KR102341557B1 - Electrode Substrate Materials for Organic Devices - Google Patents

Abstract

The electrode substrate material for organic devices 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 Materials for Organic Devices

The present disclosure relates to electrode substrate materials for organic devices.

In recent years, as a light source of a next-generation lighting device, an organic light emitting diode (Organic Light Emitting Diode) is attracting attention. 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 the energy generated at that time. In addition, as a next-generation solar cell device, organic solar cells such as perovskite type and dye-sensitized type are attracting attention. An organic solar cell includes a photoelectric conversion layer between an anode and a cathode, and generates electricity by emitting electrons and holes excited by incident sunlight from the anode and the cathode.

In these devices, while being able to form organic functional layers, such as an organic light emitting layer and a photoelectric conversion layer, into a film, the electrode substrate material which can extract or introduce|transduce light is calculated|required.

The electrode substrate material is required to have smoothness that can form an organic functional layer into a film so that pinholes or the like do not occur, in particular, there is no step or projection. In recent years, large-area OLED and organic solar cells are required. In order to uniformly emit light on 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 within the device. Therefore, a low surface resistance is required for the electrode substrate material. In addition, since OLEDs and organic solar cells are produced by a roll-to-roll process to increase productivity, and can be molded into a curved surface and used, high flexibility is also required for electrode substrate materials.

Development of the electrode substrate material for organic devices which satisfy|fills these requirements is advancing. 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, , refer to Patent Document 1).

Further, an electrode substrate material for an organic device formed by laminating a metal vapor deposition film in a mesh shape on a gas barrier film or the like is also studied (for example, refer to Patent Document 2).

Japanese Patent Laid-Open No. 2008-031496 Japanese Patent Laid-Open 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 and therefore does not bend, making it impossible to roll-to-roll manufacturing. In addition, in order to adapt to the application process, it takes time for pretreatment to ensure wettability.

An electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a gas barrier film or the like has a significantly higher surface resistance than a metal such as silver, aluminum or copper. It can also be bent, but if the bending radius of curvature is reduced, cracks are generated in the ITO layer and the surface resistance is increased.

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

The subject of this indication is making it possible to implement|achieve the 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, wherein, in a 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 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.

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 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 main components, The thickness can be 20 nm or more.

One aspect of the electrode substrate material for organic devices WHEREIN: The light transmittance of wavelength 400nm - 800nm of a planarization layer can be 85 % or more.

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

One aspect of the electrode substrate material for organic devices WHEREIN: A conductor layer can be made into 6 micrometers or more and 30 micrometers or less aluminum foil in thickness.

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

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the OLED using the surface electrode material for OLEDs of one Embodiment.
2 is a perspective view showing a surface electrode material for OLED according to an embodiment.
FIG. 3 is a cross-sectional view taken along line III-III of FIG. 2 .
4 is a plan view showing a modified example of the conductor layer pattern.
5 is a cross-sectional view showing a modified example of the surface electrode material for OLED.
6 is a cross-sectional view showing a modified example of the surface electrode material for OLED.
7 is a cross-sectional view showing a modified example of the surface electrode material for OLED.
8 is a cross-sectional view showing a modified example of the surface electrode material for OLED.
9A is a perspective view showing one step of a method for manufacturing a surface electrode material for OLED.
9B is a perspective view showing one step of a method for manufacturing a surface electrode material for OLED.
9C is a perspective view showing one step of a method for manufacturing a surface electrode material for OLED.
9D is a perspective view showing one step of a method for manufacturing a surface electrode material for OLED.
10A is a cross-sectional view showing one step of a method for 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 organic devices of this embodiment is provided with the conductor layer 101 and the planarization layer 102, and can be used as the anode (surface electrode) 202 of the OLED 200 as shown in FIG. have. In the OLED 200 , the light emitting layer 201 is formed 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 is deposited or applied between the cathode 203 and the anode 202, including, in addition to the organic light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a charge accumulation layer, and the like. It means the entire layer formed of, etc.

As shown in FIG.2 and FIG.3, the electrode substrate material 100 for organic devices of this embodiment is the conductor layer 101 which consists of patterned metal foil, and the planarization layer 102 formed around the conductor layer 101. to provide 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. . Thereby, an organic functional layer or the like can be easily formed on the first surface.

Since the surface of the electrode substrate material for organic devices of this embodiment consists of the conductor layer 101 which consists of metal foil, and the planarization layer 102, and an ITO layer does not exist, applicability|paintability can be improved easily. Therefore, when manufacturing an organic device by the application|coating method, the advantage of being able to shorten the pre-processing time, such as ultraviolet-ray ozone cleaning, can also be acquired.

<Conductor layer>

The conductor layer 101 of this embodiment consists of the metal foil patterned into the predetermined shape. Unlike a conductor layer made of a metal vapor deposition film or the like, the conductor layer 101 made of metal foil is not easily broken 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 the organic device, the conductor layer 101 contacts the light emitting layer 201 of the OLED, and applies a voltage to the light emitting layer 201 .

The metal foil used as the conductor layer 101 is not specifically limited, For example, aluminum foil, copper foil, gold foil, or silver foil etc. can be used. Among them, an aluminum foil having high light reflectivity while being lightweight and easily oxidized in the deep part is preferable.

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

The pattern of the conductor layer 101 can be designed according to the characteristic 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 grid 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 may 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 interposing the terminal 124 . The external device may be, for example, a power supply unit for supplying power to the organic device.

Although the thickness of the conductor layer 101 is not specifically limited, 6 micrometers or more are preferable from a viewpoint of ensuring flexibility and a viewpoint of reducing surface resistance. Moreover, from a viewpoint of improving the light transmittance, 30 micrometers or less are preferable.

Although the line width of the conductor layer 101 is not specifically limited, From a viewpoint of reducing surface resistance, 20 micrometers or more are preferable, and from a viewpoint of reducing light emission nonuniformity, 200 micrometers or less are preferable. 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.

<flattening layer>

The planarization layer 102 is formed around the conductor layer 101 to fill the opening 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 on 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 portion thereof, and the first surface 111 as a whole becomes a flat surface. Since the 1st surface 111 becomes such a continuous flat surface, the uniform light emitting layer 201 can be formed into a film on the surface of the electrode substrate material for organic devices of this embodiment. Here, the first surface 111 may be in close contact with the entire surface of the light emitting layer 201 , but the level difference 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 making the transmittance|permeability of a 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 fluororesin can be used These resins can be used individually or in mixture of 2 or more types. A transparent conductive material such as indium tin oxide (ITO) or polyethylenedioxythiophene/polystyrenesulfonic acid (PEDOT/PSS) can also be used.

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

As shown in FIG. 3 , when the conductor layer 101 is not covered with the planarization layer 102 even on the second surface 112 opposite to the first surface 111 , the degree of freedom of the 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 exist. For example, as shown in FIG. 6, it can be set as the structure in which the unevenness|corrugation corresponding to the pattern of the conductor layer 101 exists in the 2nd surface 112. As shown in FIG.

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

As shown in FIG. 7, the transparent support body 105 can also be joined to the 2nd 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, for example, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride ( PVC) and glass. The transparent support may be a layer having an antireflection function.

Moreover, as shown in FIG. 8, the black protective layer 106 can also be formed in the 2nd surface 112 side so that the conductor layer 101 may be covered. 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 surface side, and design properties are improved. In addition, both the transparent support 105 and the protective layer 106 may be formed.

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

When the electrode substrate material 100 for organic devices has the above structures, the surface resistance can be lowered than that of the conventional electrode substrate material for organic devices, and flexibility can be improved. Moreover, the luminous efficiency at the time of using for 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 an organic device are weak to water vapor, and will deteriorate even with a little water vapor. Accordingly, the organic light emitting layer or the photoelectric conversion layer is sealed with glass, metal, or a gas barrier film or the like. However, there are cases where water vapor on the electrode substrate side is not sufficiently prevented. When the electrode substrate material has a water vapor barrier property, it is possible to make it difficult for water vapor to penetrate from the electrode substrate side, thereby suppressing deterioration of the organic functional layer.

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

When the gas barrier layer 103 is formed, the surface of the conductor layer 101 and the surface of the gas barrier layer 103 can form a continuous flat surface. The level difference 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 this embodiment can be formed as follows, for example.

First, as shown in FIG. 9A, the metal foil 302 which will become a conductor layer is laminated|stacked on the base material 301 which has a smooth surface and has difficult adhesion with respect to resin and a metal. The base material having difficulty in adhesion refers to a base material having the ability to be easily peeled off even when a resin or a metal comes into contact. The base material itself may be formed of a material having a difficult-to-adhesive property, or a non-adhesive coating layer may be formed on the surface thereof. For example, as the substrate, one or two of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic and polyvinyl chloride (PVC) More than one species can be used.

For the metal foil 302 , a material and thickness capable of forming the aforementioned conductor layer 101 is used. From the viewpoint of improving the adhesion between the conductor layer 101 and the light emitting layer 201 formed of the metal foil 302 , the surface of the metal foil 302 to be bonded to the substrate 301 is preferably smooth, 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 with poor adhesion or poor 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|stacked on the surface of the base material 301 is patterned, and the conductor layer 101 is formed. The patterning of the metal foil 302 may be performed by a known method, such as wet etching or dry etching, for example. As the pattern formed by etching, a known electrode pattern employed as an electrode of an organic device can be employed as described above. Moreover, it can also be set as the pattern which has the base pattern 121 and the peripheral pattern 122 as shown in FIG.

Next, as shown in FIG. 9C, the transparent material is coated and the planarization layer 102 is formed. The transparent material may use the same material as described above, and in the case of a material having fluidity at room temperature, it may be coated using, for example, a coater. The material having fluidity at room temperature can be, for example, a resin having fluidity by being dissolved in a solvent, a resin having fluidity at a specific temperature condition, a resin having fluidity at room temperature and curable by heat or light, etc.

Next, as shown in FIG. 9D, the base material 301 is peeled. By making the base material difficult to adhere, it can be easily peeled off. On the first surface formed by peeling the base material 301 , the conductor layer 101 is exposed without being coated with the planarization layer 102 . In addition, the 1st surface becomes the surface to which the surface state of the base material 301 was transcribe|transferred. By using the base material 301 having a smooth surface, a smooth first surface is obtained.

And after forming the planarization layer 102, before peeling the base material 301, you may provide the process of bonding the transparent support body 105 together. By forming the transparent support body 105, even when the thickness of the planarization layer 102 is thin, peeling of the base material 301 becomes easy. In addition, after peeling the base material 301, the transparent support body 105 can also be joined.

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, on the surface of the base material 301 after the conductor layer 101 is formed, both the portion where the metal foil 302 is removed and the portion where the metal foil 302 remains is covered with a gas barrier. 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, etc., a layer containing aluminum and oxygen as main components (for example, a layer _{made of Al 2} O ₃ etc.) is formed, or using a chemical vapor deposition (CVD) method, silicon and , and forming a layer (e.g., a layer composed of SiO _x, SiN, SiON, or SiONC, etc.) as a main component and at least one of nitrogen, oxygen and carbon. Moreover, the laminated body which combined these layers can also be formed. 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 the transparent resin layer 104. Although FIG. 10B shows an example in which the transparent resin layer 104 completely fills the concave portion, the concave portion does not have to be completely filled. Also, the transparent resin layer 104 may completely cover the gas barrier layer 103 . When the base material 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, If a 1st surface can be made flat, it can also form by another method.

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 examples and are not intended to limit the present invention.

<Smoothness evaluation>

The smoothness evaluation of the electrode substrate material for an organic device was performed using the NIKON CORP. ultra-high-resolution non-contact three-dimensional surface shape measurement system BW-D500, observing the concavo-convex shape of the surface in a field of view of 2.2 mm × 2.2 mm, and the maximum size in the plane Sz was measured. It is a value calculated by extending the maximum size Rz defined by JIS-B0601-2001 in three dimensions so that it can be applied to the entire observed surface. Smoothness made good (circle) a thing with Sz 200 nm or less, and made bad (x) a thing exceeding 200 nm.

<Water vapor barrier property evaluation>

Water vapor barrier property evaluation of the electrode substrate material for organic devices is water vapor transmission rate defined by JISK7129-7:2016. A sample was installed on the deposited metallic calcium, and after 100 hours had elapsed in an environment of 40°C and 90%, it was calculated by calculating the area of the corroded calcium.

<Evaluation of surface resistance>

The surface resistance of the electrode substrate material for an organic device 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 considered good (○), and those exceeding 10 Ω/cm 2 were considered defective (x).

<Flexibility evaluation>

The surface resistance before and after the bending test of the target sample was measured, and the rate of decrease of the surface resistance was calculated|required. The bending test was performed 50 times with a 10 mmφ mandrel using a coating film bending tester. What the decrease rate of the surface resistance was 5 % or less was made into good (circle) in softness|flexibility, and the thing exceeding 5 % was made into bad (x).

(Example 1)

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

Next, an alkali developing dry film resist having a thickness of 15 μm is bonded to the back side of the aluminum foil, exposed to ultraviolet (UV) light using a mesh-shaped photomask, and developed, and the part where the dry film resist is not left is iron chloride ( II) It was etched with an aqueous solution to form a conductor layer. The conductor layer had a line width of 75 µm, a lattice shape with a pitch of 1500 µm, and a wiring density of 10%.

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

Next, an epoxy resin having an average transmittance of 90% at a wavelength of 400 to 800 nm was applied to the surface of the formed gas barrier layer, and the thickness from the surface where the gas barrier layer was formed on the adhesive was 20 μm, and the unevenness of the conductor layer was reduced. It was coated so as to be buried, and a planarization layer was formed. A commercially available antireflection film having a thickness of 30 µm was bonded to the surface of the planarization layer as a transparent support, and dried at 100°C. Then, the base material was peeled and it was set as the electrode substrate material for organic devices.

The smoothness of the obtained electrode substrate material for organic devices was Rz 127 nm, the water vapor barrier property was 10 ^-5 g/m 2 /day or less, the surface resistance was 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-polystyrene sulfonate (PEDOT/PSS, manufactured by Sigma Aldrich) was spin-coated on a target sample 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 3000rpm After spin coating, drying in a nitrogen atmosphere, poly(9,9-dioctylfluorine-alt-benzothiadiazole) (F8BT, manufactured by Sigma Aldrich) dissolved in toluene was spin-coated at 2000 rpm. Next, lithium fluoride was vacuum-deposited using a vacuum deposition apparatus (manufactured by JEOL, JEE-4X), and aluminum was further vacuum-deposited as an anode.

A voltage of 7V was applied to the obtained device to emit light, and the luminance with respect to 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, 0.9 It was cd/A.

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

(Example 2)

It carried out similarly to Example 1 except having made the aluminum foil into copper foil (purity 99.96%) of thickness 15 micrometers, and having made the epoxy resin into the acrylic resin.

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

Moreover, it was 1.4 cd/A when the OLED which uses the target sample as an anode was formed similarly to Example 1, and the luminous efficiency was measured. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 67 mN/m at 1 minute, 73 mN/m at 5 minutes, and 73 mN/m at 10 minutes.

(Example 3)

It carried out similarly to Example 1 except that the line|wire width of the conductive layer was 100 micrometers, the pitch was 2000 micrometers, and the wiring density was 9 %.

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

Moreover, it was 1.0 cd/A when the OLED which uses the target sample as an anode was formed similarly to Example 1, and the luminous efficiency was measured. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 63 mN/m at 1 minute, 73 mN/m at 5 minutes, and 73 mN/m at 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 from which the aluminum foil was removed by etching and the surface with the conductor layer were directly filled with an epoxy resin.

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

It was 0.9 cd/A when OLED which uses the target sample as an anode was formed similarly to Example 1, and the luminous efficiency was measured. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 68 mN/m at 1 minute, 68 mN/m at 5 minutes, and 73 mN/m at 10 minutes.

(Example 5)

Without forming a gas barrier layer, that is, the part where the aluminum foil was removed by etching and the surface with the conductor layer were directly filled with an epoxy resin, the transparent support was 75 μm thick and the water vapor transmission rate was 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 that a commercially available gas barrier film was used.

The smoothness of the obtained electrode substrate material for organic devices was Rz 142 nm, the surface resistance was 0.02 ohm/cm<2>, and the surface resistance after a bending test did not change. The water vapor barrier property was 3x10 ^-2 g/m 2 /day.

It was 0.5 cd/A when the OLED which uses the target sample as an anode was formed similarly to Example 1, and the luminous efficiency was measured. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 66 mN/m at 1 minute, 73 mN/m at 5 minutes, and 73 mN/m at 10 minutes.

(Comparative Example 1)

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

The smoothness of the obtained electrode substrate material for organic devices was Rz: 17 nm, and the water vapor barrier property was 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 bent slightly.

Moreover, it was 5.2 cd/A when the OLED which uses the target sample as an anode was formed similarly to Example 1, and the luminous efficiency was measured. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 48 mN/m at 1 minute, 61 mN/m at 5 minutes, and 67 mN/m at 10 minutes.

(Comparative Example 2)

By laminating indium tin oxide (ITO) 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 transmission rate of 4 × 10 ^{−4 g/m 2 /day, an electrode substrate material for an organic device} got it

The smoothness of the obtained electrode substrate material for an organic device was Rz: 58 nm, and the water vapor barrier property was 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 , which increased rapidly.

In addition, in the same manner as in Example 1, an OLED having the target sample as an anode was formed, but no light was emitted. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 52 mN/m at 1 minute, 58 mN/m at 5 minutes, and 62 mN/m at 10 minutes.

The crystallinity of the ITO film formed into a film on the film was bad, and the surface resistance became large. 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 wetting tension, a long pretreatment time was required.

(Comparative Example 3)

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

Next, a thin wire is formed by bonding a commercially available dry film to the back side of the aluminum foil, exposing and developing it under ultraviolet conditions using a mesh-shaped photomask, and etching the portion where the dry film does not remain with an aqueous iron (II) chloride solution. Then, the surface electrode material for OLED was obtained by peeling the dry film with an aqueous sodium hydroxide solution.

The water vapor barrier property of the obtained electrode substrate material for an organic device was 4×10 ⁻⁴ g/m 2 /day, but 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 did not emit light. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 70 mN/m at 1 minute, 73 mN/m at 5 minutes, and 73 mN/m at 10 minutes.

Since the conductor layer was formed of aluminum foil, there were no problems in surface resistance and flexibility, but a level difference occurred because the planarization layer was not formed, and 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 transmission rate of 4×10 ⁻⁴ g/m 2 /day to form an aluminum 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 to ultraviolet light using a mesh-shaped photomask and developed, and the portion where the dry film did not remain was etched with an iron (II) chloride aqueous solution and patterned. Then, the electrode substrate material for organic devices was obtained by peeling a dry film using sodium hydroxide aqueous solution.

The water vapor barrier property of the obtained electrode substrate material for an organic device 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 Silver Rz: 343 nm.

As in Example 1, an OLED using the target sample as an anode was formed, but did not emit light. As in Example 1, when the wetting tension after ultraviolet ozone washing was evaluated, it was 50 mN/m at 1 minute, 73 mN/m at 5 minutes, and 73 mN/m at 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 the surface resistance was increased. Moreover, since the level|step difference by the conductor layer generate|occur|produced, the smoothness was not good.

In Table 1, the results of each Example and Comparative Example are summarized and shown.

[Table 1]

The electrode substrate material for an organic device of the present disclosure can realize high smoothness, gas barrier properties, light transmittance, low surface resistance and high flexibility, and shorten the pretreatment time in the coating step, 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 surface 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 (11)

A conductor layer made of a patterned metal foil;
an insulating planarization layer formed around the conductor layer;
In the first side, 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;
on a second surface opposite to the first surface, a surface of the conductor layer is covered by the planarization layer;
a portion covering the second surface of the planarization layer has irregularities corresponding to the pattern of the conductor layer;
An electrode substrate material for an organic device. According to claim 1,
The said conductor layer forms the pattern whose line|wire width is 20 micrometers or more and 200 micrometers or less, The density of the said conductor layer per unit area of the said 1st surface is 15% or less, The electrode substrate material for organic devices. According to claim 1,
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. 4. The method of claim 3,
The gas barrier layer is a layer comprising at least one of aluminum oxide, silicon nitride, carbon-containing silicon nitride, silicon oxide, carbon-containing silicon oxide, silicon oxynitride and carbon-containing silicon oxynitride, and has a thickness of 20 nm or more, organic An electrode substrate material for a device. According to claim 1,
The said planarization layer is an electrode substrate material for organic devices whose light transmittance with a wavelength of 400 nm - 800 nm is 85 % or more. 6. The method of claim 5,
The planarization layer is one of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC), and fluororesin; 2 or more types of electrode substrate materials for organic devices. 7. The method according to any one of claims 1 to 6,
The conductive layer includes a base pattern and a peripheral pattern formed outside the base pattern and connectable to an external device, the electrode substrate material for an organic device. 7. The method according to any one of claims 1 to 6,
The said conductor layer is 6 micrometers or more and 30 micrometers or less aluminum foil in thickness, The electrode substrate material for organic devices. 7. The method according to any one of claims 1 to 6,
on a second side opposite to the first side, a surface of the conductor layer is exposed from the planarization layer. 7. The method according to any one of claims 1 to 6,
in a second side opposite to the first side, a surface of the conductor layer is covered by the planarization layer. A step of attaching the metal foil to the surface of the substrate;
A process of forming an electrode pattern by patterning the metal foil attached to the substrate;
forming a planarization layer by coating a transparent material on the surface of the substrate on which the electrode pattern is formed;
a step of peeling the base material after the step of forming the planarization layer;
In the step of forming the planarization layer, the surface of the conductor layer is covered with the planarization layer, and irregularities corresponding to the pattern of the conductor layer are formed in the planarization layer;
A method of manufacturing an electrode substrate material for an organic device.

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