TWI804558B - Electrode substrate material for organic device and manufacturing method thereof - Google Patents

Abstract

The purpose of the present invention is to provide an electrode substrate material for organic devices, which has a conductor layer 101 made of patterned metal foil and a planarization layer 102 around the conductor layer 101 . 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 planar surface.

Description

Electrode substrate material for organic device and manufacturing method thereof

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

In recent years, organic electroluminescent (EL) elements have attracted attention as light sources for next-generation lighting fixtures. An organic EL element has an organic light-emitting layer between an anode and a cathode. In the organic EL element, holes and electrons are recombined in the organic light-emitting layer, and the organic EL element uses the energy generated at this time to emit light. 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 has a photoelectric conversion layer between an anode and a cathode. In an organic solar cell, electrons and holes are excited by incident sunlight, and the organic solar cell generates electricity by extracting the electrons and holes from the anode and cathode.

These devices require an electrode substrate material in which organic functional layers such as an organic light-emitting layer and a photoelectric conversion layer can be formed, and which can also take out or take in light.

The electrode substrate material needs to have smoothness, and especially needs to be free of steps and protrusions. Among them, the smoothness can ensure that pinholes (pinholes) and the like are not generated when the organic functional layer is formed. In recent years, organic EL elements and organic solar cells have been increasingly required to have larger areas. In order to uniformly emit light from a large-area organic EL element, it is important to supply power to the entire light-emitting surface. For large-area organic solar cells, it is important to efficiently transport excited electrons and holes in the device. Therefore, the surface resistance of the electrode substrate material is required to be low. In order to improve productivity, roll-to-roll (Roll-to-Roll) process is used to produce organic EL elements and organic solar cells. Furthermore, since organic EL elements and organic solar cells are required to be molded into curved surfaces for use, electrode substrate materials are also required to have high flexibility.

Electrode substrate materials for organic devices that meet these requirements are already under development. For example, electrode substrate materials for organic devices formed by laminating indium tin oxide (ITO) on a glass substrate or electrode substrate materials for organic devices formed by laminating indium tin oxide (ITO) on a gas barrier film (for example, see Patent Document 1).

Furthermore, electrode substrate materials for organic devices formed by laminating a network-shaped vapor-deposited metal film on a gas barrier film or the like have also been studied (for example, refer to Patent Document 2).

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-031496

[Patent Document 2] Japanese Patent Laid-Open No. 2001-0110574

However, an electrode substrate material for an organic device formed by laminating indium tin oxide (ITO) on a glass substrate cannot be bent due to inflexibility, and cannot be manufactured by a roll-to-roll method. In addition, pretreatment to ensure wettability is required in order to adapt to the coating process, which takes time.

The electrode substrate material for organic devices is formed by laminating indium tin oxide (ITO) on a gas barrier film or the like, and its surface resistance is much higher than that of metals such as silver, aluminum, or copper. Furthermore, although this organic device electrode substrate material is bendable, if the radius of curvature of the bend is reduced, cracks will occur in the ITO layer, resulting in an increase in surface resistance.

On the other hand, if an electrode substrate material for an organic device is formed on a gas barrier film or the like with a metal vapor-deposition film, the mesh wiring portion becomes a stepped portion. In addition, although it can be bent, if the radius of curvature of the bend is small, cracks will occur in the deposited metal film, resulting in an increase in surface resistance, so sufficient flexibility cannot be obtained.

The purpose of this disclosure is to achieve a smoothness, low surface resistance, Highly flexible electrode substrate material for organic devices.

One aspect of the electrode substrate material for organic devices disclosed in this disclosure has a conductor layer made of patterned metal foil and a planarization layer arranged around the conductor layer. On the first surface, the surface of the conductor layer is flattened from layer is exposed, and the surface of the conductor layer forms a continuous planar surface with the surface of the planarization layer.

An aspect of the electrode substrate material for organic devices can be: the conductor layer has a pattern with a line width of 20 μm to 200 μm, and the density of the conductor layer on the first surface per unit area is 15% or less.

An aspect of the electrode substrate material for an organic device may be that 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 form a continuous smooth surface.

An aspect of the electrode substrate material for an organic device may be: the gas barrier layer includes at least one of a layer mainly composed of aluminum and oxygen and a layer mainly composed of at least one of silicon, nitrogen, oxygen, and carbon, And the thickness is more than 20nm.

An aspect of the electrode substrate material for an organic device may be: the light transmittance of the planarization layer to light with a wavelength of 400 nm to 800 nm is more than 85%.

One aspect of the electrode substrate material for organic devices can be: the planarization layer is made of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), poly One or more of carbonate (PC), acrylic acid, polyvinyl chloride (PVC), fluorocarbon resin, indium tin oxide (ITO) and polyethylene dioxythiophene/polystyrene sulfonic acid (PEDOT/PSS) .

One aspect of the electrode substrate material for organic devices may be: an aluminum foil with a conductive layer thickness of 6 μm or more and 30 μm or less.

An aspect of the electrode substrate material for organic devices can be: the conductor layer includes a substrate pattern A pattern and a peripheral pattern arranged outside the pattern of the substrate and capable of being connected to an external device.

One aspect of the electrode substrate material for an organic device may be: on the second surface opposite to the first surface, the surface of the conductor layer is exposed from the planarization layer. Alternatively, on the second surface, the surface of the conductor layer is covered with a planarization layer.

Using the electrode substrate material for organic devices disclosed in the present disclosure can achieve higher smoothness, lower surface resistance and higher flexibility.

100: Electrode substrate materials for organic devices

101: conductor layer

102: Planarization layer

103: gas barrier layer

104: transparent resin layer

105: transparent support body

106: protective layer

111: The first side

112: The second side

121: Substrate pattern

122: Peripheral pattern

122A: the first peripheral pattern

122B: the second peripheral pattern

123: electrode

124: terminal

200: Organic EL element

201: luminous layer

202: anode

203: Cathode

301: Substrate

302: metal foil

FIG. 1 is a cross-sectional view showing an organic device manufactured using an electrode substrate material for an organic device according to an embodiment.

Fig. 2 is a perspective view showing an electrode substrate material for an organic device according to an embodiment.

Fig. 3 is a sectional view taken along line III-III in Fig. 2 .

FIG. 4 is a plan view showing a modified example of the pattern of the conductor layer.

Fig. 5 is a cross-sectional view showing a modified example of an electrode substrate material for an organic device.

Fig. 6 is a cross-sectional view showing a modified example of an electrode substrate material for an organic device.

Fig. 7 is a cross-sectional view showing a modified example of an electrode substrate material for an organic device.

Fig. 8 is a cross-sectional view showing a modified example of an electrode substrate material for an organic device.

FIG. 9A is a perspective view showing a process of a manufacturing method of an electrode substrate material for an organic device.

FIG. 9B is a perspective view showing a manufacturing process of the electrode substrate material for organic devices.

FIG. 9C is a perspective view showing a process of a manufacturing method of an electrode substrate material for an organic device.

FIG. 9D is a perspective view showing a manufacturing process of the electrode substrate material for organic devices.

FIG. 10A is a cross-sectional view showing a process of a method of manufacturing an electrode substrate material for an organic device.

FIG. 10B is a cross-sectional view showing a process of a manufacturing method of an electrode substrate material for an organic device.

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

In this embodiment, the light-emitting layer 201 refers to all layers formed between the cathode 203 and the anode 202 through evaporation or coating, including not only the organic light-emitting layer, but also the hole injection layer, hole transport layer, and electron injection layer. , electron transport layer, charge confinement layer, etc.

As shown in FIGS. 2 and 3 , the electrode substrate material 100 for an organic device according to this embodiment has a conductor layer 101 made of patterned metal foil and a planarization layer 102 provided around the conductor layer 101 . 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 planar surface. Therefore, it is easy to form an organic functional layer and the like on the first face.

The surface of the electrode substrate material 100 for an organic device according to the present embodiment is composed of a conductive layer 101 and a planarization layer 102 formed of a metal foil, and has no ITO layer, so it is easy to improve wettability. Therefore, when manufacturing organic devices by the coating method, there is also the advantage of shortening the pre-treatment time such as UV ozone cleaning.

<conductor layer>

The conductor layer 101 of the present embodiment is composed of a metal foil patterned into a predetermined shape. Conductor layer 101 formed of metal foil is different from a conductor layer formed of a metal vapor-deposited film or the like. Conductor layer 101 formed of metal foil is less likely to be disconnected even when bent, and thus can achieve sufficient flexibility. When the organic device electrode substrate material 100 is used to form the anode 202 of the organic device, the conductive layer 101 is in contact with the light emitting layer 201 of the organic EL element, and a voltage is applied to the light emitting layer 201 .

The metal foil used as the conductor layer 101 is not particularly limited, and for example, aluminum foil, copper foil, gold foil, or silver foil can be used. Among them, an aluminum foil that is light in weight, hard to oxidize in depth, and highly reflective in light is preferable.

In addition, the metal foil used as the conductor layer 101 may be a metal thin film formed on the surface by plating or vapor deposition, and formed of at least one metal selected from nickel, copper, silver, platinum, and gold.

The pattern of the conductive layer 101 can be designed according to the required properties of the electrode substrate material 100 for organic devices. The pattern of the conductor layer 101 can be a well-known surface electrode pattern used as an electrode of an organic device, such as a grid shape, a mesh shape, a spiral shape, a stripe shape, a meandering shape, and other amorphous patterns. wait.

As shown in FIG. 4 , the pattern of the conductor layer 101 includes not only the substrate pattern 121 constituting one electrode of the organic device, but also the peripheral pattern 122 provided outside the substrate pattern 121 . The peripheral pattern 122 may include a first peripheral pattern 122A and a second peripheral pattern 122B. The first peripheral pattern 122A is connected to the substrate pattern 121 and the terminal 124, and the second peripheral pattern 122B is arranged on the opposite side of the organic device from the substrate pattern 121. surface and connect the electrode 123 and the terminal 124 . The terminal 124 can be connected to an external device or the like. In addition, the peripheral pattern 122 may be directly connected to an external device or the like without passing through the terminal 124 . The external device may be, for example, a power supply unit that supplies power to the organic device.

The thickness of the conductive layer 101 is not particularly limited, but is preferably 6 μm or more from the viewpoint of securing flexibility and reducing surface resistance. In addition, from the viewpoint of increasing light transmittance, it is preferably 30 μm or less.

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

<planarization layer>

The planarization layer 102 is disposed around the conductor layer 101 to bury the openings of the patterned conductor layer 101 . On at least 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.

The surface of the conductor layer 101 and the surface of the planarization layer 102 form a continuous planar surface on at least the first surface 111 . Specifically, the surface of the conductor layer 101 and the surface of the planarization layer 102 are formed as a continuous surface without a step at the boundary portion thereof, and the first surface 111 is a flat surface as a whole. Since the first surface 111 is 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 according to this embodiment. In addition, the first surface 111 only needs to be in close contact with the opposite surface of the light-emitting layer 201 , and the height difference between the surface of the conductive layer 101 and the surface of the planarization layer 102 is preferably less than 300 nm.

The planarization layer 102 only needs to be visually transparent, and the light transmittance to light with a wavelength of 400 nm to 800 nm is preferably 85% or more. By setting the light transmittance of the planarization layer within this range, the luminous efficiency can be improved.

The composition of the planarizing layer 102 is not limited as long as it can make the planarizing layer 102 transparent. For example, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC) and Transparent resin such as fluorocarbon resin forms the planarization layer 102 . These resins may be used alone or in combination of two or more. In addition, transparent conductive materials 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 multiple layers. By making the planarization layer 102 a plurality of layers with different refractive indices, the diffusion of light can be controlled, total reflection can be reduced, and light extraction efficiency can be improved.

As shown in FIG. 3 , if the conductor layer 101 is not covered by the planarization layer 102 on the second surface 112 opposite to the first surface 111 , the advantage of a greater degree of freedom of power supply locations can be obtained. However, as shown in FIG. 5 , on the second surface 112 , the planarization layer 102 can also cover the conductive layer 101 . In addition, from the viewpoint of light extraction, the second surface 112 is preferably a flat surface, but unevenness may also exist. For example, as shown in FIG. 6 , unevenness corresponding to the pattern of the conductor layer 101 may exist on the second surface 112 .

If the conductor layer 101 is also exposed on the second surface 112 , the thickness of the planarization layer 102 should be equal to that of the conductor layer 101 . In order to cover the conductive layer 101 with the planarization layer 102 on the second surface 112 , the planarization layer 102 only needs to be thicker than the conductive layer 101 . However, from the viewpoint of flexibility and light transmittance, it is preferably 60 μm or less.

As shown in FIG. 7 , the transparent support 105 can be pasted on the second surface 112 side. Attaching the transparent support 105 can increase the strength of the electrode substrate material 100 for organic devices. The transparent support 105 is not particularly limited, for example, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic , polyvinyl chloride (PVC) and glass etc. at least one. The transparent support may be a layer having an antireflection function.

In addition, as shown in FIG. 8 , a black protective layer 106 may also be provided on the side of the second surface 112 to cover the conductor layer 101 . By providing the black protective layer 106 on the back surface of the conductive layer 101, the pattern of the conductive layer 101 is difficult to see when the organic device is viewed from the front side, and the design aesthetics are improved. Moreover, the transparent support body 105 and the protective layer 106 may be provided simultaneously.

Make the dry film photoresist used in the etching process described later to be black, do not peel off the dry film photoresist left after exposure and development after etching, but use the dry film photoresist directly, so that the protective layer 106 can be formed .

Since the electrode substrate material 100 for an organic device has the above structure, it can have a lower surface resistance and higher flexibility than conventional electrode substrate materials for an organic device. In addition, the luminous efficiency after device formation can also be improved.

The planarization layer 102 may include a gas barrier layer 103 and a transparent resin layer 104 . The organic light-emitting layer and photoelectric conversion layer of an organic device have weak resistance to water vapor, and these layers will be degraded by a little water vapor. Therefore, the organic light-emitting layer and the photoelectric conversion layer are sealed with glass, metal, or a gas barrier film. However, water vapor on the electrode substrate side may not be sufficiently prevented in some cases. Since the electrode substrate material has water vapor barrier properties, 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 water vapor barrier properties. For example, a layer mainly composed of aluminum and oxygen may be formed by atomic deposition. In addition, a layer mainly composed of silicon, nitrogen, oxygen, and carbon may also be formed by chemical vapor deposition (CVD). The gas barrier layer 103 is not limited to one layer, and may be a laminate composed of a plurality of layers. From the viewpoint of preventing water vapor, the thickness of the gas barrier layer 103 is preferably 20 nm or more.

When forming the gas barrier layer 103, the surface of the conductive layer 101 and the surface of the gas barrier layer 103 can form a continuous flat surface. The height difference between the surface of the conductive layer 101 and the surface of the gas barrier layer 103 is preferably less than 300 nm. In addition, the thickness of the transparent resin layer 104 can be made thinner than the thickness of the conductor layer 101 .

<Manufacturing method>

The electrode substrate material 100 for an organic device of this embodiment can be formed, for example, in the following manner.

First, as shown in FIG. 9A , a metal foil 302 to be a conductor layer is laminated on a non-adhesive substrate 301 that has a smooth surface and is difficult for resin and metal to adhere to. A base material having poor adhesion has the property that the base material can be easily peeled off even if resin and metal are in contact with the base material. The substrate itself may be made of a material having low adhesion, or a coating having low adhesion may be formed on the surface of the substrate. For example, substrates can be polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, and polyvinyl chloride ( PVC) etc. one or more than two.

The metal foil 302 has a material and a thickness that can form the aforementioned conductive layer 101 . From the viewpoint of improving the adhesion between the conductive layer 101 formed of the metal foil 302 and the light emitting layer 201 , it is preferable that the surface of the metal foil 302 bonded to the substrate 301 is a smooth surface. Specifically, the arithmetic average roughness (Ra) is preferably 50 nm or less. When laminating the metal foil 302 on the substrate 301, It is also possible to coat the surface of at least one of the substrate 301 and the metal foil 302 with an adhesive or the like having poor adhesion or micro-adhesion. So easy to layer.

Next, as shown in FIG. 9B , the metal foil 302 laminated on the surface of the substrate 301 is patterned to form the conductor layer 101 . The patterning of the metal foil 302 can be performed by known methods such as wet etching or dry etching, for example. As mentioned above, the pattern formed by etching can adopt the existing electrode pattern commonly used for electrodes of organic devices. In addition, a pattern having the substrate pattern 121 and the peripheral pattern 122 shown in FIG. 4 may also be used.

As shown in FIG. 9C , a planarization layer 102 is formed by coating a transparent material. As the transparent material, the aforementioned materials can be used. If a material having fluidity at normal temperature is used, it can be applied, for example, with a coater. The material having fluidity at normal temperature may be, for example, a resin having fluidity by being dissolved in a solvent, a resin having fluidity under specific temperature conditions, a resin having fluidity at normal temperature and curable by light or heat, and the like.

As shown in FIG. 9D , the substrate 301 is peeled off. Since the base material is made difficult to adhere, the base material 301 is easily peeled off. On the first surface formed after peeling off the base material 301 , the conductive layer 101 is exposed without being covered by the planarization layer 102 . In addition, the surface state of the substrate 301 will be transferred to the first surface. By using the substrate 301 with a smooth surface, a smooth first surface can be obtained.

In addition, after the planarization layer 102 is formed and before the substrate 301 is peeled off, a process of attaching the transparent support 105 may also be provided. By providing the transparent support 105, even if the thickness of the planarization layer 102 is thin, the substrate 301 can be easily peeled off. In addition, the transparent support body 105 may be pasted after peeling the base material 301 .

The planarization layer 102 may include a gas barrier layer 103 and a transparent resin layer 104 . In this case, as shown in FIG. 10A , a gas barrier layer 103 is formed on the surface of the substrate 301 after the conductor layer 101 is formed to cover the portion where the metal foil 302 is removed and the portion where the metal foil 302 remains. . The gas barrier layer 103 may be formed of a material with high water vapor barrier properties. For example, a layer mainly composed of aluminum and oxygen (for example, a layer formed of Al2O3, etc.) is formed by using an atomic deposition method, or using Chemical vapor deposition (CVD) may be used to form a layer mainly composed of at least one of silicon, nitrogen, oxygen, and carbon (for example, a layer formed of SiOx, SiN, SiON, or SiONC). In addition, it is also possible to form a laminated body in which these layers are combined. As shown in FIG. 10B , after the gas barrier layer 103 is formed, a transparent material is coated on the surface of the gas barrier layer 103 to form a transparent resin layer 104 . In FIG. 10B , an example is shown in which the transparent resin layer 104 completely fills the concave portion, but the concave portion may not be completely filled with the transparent resin layer 104 . In addition, the transparent resin layer 104 can also completely cover the gas barrier layer 103 . After the substrate 301 is peeled off, the flat surface formed by the surface of the conductor layer 101 and the surface of the gas barrier layer 103 , that is, the first surface, is exposed.

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

(Example)

The following examples are used to further describe the electrode substrate material for organic devices disclosed in this disclosure. The following examples are only examples, and are not intended to limit the present invention.

<Evaluation of smoothness>

The evaluation of the smoothness of the electrode substrate material for organic devices is carried out as follows: use the ultra-high resolution non-contact three-dimensional surface shape measurement system BW-D500 manufactured by NIKON CORPORATION to observe the uneven shape of the surface with a field of view of 2.2mm×2.2mm, And measure the maximum height Sz in the plane. The value calculated by placing the maximum height Rz defined by JIS-B0601-2001 in the three-dimensional space is the maximum height Sz in the plane, and the maximum height Sz in the plane can be applied to the entire surface under observation. Those whose smoothness is below 200 nm in Sz were judged as good (◯), and those exceeding 200 nm were judged as poor (×).

<Evaluation of Water Vapor Barrier>

The water vapor barrier property evaluation of electrode substrate materials for organic devices was performed based on the water vapor permeability defined in JIS K 7129-7:2016. Set the sample on the vapor-deposited metallic calcium, and after 100 hours at 40°C and 90% environment, calculate the water vapor permeability based on the area of the corroded calcium.

<Evaluation of surface resistance>

The surface resistance of the electrode substrate material for organic devices is obtained by measuring the resistance value between two ends on the diagonal of a 50mm×50mm sample with a resistance meter (manufactured by SANWA ELECTRIC INSTRUMENT CO., LTD., RD701 DIGITALMULTIMETER). Those whose surface resistance was less than 10Ω/cm were judged as good (◯), and those exceeding 10Ω/cm2 were judged as bad (×).

<Evaluation of Flexibility>

The surface resistance of the target sample was measured before and after the bending test, and the decrease rate of the surface resistance was obtained. The bending test was performed 50 times with a 10 mmφ mandrel using a coating film bending tester. When the drop rate of the surface resistance was 5% or less, the flexibility was good (◯), and when it exceeded 5%, it was judged as poor (×).

(Example 1)

Apply a difficult-to-adhesive adhesive to one surface (principal surface) of an aluminum foil (manufactured by TOYO ALUMINUM K.K., 1N30) with a thickness of 3 cm x 3 cm and a thickness of 15 μm (arithmetic mean roughness Ra: 7 nm), and heat it at 100 ° C. After drying, the substrate was attached to the coated surface on the side of the adhesive, and aged at 50° C. for 4 days. As the substrate, a PET film (manufactured by Teijin Film Solutions Limited) having a thickness of 38 μm was used.

Paste an alkaline-developing dry film photoresist with a thickness of 15 μm on the back of the aluminum foil, expose and develop it with a mesh mask through ultraviolet (UV), and use an aqueous solution of iron (II) to remove any remaining dry film photoresist. Parts are etched, thereby forming a conductor layer. The conductor layer was formed in a grid shape with a line width of 75 μm and a pitch of 1500 μm, and a wiring density of 10%.

A 150nm SiN film was formed on the etched and remaining part of the aluminum foil by plasma CVD, and then a 20nm Al2O3 film was formed by atomic deposition to form a gas barrier layer.

An epoxy resin with an average light transmittance of 90% for light with a wavelength of 400-800nm is coated on the surface of the formed gas barrier layer to form a film, calculated from the surface on which the gas barrier layer is formed on the adhesive The thickness of the film reaches 20 μm, and the film buries the concavity and convexity of the conductor layer. Tanning layer. A commercially available antireflection film having a thickness of 30 μm was pasted on the surface of the planarizing layer as a transparent support, and dried at 100°C. Thereafter, the base material is peeled off to form an electrode substrate material for an organic device.

The smoothness of the obtained electrode substrate material for organic devices is Rz: 127nm, the water vapor barrier property is 10-5g/m2/day or less, and the surface resistance is 0.02Ω/cm2. There is no change in the surface resistance before and after the bending test.

An organic EL light-emitting element using the subject sample as an anode was formed. The device is formed in the following manner. First, polyethylene dioxythiophene-polystyrene sulfonic acid (PEDOT/PSS, manufactured by sigma aldrich) was coated with a spin coater (manufactured by MIKASA CO., LTD, SpinCoater MS-A150) at a speed of 3000 rpm. on the subject sample and allowed to dry in the atmosphere. Next, Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl)diphenylamine)] (TFB, manufactured by sigma aldrich) was dissolved in toluene And form a solution, rotate with the rotating speed of 3000rpm and coat the obtained solution, and make it dry in nitrogen environment.Poly (9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT, sigma Aldrich) was dissolved in toluene to form a solution, and the obtained solution was coated by rotating at a speed of 2000 rpm. Lithium fluoride was evaporated under vacuum with a vacuum evaporation device (JEOL Ltd., JEE-4X). Aluminum was evaporated as the anode.

A voltage of 7V was applied to the obtained element to make it emit light, and the luminance of the light-emitting element with respect to current and voltage was measured with a luminance meter (manufactured by KONICA MINOLTA, INC., color luminance meter CS-200), and the luminance per 1A was calculated as Luminous efficiency, the luminous efficiency is 0.9cd/A.

Use the UV/O3 cleaning modification device SKB401Y-02 manufactured by Sun Energy Corporation to conduct UV ozone on the electrode substrate material for organic devices with a wavelength of 254nm, an illumination intensity of 10.0mW/cm2, and three levels of 1, 5, and 10 minutes. Cleaning, respectively, was evaluated according to the wetting tension test method defined by JIS-K-6768-1999. The wetting tension at 1 minute was 63mN/m, the wetting tension at 5 minutes was 73mN/m, and the The wetting tension was 73 mN/m.

(Example 2)

The other points were the same as in Example 1 except that the aluminum foil was changed to a 15 μm-thick copper foil (purity: 99.96%), and the epoxy resin was changed to an acrylic resin.

The smoothness of the obtained electrode substrate material for organic devices is Rz: 72nm, the water vapor barrier is 10-5g/m2/day or less, and the surface resistance is 0.01Ω/cm2. There is no change in the surface resistance before and after the bending test.

In addition, as in Example 1, an organic EL light-emitting element was formed using the subject sample as an anode, and the luminous efficiency was measured to be 1.4 cd/A. Same as Example 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 67mN/m, the wetting tension in 5 minutes is 73mN/m, and the wetting tension in 10 minutes is 73mN/m.

(Example 3)

Except that the line width of the conductive layer is 100 μm, the pitch is 2000 μm, and the wiring density is 9%, other aspects are the same as in Example 1.

The smoothness of the obtained electrode substrate material for organic devices is Rz: 158nm, the water vapor barrier property is 10-5g/m2/day or less, and the surface resistance is 0.01Ω/cm2. There is no change in the surface resistance before and after the bending test.

In addition, in the same manner as in Example 1, an organic EL light-emitting element was formed using the subject sample as an anode, and the luminous efficiency was measured to be 1.0 cd/A. Same as embodiment 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 63mN/m, the wetting tension in 5 minutes is 73mN/m, and the wetting tension in 10 minutes is 73mN/m.

(Example 4)

No gas barrier layer was formed, but epoxy resin was directly filled on the etched and removed part of the aluminum foil and the surface where the conductor layer existed. Other aspects were the same as in Example 1, thereby obtaining an electrode substrate material for organic devices. .

The smoothness of the obtained electrode substrate material for organic devices is Rz: 127nm, the surface resistance is 0.02Ω/cm2, and the surface resistance does not change before and after the bending test. The water vapor barrier property is 5.68g/m2/day.

In the same manner as in Example 1, an organic EL light-emitting element was formed using the subject sample as an anode, and the luminous efficiency was measured to be 0.9 cd/A. Same as Example 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 68mN/m, the wetting tension in 5 minutes is 68mN/m, and the wetting tension in 10 minutes is 73mN/m.

(Example 5)

No gas barrier layer is formed, but epoxy resin is directly filled on the etched and removed part of the aluminum foil and on the surface where the conductor layer exists. Day's commercially available gas barrier film was the same as that of Example 1 except that, thereby obtaining an electrode substrate material for an organic device.

The smoothness of the obtained electrode substrate material for organic devices is Rz: 142nm, the surface resistance is 0.02Ω/cm2, and the surface resistance does not change before and after the bending test. The water vapor barrier is 3×10-2g/m2/day.

In the same manner as in Example 1, an organic EL light-emitting element was formed using the subject sample as an anode, and the luminous efficiency was measured to be 0.5 cd/A. Same as Example 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 66mN/m, the wetting tension in 5 minutes is 73mN/m, and the wetting tension in 10 minutes is 73mN/m.

(comparative example 1)

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

The smoothness of the obtained electrode substrate material for organic devices is Rz: 17nm, the water vapor barrier is 10-5g/m2/day or less, but the surface resistance is 0.68Ω/cm2, and the glass is slightly bent The substrate will crack.

In addition, as in Example 1, an organic EL light-emitting element was formed using the subject sample as an anode, and the luminous efficiency was measured to be 5.2 cd/A. Same as Example 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 48mN/m, the wetting tension in 5 minutes is 61mN/m, and the wetting tension in 10 minutes is 67mN/m.

(comparative example 2)

Electrodes for organic devices are obtained by laminating indium tin oxide (ITO) with a film thickness of 120 nm on a commercially available gas barrier film with a thickness of 75 μm and a water vapor transmission rate of 4×10-4 g/m2/day by sputtering Substrate material.

The smoothness of the obtained electrode substrate material for organic devices is Rz: 58nm, and the water vapor barrier property is 1×10-4g/m2/day, but the surface resistance is 9.40Ω/cm2, and the resistance value after the bending test increases rapidly to 2296.00Ω/cm2.

In addition, as in Example 1, an organic EL light-emitting element was formed using the subject sample as an anode, but the organic EL light-emitting element did not emit light. Same as Example 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 52mN/m, the wetting tension in 5 minutes is 58mN/m, and the wetting tension in 10 minutes is 62mN/m.

The crystallinity of the ITO film formed on the thin film is poor, and the surface resistance is large. Because it is a thin film, it can be bent, but when bent with a small radius of curvature, the ITO film cracks and the resistance increases. In addition, in order to increase the wetting tension, the pretreatment time is longer.

(comparative example 3)

Coat a commercially available acrylic adhesive on one surface (main surface) of an aluminum foil (manufactured by TOYO ALUMINUM K.K., 1N30) with a thickness of 3cm x 3cm and a thickness of 15μm (Ra: 7nm). A commercially available gas barrier film of 4 x 10-4 g/m2/day was attached to the coated surface on the side of the adhesive.

Next, a commercially available dry film is pasted on the back of the aluminum foil, exposed and developed with a mesh mask under UV conditions, and the part where the dry film is not left is etched with an aqueous solution of ferric chloride (II) to form a fine line. An aqueous solution of sodium hydroxide peels off the dry film, thereby obtaining an electrode substrate material for an organic device.

The water vapor barrier property of the obtained electrode substrate material for organic devices is 4×10-4g/m2/day, but the surface resistance is 0.04Ω/cm2, and the resistance value after the bending test does not change, but the smoothness is Rz: 1621nm.

As in Example 1, an organic EL light-emitting element using the subject sample as an anode was formed, but did not emit light. Same as Example 1, the wetting tension after UV ozone cleaning is evaluated, the wetting tension in 1 minute is 70mN/m, the wetting tension in 5 minutes is 73mN/m, and the wetting tension in 10 minutes is 73mN/m.

Since the conductive layer is made of aluminum foil, there are no problems in terms of surface resistance and flexibility. However, since the planarization layer is not formed, steps are generated, and the smoothness is poor.

(comparative example 4)

Aluminum was evaporated on a commercially available gas barrier film with a thickness of 75 μm and a water vapor transmission rate of 4×10-4 g/m2/day to form an evaporated aluminum film with a thickness of 300 nm. A commercially available dry film was pasted on the surface of the vapor-deposited aluminum film, exposed and developed through UV with a mesh mask, and the part where the dry film did not remain was etched with an aqueous solution of iron (II) to form a pattern. Thereafter, the dry film was peeled off with an aqueous sodium hydroxide solution, whereby an electrode substrate material for an organic device was obtained.

The water vapor barrier property of the obtained electrode substrate material for organic devices is 4×10-4g/m2/day, and the surface resistance is 0.42Ω/cm2, but the resistance value after the bending test increases to 12.6Ω/cm2, and it is smooth The property is Rz: 343nm.

As in Example 1, an organic EL light-emitting element using the subject sample as an anode was formed, but did not emit light. As in Example 1, the wetting tension after UV ozone cleaning was evaluated. The wetting tension in 1 minute was 50 mN/m, the wetting tension in 5 minutes was 73 mN/m, and the wetting tension in 10 minutes was 73 mN/m. The force is 73mN/m.

Since the conductor layer was formed of the vapor-deposited aluminum film, cracks appeared on the conductor layer after 50 bending tests, and the surface resistance increased. In addition, since a step portion is generated due to the conductor layer, smoothness is poor.

Table 1 shows the results of each Example and Comparative Example together.

[Industrial availability]

The electrode substrate material for organic devices disclosed in this disclosure can achieve high smoothness, gas barrier properties, light transmittance, low surface resistance and high flexibility, can shorten the pretreatment time in the coating process, and is very useful as an electrode material for organic devices.

100: Electrode substrate materials for organic devices

101: conductor layer

102: Planarization layer

Claims (10)

An electrode substrate material for organic devices, which has a conductor layer made of patterned metal foil and a planarization layer arranged around the conductor layer; on the first surface, the surface of the conductor layer is exposed from the planarization layer , and the surface of the aforementioned conductor layer forms a continuous flat surface with the surface of the aforementioned planarization layer; on the second surface opposite to the aforementioned first surface, the aforementioned planarization layer has concavities and convexities corresponding to the pattern of the aforementioned conductor layer. The electrode substrate material for organic devices as described in claim 1, wherein the conductive layer has a pattern with a line width of 20 μm to 200 μm, and the density of the conductive layer on the first surface per unit area is 15% or lower. The electrode substrate material for organic devices as described in claim 1, wherein the planarization layer includes a gas barrier layer and a transparent resin layer; the surface of the gas barrier layer and the exposed surface of the conductor layer form a continuous smooth surface. The electrode substrate material for organic devices as described in claim 3, wherein the gas barrier layer includes at least one of a layer mainly composed of aluminum and oxygen and a layer mainly composed of at least one of silicon, nitrogen, oxygen and carbon. One, and the thickness is more than 20nm. The electrode substrate material for organic devices as described in claim 1, wherein the light transmittance of the planarization layer to light with a wavelength of 400nm to 800nm is above 85%. The electrode substrate material for organic devices as described in claim 5, wherein the planarization layer is made of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS ), polycarbonate (PC), acrylic, polyvinyl chloride (PVC), fluorocarbon resin, indium tin oxide (ITO) and polyethylene dioxythiophene/polystyrene sulfonic acid (PEDOT/PSS) or both more than one form. The electrode substrate material for organic devices as described in any one of Claims 1 to 6, wherein the aforementioned conductor layer includes a substrate pattern and is arranged outside the substrate pattern and can be connected to the outside Peripheral patterns for external device connections. The electrode substrate material for organic devices as described in any one of Claims 1 to 6, wherein the conductor layer is an aluminum foil with a thickness of not less than 6 μm and not more than 30 μm. The electrode substrate material for organic devices according to any one of claims 1 to 6, wherein on the second surface opposite to the first surface, the surface of the conductor layer is covered by the planarization layer. A method for manufacturing an electrode substrate material for an organic device, which is used to manufacture the electrode substrate material for an organic device as described in any one of Claims 1 to 9, comprising: a process of attaching a metal foil to the surface of the substrate; A process of patterning the aforementioned metal foil bonded to the aforementioned substrate to form an electrode pattern; a process of coating a transparent material on the surface of the substrate on which the aforementioned electrode pattern is formed to form a planarization layer; and forming the aforementioned planarization After the process of layering, the process of peeling off the aforementioned base material; in the process of forming the aforementioned planarization layer, the unevenness corresponding to the pattern of the conductor layer is formed on the aforementioned planarization layer.

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