KR20200098664A - Electrode substrate material for organic devices - Google Patents

Abstract

The electrode substrate material for an organic device includes a conductor layer 101 made of a patterned metal foil and a planarization layer 102 formed around the conductor layer 101. In the first surface 111, the surface of the conductor layer 101 is exposed from the planarization layer 102, and the surface of the conductor layer 101 and the surface of the planarization layer 102 form a continuous flat surface. .

Description

Electrode substrate material for organic devices

The present disclosure relates to an electrode substrate material for an organic device.

In recent years, organic light emitting diodes are attracting attention as light sources of next-generation lighting equipment. OLED has an organic light emitting layer between the anode and the cathode, recombines holes and electrons in the organic light emitting layer, and emits light by energy generated at that time. In addition, organic solar cells such as perovskite type and dye-sensitized type are attracting attention as next-generation solar cell devices. An organic solar cell generates power by providing a photoelectric conversion layer between an anode and a cathode, and discharging electrons and holes excited by incident sunlight from the anode and cathode.

In these devices, in addition to being able to form organic functional layers such as an organic light emitting layer and a photoelectric conversion layer, there is a demand for an electrode substrate material capable of extracting or introducing light.

The electrode substrate material is required to have a smoothness capable of forming an organic functional layer so as not to generate pinholes or the like, particularly without steps or protrusions. In recent years, OLEDs and organic solar cells are required to have a large area. In order to uniformly emit light of a large area OLED, it is important to be able to supply power to the entire surface of the device. In a large-area organic solar cell, it is important to efficiently transport excited electrons and holes in the device. Therefore, a low surface resistance is required for the electrode substrate material. In addition, since OLEDs and organic solar cells are produced in a roll-to-roll process to increase productivity, they are required to be molded into curved surfaces and used, so that high flexibility is also required for electrode substrate materials.

Development of electrode substrate materials for organic devices that satisfy these demands is underway. For example, an electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a glass substrate, or an electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a gas barrier film is being studied (for example, , See Patent Document 1).

Further, an electrode substrate material for organic devices formed by laminating a mesh-like metal vapor deposition film on a gas barrier film or the like is also being studied (see, for example, Patent Document 2).

Japanese Patent Laid-Open Publication No. 2008-031496 Japanese Patent Laid-Open Publication No. 2001-0110574

However, the electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a glass substrate is not flexible, so it is not bent and thus cannot be manufactured roll-to-roll. In addition, in order to adapt to the application process, it takes time for pretreatment to ensure wettability.

The electrode substrate material for organic devices in which indium tin oxide (ITO) is laminated on a gas barrier film or the like has a considerably higher surface resistance compared to metals such as silver, aluminum or copper. In addition, it can be bent, but if the bending radius of curvature is decreased, cracks are formed in the ITO layer, thereby increasing the surface resistance.

On the other hand, when an electrode substrate material for organic devices is formed with a metal vapor deposition film on a gas barrier film or the like, a level difference occurs in the mesh-shaped wiring portion. In addition, although it can be bent, if the bending radius of curvature is small, cracks are generated in the metal deposition film and surface resistance is increased, so sufficient flexibility cannot be obtained.

An object of the present disclosure is to provide an electrode substrate material for organic devices with high smoothness, low surface resistance, and high flexibility.

One aspect of the electrode substrate material for an organic device of the present disclosure includes a conductor layer made of a patterned metal foil and a planarization layer formed around the conductor layer, and in the first surface, the surface of the conductor layer is exposed from the planarization layer, Further, the surface of the conductor layer and the surface of the planarization layer form a continuous flat surface.

In one aspect of the electrode substrate material for organic devices, the conductor layer may form a pattern having a line width of 20 µm or more and 200 µm or less, and the density of the conductor layer per unit area of the first surface may be 15% or less.

In one aspect of the electrode substrate material for an organic device, the planarization layer includes a gas barrier layer and a transparent resin layer, and the surface of the gas barrier layer and the exposed surface of the conductor layer can be made to form a continuous smooth surface.

In one aspect of the electrode substrate material for an organic device, the gas barrier layer comprises at least one of a layer containing aluminum and oxygen as main components, and a layer containing silicon and at least one of nitrogen, oxygen and carbon as a main component, The thickness can be 20 nm or more.

In one aspect of the electrode substrate material for organic devices, the planarization layer can have a light transmittance of 85% or more at a wavelength of 400 nm to 800 nm.

In one embodiment of the electrode substrate material for organic devices, the planarization layer is polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride. (PVC), fluororesin, indium tin oxide (ITO), and polyethylenedioxythiophene/polystyrenesulfonic acid (PEDOT/PSS) can be used as one or two or more.

In one aspect of the electrode substrate material for organic devices, the conductor layer can be an aluminum foil having a thickness of 6 µm or more and 30 µm or less.

In one aspect of the electrode substrate material for organic devices, the conductor layer may include a base pattern and a peripheral pattern formed outside the base pattern and connectable to an external device.

In one aspect of the electrode substrate material for an organic device, on the second side opposite to the first side, the surface of the conductor layer may be exposed from the planarization layer, and on the second side, the surface of the conductor layer is by the planarization layer. It may be covered.

According to the electrode substrate material for organic devices of the present disclosure, high smoothness, low surface resistance, and high flexibility can be realized.

1 is a cross-sectional view showing an OLED using a surface electrode material for OLED according to an embodiment.
2 is a perspective view showing a surface electrode material for an OLED according to an embodiment.
3 is a cross-sectional view taken along line III-III of FIG. 2.
4 is a plan view showing a modified example of a conductor layer pattern.
5 is a cross-sectional view showing a modified example of a surface electrode material for OLED.
6 is a cross-sectional view showing a modified example of a surface electrode material for OLED.
7 is a cross-sectional view showing a modified example of a surface electrode material for OLED.
8 is a cross-sectional view showing a modified example of a surface electrode material for OLED.
9A is a perspective view showing one step of a method of manufacturing a surface electrode material for OLED.
9B is a perspective view showing one step of a method of manufacturing a surface electrode material for OLED.
9C is a perspective view showing one step of a method of manufacturing a surface electrode material for OLED.
9D is a perspective view showing one step of a method of manufacturing a surface electrode material for OLED.
10A is a cross-sectional view showing one step of a method of manufacturing a surface electrode material for OLED.
10B is a cross-sectional view showing one step of a method for manufacturing a surface electrode material for OLED.

The electrode substrate material for an organic device of this embodiment includes a conductor layer 101 and a planarization layer 102, and can be used as the anode (surface electrode) 202 of the OLED 200 as shown in FIG. 1. have. In the OLED 200, a light emitting layer 201 is formed between the anode 202 and the cathode 203. Light generated by the light emitting layer 201 is output from the anode 202 side.

In this embodiment, the light emitting layer 201 is deposited or applied between the cathode 203 and the anode 202, including a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a charge storage layer, etc., in addition to the organic light emitting layer. It means the whole layer formed by etc.

2 and 3, the electrode substrate material 100 for an organic device according to the present embodiment includes a conductor layer 101 made of a patterned metal foil, and a planarization layer 102 formed around the conductor layer 101. It is equipped with. On the first surface 111, the surface of the conductor layer 101 is exposed from the planarization layer 102, and the surface of the conductor layer 101 and the surface of the planarization layer 102 form a continuous flat surface. . Thereby, an organic functional layer or the like can be easily formed on the first surface.

The electrode substrate material for an organic device of the present embodiment comprises a conductor layer 101 and a planarization layer 102 made of a metal foil, and does not have an ITO layer, so that the coating property can be easily improved. Therefore, when manufacturing an organic device by a coating method, it is also possible to obtain an advantage that the pretreatment time such as ultraviolet ozone washing can be shortened.

<Conductor layer>

The conductor layer 101 of this embodiment is made of a metal foil patterned into a predetermined shape. The conductor layer 101 made of a metal foil, unlike a conductor layer made of a metal vapor deposition film or the like, is difficult to break even when bent, so that sufficient flexibility can be realized. When the electrode substrate material 100 for an organic device is used as the electrode 202 of an organic device, the conductor layer 101 contacts the light emitting layer 201 of an OLED, and applies a voltage to the light emitting layer 201.

The metal foil used as the conductor layer 101 is not particularly limited, and can be, for example, an aluminum foil, a copper foil, a gold foil, or a silver foil. Among them, an aluminum foil that is lightweight and hardly oxidizes in the deep layer and has high light reflectivity is preferred.

Further, the metal foil used as the conductor layer 101 may be provided with a metal thin film formed on the surface of at least one of nickel, copper, silver, platinum, gold, etc. formed by plating or vapor deposition.

The pattern of the conductor layer 101 can be designed according to characteristics required for the electrode substrate material 100 for organic devices. For example, a known surface electrode pattern employed as an electrode of an organic device, such as a lattice shape, a mesh shape, a spiral shape, an arc shape, a meander shape, and other irregular shapes, can be employed.

As shown in FIG. 4, the pattern of the conductor layer 101 may include not only the base pattern 121 serving as one electrode of the organic device, but also the peripheral pattern 122 formed outside the base pattern 121. The peripheral pattern 122 includes a first peripheral pattern 122A connecting the base pattern and the terminal 124, and an electrode 123 and a terminal 124 formed on a surface opposite to the base pattern 121 of the organic device. It may include a second peripheral pattern 122B to be connected. The terminal 124 can be connected to an external device or the like. Further, the peripheral pattern 122 may be directly connected to an external device or the like without interposing the terminal 124. The external device can be, for example, a power supply unit that supplies electric power to an organic device.

The thickness of the conductor layer 101 is not particularly limited, but it is preferably 6 μm or more from the viewpoint of securing flexibility and reducing surface resistance. Further, from the viewpoint of improving the light transmittance, 30 µm or less is preferable.

The line width of the conductor layer 101 is not particularly limited, but it is preferably 20 µm or more from the viewpoint of reducing the surface resistance, and 200 µm or less from the viewpoint of reducing the light emission unevenness. From the viewpoint of securing light transmittance, the density of the conductor layer per unit area of the first surface 111 is preferably 15% or less.

<Planning layer>

The planarization layer 102 is formed around the conductor layer 101 so as to fill the openings of the patterned conductor layer 101. At least on the first surface 111, the planarization layer 102 does not cover the conductor layer 101 and the surface of the conductor layer 101 is exposed.

At least in the first surface 111, the surface of the conductor layer 101 and the surface of the planarization layer 102 form a continuous flat surface. Specifically, the surface of the conductor layer 101 and the surface of the planarization layer 102 become a continuous surface without a step at the boundary thereof, and the first surface 111 as a whole becomes a flat surface. Since the first surface 111 becomes such a continuous flat surface, a uniform light emitting layer 201 can be formed on the surface of the electrode substrate material for an organic device of the present embodiment. Here, the first surface 111 may be in close contact with the entire surface of the light-emitting layer 201, but the difference in level between the surface of the conductor layer 101 and the surface of the planarization layer 102 is preferably 300 nm or less.

The planarization layer 102 may be transparent to the naked eye, but it is preferable that the transmittance at a wavelength of 400 nm to 800 nm is 85% or more. It is also possible to improve the luminous efficiency by setting the transmittance of the planarization layer into this range.

The composition of the planarization layer 102 is not limited as long as it can be made transparent. For example, transparent resins such as polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC), and fluoro resins are used. Can be used. These resins may be used alone or in combination of two or more. Further, a transparent conductive material such as indium tin oxide (ITO) or polyethylenedioxythiophene/polystyrenesulfonic acid (PEDOT/PSS) can also be used.

The planarization layer 102 may be one layer or a plurality of layers. By forming the planarization layer 102 into a plurality of layers having different refractive indices, diffusion of light is controlled, total reflection is reduced, and light extraction efficiency can be improved.

As shown in Fig. 3, when the conductor layer 101 is not covered by the planarization layer 102 even on the second surface 112 opposite to the first surface 111, the degree of freedom of the power feeding portion increases. Can get an advantage. However, as shown in FIG. 5, on the second surface 112, the planarization layer 102 may cover the conductor layer 101. In addition, the second surface 112 is preferably a flat surface from the viewpoint of light extraction, but irregularities may be present. For example, as shown in FIG. 6, it is possible to have a configuration in which irregularities corresponding to the pattern of the conductor layer 101 are present on the second surface 112.

The thickness of the planarization layer 102 is the same as the thickness of the conductor layer 101 when the conductor layer 101 is exposed also on the second surface 112. In the case of covering the conductor layer 101 on the second surface, it is sufficient to make it thicker than the conductor layer 101, but from the viewpoint of flexibility and light transmittance, it is preferably set to 60 µm or less.

As shown in FIG. 7, the transparent support 105 may be bonded to the second surface 112 side. By bonding the transparent support 105, the strength of the surface electrode material 100 for OLED can be increased. The transparent support 105 is not particularly limited, but, for example, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride ( PVC) and glass. The transparent support can also be made into a layer having an antireflection function.

In addition, as shown in FIG. 8, a black protective layer 106 may be formed on the second surface 112 side to cover the conductor layer 101. By forming the black protective layer 106 on the back side of the conductor layer 101, the pattern of the conductor layer 101 becomes invisible when the organic device is viewed from the front side, thereby improving design. In addition, both the transparent support 105 and the protective layer 106 may be formed.

The protective layer 106 can be formed, for example, by using a black dry film resist used in an etching step described later, and using the dry film resist remaining after exposure and development without peeling off after etching.

When the organic device electrode substrate material 100 has the above configuration, the surface resistance can be lower than that of the conventional electrode substrate material for organic devices, and flexibility can be improved. In addition, the luminous efficiency when used in a device can also be improved.

The planarization layer 102 may be configured to include a gas barrier layer 103 and a transparent resin layer 104. The organic light emitting layer and the photoelectric conversion layer of the organic device are weak to water vapor and deteriorate even with a little water vapor. Accordingly, the organic light emitting layer or the photoelectric conversion layer is sealed with glass, metal, or gas barrier film. However, there are cases where water vapor on the electrode substrate side is not sufficiently blocked. When the electrode substrate material has a water vapor barrier property, it is difficult for water vapor to enter from the electrode substrate side, and deterioration of the organic functional layer can be suppressed.

The gas barrier layer 103 may be formed of any material as long as it has high transparency and moisture vapor barrier properties. For example, a layer containing aluminum and oxygen as main components can be formed by an atomic layer deposition method. In addition, a layer containing silicon, nitrogen, oxygen and carbon as main components can also be formed by chemical vapor deposition (CVD). The gas barrier layer 103 is not limited to one layer, and may be a multilayer laminate. The thickness of the gas barrier layer 103 is preferably 20 nm or more from the viewpoint of blocking water vapor.

In the case of forming the gas barrier layer 103, the surface of the conductor layer 101 and the surface of the gas barrier layer 103 can form a continuous flat surface. The difference in the level of the boundary between the surface of the conductor layer 101 and the surface of the gas barrier layer 103 is preferably 300 nm or less. Here, the thickness of the transparent resin layer 104 can be made thinner than the thickness of the conductor layer 101.

<Production method>

The electrode substrate material 100 for organic devices of the present embodiment can be formed, for example, as follows.

First, as shown in FIG. 9A, a metal foil 302 to be a conductor layer is laminated on a substrate 301 having a smooth surface and having non-adhesion properties to resin and metal. A substrate having non-adhesive property refers to a substrate having the ability to be easily peeled even when a resin or metal is in contact. The base material itself may be formed of a material having non-adhesive properties, or a non-adhesive coating layer may be formed on the surface thereof. For example, as a substrate, one or two of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic and polyvinyl chloride (PVC), etc. You can use more than one species.

For the metal foil 302, a material and thickness capable of forming the above-described conductor layer 101 are used. From the viewpoint of improving the adhesion between the conductor layer 101 formed of the metal foil 302 and the light emitting layer 201, the surface of the metal foil 302 to be bonded to the substrate 301 is preferably smooth, and specifically It is preferable that the arithmetic mean roughness (Ra) is 50 nm or less. When laminating the metal foil 302 on the substrate 301, an adhesive or the like having poor adhesion or weak adhesion may be applied to at least one surface of the substrate 301 and the metal foil 302. In this way, lamination becomes easy.

Next, as shown in FIG. 9B, the metal foil 302 laminated on the surface of the substrate 301 is patterned to form a conductor layer 101. Patterning of the metal foil 302 can be performed by a known method such as wet etching or dry etching. As the pattern formed by etching, as described above, a known electrode pattern employed as an electrode of an organic device can be employed. In addition, it may be a pattern having a base pattern 121 and a peripheral pattern 122 as shown in FIG. 4.

Next, as shown in Fig. 9C, a transparent material is applied to form a planarization layer 102. As the transparent material, a material as described above can be used, and in the case of a material having fluidity at room temperature, coating treatment can be performed using, for example, a coating machine. The material having fluidity at room temperature may be, for example, a resin having fluidity by being dissolved in a solvent, a resin having fluidity in a specific temperature condition, a resin having fluidity at room temperature and curable by heat or light, or the like.

Next, as shown in FIG. 9D, the base material 301 is peeled. By making the substrate non-adhesive, it can be easily peeled off. On the first surface formed by peeling off the substrate 301, the conductor layer 101 is exposed without being coated on the planarization layer 102. Further, the first surface is a surface to which the surface state of the substrate 301 is transferred. By using the substrate 301 having a smooth surface, a smooth first surface is obtained.

And, after forming the planarization layer 102, before peeling off the base material 301, a process of bonding the transparent support body 105 may be provided. By forming the transparent support 105, even when the thickness of the planarization layer 102 is thin, peeling of the substrate 301 becomes easy. And, after peeling the base material 301, the transparent support body 105 may be bonded.

The planarization layer 102 may be configured to include a gas barrier layer 103 and a transparent resin layer 104. In this case, as shown in Fig. 10A, a gas barrier is applied to cover both the portion from which the metal foil 302 is removed and the portion where the metal foil 302 remains on the surface of the substrate 301 after the conductor layer 101 is formed. A layer 103 is formed. The gas barrier layer 103 can be formed of a material having high water vapor barrier properties. For example, by using an atomic layer deposition method or the like, a layer containing aluminum and oxygen as main components (e.g., a layer composed of Al ₂ O ₃ etc.) is formed, or by using a chemical vapor deposition (CVD) method, silicon and , Nitrogen, oxygen, and at least one of carbon as a main component layer (for example, SiO _x , SiN, SiON, SiONC, or the like). Further, a laminate in which these layers are combined can also be formed. As shown in FIG. 10B, after the gas barrier layer 103 is formed, a transparent material is applied on the surface of the gas barrier layer 103 to form a transparent resin layer 104. In FIG. 10B, an example in which the transparent resin layer 104 completely fills the concave portion is shown, but the concave portion does not need to be completely filled. In addition, the transparent resin layer 104 may completely cover the gas barrier layer 103. When the substrate 301 is peeled off, the first surface, which is a flat surface in which the surface of the conductor layer 101 and the surface of the gas barrier layer 103 are continuous, is exposed.

The manufacturing method of the electrode substrate material for organic devices is not limited to such a method, and may be formed by other methods as long as the first surface can be made flat.

Example

The electrode substrate material for an organic device of the present disclosure will be described in more detail using examples. The following examples are illustrative and are not intended to limit the present invention.

<Smoothness evaluation>

To evaluate the smoothness of the electrode substrate material for organic devices, use the ultra-high resolution non-contact three-dimensional surface shape measurement system BW-D500 manufactured by NIKON CORP. Sz was measured. It is a value calculated by expanding the maximum size Rz defined by JIS-B0601-2001 in three dimensions so that it can be applied to the entire observed surface. Those having a smoothness of 200 nm or less in Sz were regarded as good (circle), and those having a smoothness exceeding 200 nm were regarded as poor (x).

<Water vapor barrier evaluation>

The water vapor barrier property evaluation of the electrode substrate material for organic devices is the water vapor transmission rate defined in JIS K 7129-7:2016. A sample was placed on the deposited metal calcium, and after 100 hours elapsed in a 40°C 90% environment, it was calculated by calculating the corroded calcium area.

<surface resistance evaluation>

The surface resistance of the electrode substrate material for organic devices was determined by measuring the resistance value between two points on a diagonal of a 50 mm x 50 mm sample using an ohmmeter (manufactured by SANWA ELECTRIC INSTRUMENT, RD701 DIGITALMULTIMETER). Those having a surface resistance of 10 Ω/cm 2 or less were regarded as good ((circle)), and those having a surface resistance exceeding 10 Ω/cm 2 were regarded as bad (x).

<Flexibility evaluation>

The surface resistance before and after the bending test of the target sample was measured, and the reduction rate of the surface resistance was determined. The bending test was carried out 50 times with a 10 mmφ mandrel using a coating film bending tester. When the reduction rate of the surface resistance was 5% or less, the flexibility was good ((circle)), and the thing exceeding 5% was made into defect (x).

(Example 1)

A non-adhesive adhesive was applied to one surface (main surface) of an aluminum foil (manufactured by Toyo Aluminum KK, 1N30) of 3cm×3cm, thickness 15㎛ (arithmetic mean roughness (Ra): 7nm), and dried at 100℃ After that, the substrate was bonded to the coated surface on the adhesive side, followed by aging treatment at 50°C for 4 days. The substrate was a PET film (manufactured by TEIJIN Film Solution) having a thickness of 38 μm.

Next, on the back side of the aluminum foil, an alkali developing dry film resist with a thickness of 15 μm was bonded, exposed and developed with ultraviolet rays (UV) using a mesh-shaped photomask, and iron chloride ( II) By etching with an aqueous solution, a conductor layer was formed. The conductor layer had a line width of 75 µm and a grid shape with a pitch of 1500 µm, and a wiring density of 10%.

Next, a 150 nm SiN film was formed on both the portion where the aluminum foil was removed by etching and the portion remaining by the plasma CVD method, and then an Al ₂ O ₃ film of 20 nm was formed by the atomic layer deposition method to form a gas barrier layer. Formed.

Next, apply an epoxy resin having an average transmittance of 90% at a wavelength of 400 to 800 nm on the surface of the formed gas barrier layer, and the film thickness from the surface on which the gas barrier layer is formed on the adhesive becomes 20 µm. Coating treatment was performed so as to be buried, and a planarization layer was formed. On the surface of the planarization layer, a commercially available antireflection film having a thickness of 30 μm was bonded as a transparent support, and dried at 100°C. Thereafter, the substrate was peeled off to obtain an electrode substrate material for organic devices.

The obtained electrode substrate material for organic devices had a smoothness of Rz of 127 nm, a water vapor barrier property of 10 ^-5 g/m 2 /day or less, a surface resistance of 0.02 Ω/cm 2, and the surface resistance after the bending test did not change.

An OLED using the target sample as an anode was formed. The device was formed as follows. First, polyethylenedioxythiophene-polystyrenesulfonate (PEDOT/PSS, manufactured by Sigma Aldrich) was spin-coated at 3000 rpm using a spin coater (manufactured by MIKASA, SpinCoater MS-A150), and dried in the air. Then, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine)](Poly[ (9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)]:TFB, manufactured by sigma aldrich) was dissolved in toluene at 3000 rpm. After spin-coating and drying in a nitrogen atmosphere, poly(9,9-dioctylfluorine-alt-benzothiadiazole) (F8BT, manufactured by Sigma Aldrich) was dissolved in toluene and spin-coated at 2000 rpm. Next, lithium fluoride was vacuum vapor-deposited using a vacuum vapor deposition apparatus (JEOL, JEE-4X), and further aluminum was vacuum vapor-deposited as an anode.

A voltage of 7V was applied to the obtained device to emit light, and the luminance against current and voltage was measured using a luminance meter (manufactured by KONICA MINOLTA, color luminance meter CS-200), and the luminance per 1A was obtained as luminous efficiency. It was cd/A.

Ultraviolet ozone for electrode substrate materials for organic devices at three levels of 1 minute, 5 minutes, and 10 minutes at wavelength 254 nm and illuminance 10.0 mW/cm 2 using SUNENERGY CORP's UV/O ₃ cleaning and reforming device SKB401Y-02. Washing was performed, and each was evaluated by the wetting tension test method defined in JIS-K-6768-1999. 63 mN/m for 1 minute, 73 mN/m for 5 minutes, and 73 mN for 10 minutes. It was /m.

(Example 2)

It was carried out in the same manner as in Example 1 except that the aluminum foil was used as a copper foil having a thickness of 15 μm (purity 99.96%) and the epoxy resin was used as an acrylic resin.

The obtained electrode substrate material for organic devices had a smoothness of Rz of 72 nm, a water vapor barrier property of 10 ^-5 g/m 2 /day or less, a surface resistance of 0.01 Ω/cm 2, and the surface resistance after the bending test did not change.

In the same manner as in Example 1, an OLED using the target sample as an anode was formed, and the luminous efficiency was measured, and it was 1.4 cd/A. In the same manner as in Example 1, the wetting tension after ultraviolet ozone washing was evaluated, and it was 67 mN/m in 1 minute, 73 mN/m in 5 minutes, and 73 mN/m in 10 minutes.

(Example 3)

It was carried out in the same manner as in Example 1 except that the line width of the conductive layer was set to 100 µm, the pitch was set to 2000 µm, and the wiring density was set to 9%.

The obtained electrode substrate material for organic devices had a smoothness of Rz 158 nm, a water vapor barrier property of 10 ^-5 g/m 2 /day or less, a surface resistance of 0.01 Ω/cm 2, and the surface resistance after the bending test did not change.

Further, in the same manner as in Example 1, when an OLED using the target sample as an anode was formed, and the luminous efficiency was measured, it was 1.0 cd/A. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 63 mN/m in 1 minute, 73 mN/m in 5 minutes, and 73 mN/m in 10 minutes.

(Example 4)

An electrode substrate material for an organic device was obtained in the same manner as in Example 1, except that the gas barrier layer was not formed, that is, the portion where the aluminum foil was removed by etching and the surface with the conductor layer was directly filled with an epoxy resin.

The obtained electrode substrate material for organic devices had a smoothness of Rz of 127 nm, a surface resistance of 0.02 Ω/cm 2, and the surface resistance after the bending test did not change. The water vapor barrier property was 5.68 g/m 2 /day.

In the same manner as in Example 1, an OLED using the target sample as an anode was formed, and the luminous efficiency was measured, and it was 0.9 cd/A. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 68 mN/m in 1 minute, 68 mN/m in 5 minutes, and 73 mN/m in 10 minutes.

(Example 5)

Without forming a gas barrier layer, i.e., the part where the aluminum foil was removed by etching and the surface with the conductor layer, the epoxy resin was directly filled, and the transparent support had a thickness of 75 µm and a water vapor transmission rate of 4×10 ^-4 g/m 2 / An electrode substrate material for an organic device was obtained in the same manner as in Example 1, except for using a daily commercial gas barrier film.

The smoothness of the obtained electrode substrate material for organic devices was Rz 142 nm, the surface resistance was 0.02 Ω/cm 2, and the surface resistance after the bending test did not change. The water vapor barrier property was 3×10 ^-2 g/m 2 /day.

In the same manner as in Example 1, an OLED using the target sample as an anode was formed, and the luminous efficiency was measured, and it was 0.5 cd/A. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 66 mN/m in 1 minute, 73 mN/m in 5 minutes, and 73 mN/m in 10 minutes.

(Comparative Example 1)

An electrode substrate material for organic devices was obtained by laminating indium tin oxide (ITO) to a film thickness of 155 nm by sputtering on a glass substrate.

The obtained electrode substrate material for organic devices had a smoothness of Rz: 17 nm and a water vapor barrier property of 10 ^-5 g/m 2 /day or less, but the surface resistance was 0.68 Ω/cm 2 and the glass substrate was broken even when slightly bent.

In the same manner as in Example 1, an OLED using the target sample as an anode was formed, and the luminous efficiency was measured, and it was 5.2 cd/A. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 48 mN/m in 1 minute, 61 mN/m in 5 minutes, and 67 mN/m in 10 minutes.

(Comparative Example 2)

Indium tin oxide (ITO) was laminated to a film thickness of 120 nm by sputtering on a commercially available gas barrier film having a thickness of 75 μm and a water vapor transmittance of 4×10 ^-4 g/m 2 /day, thereby forming an electrode substrate material for an organic device. Got it.

The obtained electrode substrate material for organic devices had a smoothness of Rz: 58 nm and a water vapor barrier property of 1×10 ^-4 g/m 2 /day, but the surface resistance was 9.40 Ω/cm 2, and the resistance value after the bending test was 2296.00 Ω/cm 2 As, it increased rapidly.

In addition, as in Example 1, an OLED using the target sample as an anode was formed, but did not emit light. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 52 mN/m in 1 minute, 58 mN/m in 5 minutes, and 62 mN/m in 10 minutes.

The crystallinity of the ITO film formed on the film was poor, and the surface resistance increased. Since it is a film, it can be bent, but when it is bent with a small radius of curvature, cracks occur in the ITO film and resistance is increased. In addition, in order to improve the wet tension, a long pretreatment time was required.

(Comparative Example 3)

Apply a commercially available acrylic adhesive to one surface (main surface) of an aluminum foil (manufactured by Toyo Aluminum KK, 1N30) with a thickness of 3 cm x 3 cm and a thickness of 15 μm (Ra: 7 nm), and a thickness of 75 μm on the coated surface of the adhesive side And a commercially available gas barrier film having a water vapor transmittance of 4×10 ^-4 g/m 2 /day was bonded.

Next, a commercially available dry film is bonded to the back side of the aluminum foil, exposed and developed under ultraviolet conditions using a mesh-shaped photomask, and the portion where the dry film is not left is etched with an aqueous iron (II) chloride solution to form a fine wire. Then, the dry film was peeled off with an aqueous sodium hydroxide solution to obtain a surface electrode material for OLED.

The water vapor barrier property of the obtained electrode substrate material for organic devices was 4×10 ^-4 g/m 2 /day, the surface resistance was 0.04 Ω/cm 2, and the resistance value after the bending test did not change, but the smoothness was Rz:1621 nm.

As in Example 1, an OLED using the target sample as an anode was formed, but it did not emit light. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 70 mN/m in 1 minute, 73 mN/m in 5 minutes, and 73 mN/m in 10 minutes.

Since the conductor layer was formed of aluminum foil, there were no problems such as surface resistance and flexibility, but since the planarization layer was not formed, a step was generated and the smoothness was not good.

(Comparative Example 4)

Aluminum was deposited on a commercially available gas barrier film having a thickness of 75 µm and a water vapor transmittance of 4×10 ^-4 g/m 2 /day to form an aluminum vapor deposition film having a thickness of 300 nm. Next, a commercially available dry film was bonded to the surface of the aluminum deposition film, exposed and developed with ultraviolet rays using a mesh-shaped photomask, and the portion where the dry film was not left was etched with an aqueous iron (II) chloride solution, followed by patterning. Thereafter, the dry film was peeled off using an aqueous sodium hydroxide solution to obtain an electrode substrate material for organic devices.

The water vapor barrier property of the obtained electrode substrate material for organic devices was 4×10 ^-4 g/m 2 /day, and the surface resistance was 0.42 Ω/cm 2, but the resistance value after the bending test increased to 12.6 Ω/cm 2 and smoothness. Was Rz: 343 nm.

As in Example 1, an OLED using the target sample as an anode was formed, but it did not emit light. In the same manner as in Example 1, the wet tension after ultraviolet ozone washing was evaluated, and it was 50 mN/m in 1 minute, 73 mN/m in 5 minutes, and 73 mN/m in 10 minutes.

Since the conductor layer was formed by an aluminum vapor deposition film, cracks occurred in the conductor layer after 50 bending tests, and surface resistance increased. In addition, the smoothness was not good because a level difference occurred due to the conductor layer.

Table 1 summarizes the results of each Example and Comparative Example.

[Table 1]

The electrode substrate material for organic devices of the present disclosure can realize high smoothness, gas barrier properties, light transmittance, low surface resistance and high flexibility, and shorten the pretreatment in the coating process, and is useful as an electrode material for organic devices. Do.

100: electrode substrate material for organic devices 101: conductor layer
102: planarization layer 103: gas barrier layer
104: transparent resin layer 105: transparent support
106: protective layer 111: first surface
112: second side 121: base pattern
122: peripheral pattern 122A: first peripheral pattern
122B: second peripheral pattern 123: electrode
124: terminal 200: OLED
201: light-emitting layer 202: electrode
203: electrode 301: substrate
302: metal foil

Claims (10)

A conductor layer made of patterned metal foil,
It has a planarization layer formed around the conductor layer,
In the first surface, the surface of the conductor layer is exposed from the planarization layer, and the surface of the conductor layer and the surface of the planarization layer form a continuous flat surface. The method of claim 1,
An electrode substrate material for an organic device, wherein the conductor layer forms a pattern having a line width of 20 µm or more and 200 µm or less, and the density of the conductor layer per unit area of the first surface is 15% or less. The method according to claim 1 or 2,
The planarization layer includes a gas barrier layer and a transparent resin layer,
The electrode substrate material for an organic device, wherein the surface of the gas barrier layer and the exposed surface of the conductor layer form a continuous smooth surface. The method of claim 3,
The gas barrier layer includes at least one of a layer mainly containing aluminum and oxygen, and a layer containing at least one of silicon, nitrogen, oxygen, and carbon as a main component, and having a thickness of 20 nm or more, an electrode substrate for an organic device material. The method according to any one of claims 1 to 4,
The planarization layer is an electrode substrate material for an organic device having a light transmittance of 85% or more at a wavelength of 400 nm to 800 nm. The method of claim 5,
The planarization layer is polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC), fluoro resin, indium tin oxide. (ITO), and one or two or more of polyethylenedioxythiophene/polystyrenesulfonic acid (PEDOT/PSS), an electrode substrate material for organic devices. The method according to any one of claims 1 to 6,
The conductor layer includes a base pattern and a peripheral pattern formed outside the base pattern and connectable to an external device. The method according to any one of claims 1 to 7,
The said conductor layer is an aluminum foil of 6 micrometers or more and 30 micrometers or less in thickness, The electrode substrate material for organic devices. The method according to any one of claims 1 to 8,
An electrode substrate material for an organic device, wherein on a second surface opposite to the first surface, the surface of the conductor layer is exposed from the planarization layer. The method according to any one of claims 1 to 9,
An electrode substrate material for an organic device, wherein on a second surface opposite to the first surface, the surface of the conductor layer is covered by the planarization layer.

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