examples 4 to 8 was greater than 10%, so that when only the work function adjustment layers were laminated, it was impossible to lower the reflectance in the visible light region to 10% or less.

(Reference test 4: work function measurement of work function adjustment layer)

The work function of the work function adjustment layer of the reference examples 4-8 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 an electrode for organic EL elements)

The reflectances of the electrodes of Examples (Examples 1 to 6) and Comparative Examples (Comparative Example 1, Comparative Example 2) were measured. The reflectance was measured in the wavelength range of 350 nm-800 nm using the spectrophotometer (the Hitachi High-Technologies Corporation make, U-4100).

The results are shown in FIGS. 8 and 9.

In FIG. 8, the reflectance of the comparative example 1 shown by the broken line was 10% or more. On the other hand, the reflectance of Example 1 represented by the solid line showed a maximum value of 7.4% (535 nm) at 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 the comparative example 2 shown by the dotted line was 10% or more. On the other hand, the reflectance of Examples 2 to 6 exhibited a low value of 10% or less in the entire visible light region of 400 nm to 700 nm.

From these results, when only the blackening layer is laminated | stacked on the conductive layer, it is impossible to reduce the reflectance in visible region to 10% or less, and by setting it as the three-layer structure which consists of a conductive layer, a blackening layer, and a work function adjustment layer, It was found that the reflectance in the visible light region can be 10% or less.

(Test 2: Measurement of sheet resistance and work function of electrode for organic EL elements)

The sheet resistance of the electrode of Example 1 and the comparative example 1 was measured by the 4-terminal method using a resistivity meter (The Mitsubishi Chemical Analyte Co., Model name MCP-T610).

The work functions of the electrodes of Examples 1 to 6 and Comparative Examples 1 and 2 were calculated using an atmospheric photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd., model name AC-2).

The results are shown in Table 3 below.

As mentioned above, it turned out that the sheet resistance value of the electrode of Example 1 showed the value small enough as 0.11 ohm / sq, and can be used as an electrode for organic electroluminescent elements. In addition, the electrode of Example 1 showed the same value as the sheet resistance value of the comparative example 1 which does not have a work function adjustment layer, and the work function adjustment layer does not affect the sheet resistance value, but the reflectance in visible region is 10 It turned out that it can be made into% or less.

In addition, since the work function of the work function adjustment layer can be set to an arbitrary value according to the type of dopant added to the transparent conductive oxide serving as the base, it can be seen that it can be used both as the anode and the cathode of the organic EL element. there was.

(Test 3: etching evaluation)

Etching evaluation was performed about the electrode of Example 2.

A photoresist (OFPR-800LB manufactured by Tokyo Oka) was coated on the conductive film of Example 2, and a patterned mask was burned by irradiating ultraviolet rays using a patterned mask disc. Using a developing solution (TMAH (tetramethylammonium hydroxide) aqueous solution), the uncured photoresist was removed to develop a pattern of the original plate, and an unnecessary portion of the conductive film from which the photoresist was removed was removed by etching (phosphate, nitric acid, acetic acid mixed solution). It removed with the used etching liquid. Then, the photoresist which remained on the electrically conductive film was peeled and washed and the etching sample of Example 2 was obtained.

Then, SEM cross-sectional analysis (Hitachi Hi-Tech Fielding S-4300) was performed about the etching sample of Example 2.

The 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 turned out that favorable etching is performed.

(Example 7: Al-Nd / nitride Mo-Nb / IGO conductive film)

An Al-Nd alloy layer (film thickness 330 nm), a nitride layer of Mo-Nb alloy (film thickness 40 nm), and an IGO layer (film thickness 30 nm) were prepared on the glass substrate in the following procedure, It was set as the electrically conductive film.

An Al-Nd alloy layer having a film thickness of 330 nm was formed on the glass substrate by a DC magnetron sputtering method.

Next, the target, the film thickness, the sputtering power, and the introduction gas were changed as follows, and a Mo-Nb alloy nitride layer was formed on the Al-Nd alloy layer.

Target: Thickness 9mm, Mo-Nb target

Sputter 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 introduction gas were changed as follows, and an IGO layer was formed on the nitride layer of the Mo-Nb alloy.

Target: IGO 6 t 5 "x 62" target

Sputter power: 2.5 W / cm 2

Film thickness: 30 nm

Ar flow rate: 500 sccm

O ₂ flow rate: 12 sccm

The conductive film of Example 7 was obtained from the above.

○ Characteristic of conductive film

The characteristic of the electrically conductive film of Example 7 formed into a film as mentioned above was measured.

Resistance value and reflectance of the conductive film of Example 7

About the electrically conductive film of Example 7, the reflectance in the visible range from 400 nm to 700 nm was measured using the spectrophotometer (The Hitachi, Ltd. make, U-4100). In addition, the resistivity was measured using a resistivity meter (Leste Star GP manufactured by Mitsubishi Chemical), and the reflectance was measured using a film thickness meter (DEKTAKXT, manufactured by Albak Corporation). The measurement result of reflectance is shown in FIG. 11, and the measurement result of a resistance value and a film thickness is shown in Table 4. FIG.

The reflectance of the conductive film of Example 7 shown by the solid line in FIG. 11 showed a low value of 10% or less in the entire visible light region of 400 nm to 700 nm.

In addition, the sheet resistance of the conductive film of Example 7 exhibited a sufficiently small value of 0.16 Ω / sq, and it was found that it can be used as the conductive film.

As mentioned above, although the electrode for organic electroluminescent element was demonstrated as an example of the electrode of this invention, since the electrode of this invention is low resistance and has a low reflectance of about 10% or less in visible region, the use is It is not limited to the electrode for organic electroluminescent elements, It is also possible to use as an electrode for electronic devices, and an electrode for optical devices.

As such an electronic device, the capacitive input device of a touch panel is mentioned as an example. The touch panel herein refers to a touch sensor integrated display device including a touch sensor and a display device integrally. As a touch panel, it was produced by bonding the touch sensor board | substrate which uses the pattern formed with the transparent conductive film on the transparent substrate as a detection electrode to the visual recognition side of display apparatuses, such as a liquid crystal device, or the board | substrate of a display apparatus. The touch sensor electrode pattern may be formed to form a touch sensor integrated display device.

In the case of an electronic device in which a substrate with electrodes is disposed on the front surface of a display device such as a touch panel, it is a necessary condition not to disturb the visibility of the display. Therefore, the electrodes may be shielded, scattered, stray light, reflection, or the like. As little as possible is required.

According to the electrode of the present invention, since the reflectance of the visible light region is 10% or less, even when used for the electrode of the capacitive touch panel input device, the glare is suppressed, the decrease in the contrast ratio of the display is suppressed, and the sheet resistance Since this is small at 1 Ω / sq or less, power consumption of electronic devices such as capacitive input devices can be reduced.

1 conductive layer
2 blackening layer
3 work function adjustment layer
10 description
20, 20 'electrode for organic EL device
30 hole transport layer
40 organic light emitting layer
50 electron transport layer
60, 60 'transparent electrode
100, 100 'organic EL device
L luminous

Claims (13)

Conductive layer mainly composed of 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 work function adjustment layer made of a transparent conductive oxide having a predetermined work function provided on the blackening layer,
The reflectance of visible region is 10% or less,
The sheet resistance is 1 ohm / sq or less, The electrode for organic electroluminescent elements characterized by the above-mentioned. The method of claim 1,
The said electrode for organic electroluminescent elements is comprised from three layers which consist of the said conductive layer, the said blackening layer, and the said work function adjustment layer, The electrode for organic electroluminescent elements characterized by the above-mentioned. The method according to claim 1 or 2,
The conductive layer is an electrode for an organic electroluminescent device, characterized in that the metal or alloy mainly composed of one or more metals selected from the group consisting of Al, Cu, Ag, Mo, Cr. The method according to any one of claims 1 to 3,
The blackening layer is an electrode for an organic electroluminescent device, characterized in that the lower oxide, lower nitride or lower oxynitride mainly containing Mo or Zn. The method according to any one of claims 1 to 4,
The work function adjusting layer is made of a transparent conductive oxide based on In ₂ O ₃ or ZnO, an organic electroluminescent device electrode. The method of claim 5,
The work function adjusting layer is composed of an organic electroluminescent material comprising at least one transparent conductive oxide added with In ₂ O ₃ selected from the group consisting of Ga, Ce, Zn, Sn, Si, W, Ti. Sense element electrode. The method of claim 5,
The work function adjusting layer is an electrode for an organic electroluminescent device, characterized in that the transparent conductive oxide is added to ZnO at least one selected from the group containing Al or Ga. The method according to any one of claims 1 to 7,
The work function adjustment layer is an electrode for organic electroluminescent devices, wherein the work function is 4.6 eV or less, and is used as a cathode of the organic electroluminescent device. The method according to any one of claims 1 to 7,
The work function adjusting layer has a work function of 4.7 eV or more, and is used as an anode of an organic electroluminescent device, characterized in that the electrode for an organic electroluminescent device. The organic electroluminescent element provided with the electrode for organic electroluminescent elements as described in any one of Claims 1-9. The organic electroluminescent display device provided with the organic electroluminescent element of Claim 10, and is not equipped with the polarizing plate. A conductive layer lamination step of laminating a conductive layer containing, as a main component, at least one metal selected from the group consisting of Al, Cu, Ag, Mo, and Cr on a substrate;
A blackening layer lamination step of laminating a blackening layer having a reflectance of 40% or less in the visible light region composed of a lower oxide, lower nitride, or lower oxynitride mainly composed of Mo or Zn on the conductive layer;
In ₂ O ₃ or on the blackening layer A work function adjustment layer lamination step of laminating a work function adjustment layer having a predetermined work function made of a transparent conductive oxide based on ZnO, and
An etching step of collectively etching the laminated conductive layer, the blackening layer and the work function adjustment layer
The manufacturing method of the electrode for organic electroluminescent elements characterized by performing the above. Conductive layer mainly composed of 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 work function adjustment layer made of a transparent conductive oxide having a predetermined work function provided on the blackening layer,
The reflectance of visible region is 10% or less,
An electrode for electronic devices, wherein the sheet resistance is 1 Ω / sq or less.

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