KR20210055209A - Transparent electrode structure and electric device including the same - Google Patents

Abstract

According to an embodiment of the present invention, provided is a transparent electrode structure, which includes a transparent substrate, a lower insulating layer formed on the transparent substrate, a transparent electrode layer laminated on the lower insulating layer, and an adhesive layer formed between the transparent substrate and the lower insulating layer and containing air bubbles. When projected in the planar direction, the ratio of the area of a region in which the air bubbles are distributed may be 2 to 35% of the area of the upper surface of the adhesive layer. Through this, optical properties of the transparent electrode structure may be improved.

Description

A transparent electrode structure and an electric device including the same TECHNICAL FIELD

The present invention relates to a transparent electrode structure and an electric device including the same. More specifically, the present invention relates to a transparent electrode structure including an insulating layer and an electrode layer, and an electric device including the same.

Electrode structures are introduced in various electric/electronic devices such as battery devices, lighting devices, and display devices. In the case of the lighting device and the display device, an electrode structure having improved transparency is employed for optical properties and image quality. In addition, in the case of a battery device such as a solar cell, an electrode structure having improved transparency is employed to improve light efficiency.

The electrode structure or functional layer such as, for example, an organic light emitting layer or a photoactive layer may be oxidized when exposed to moisture penetrating from the outside of the battery device, and operation in the functional layer may also be deteriorated.

In the case of a battery device that has recently become thinner, it may be more easily exposed to oxidation and damage caused by moisture penetration.

Therefore, there is a need for a study of an electrode structure to improve the chemical stability of the device while shaping the transparency of the electrode. For example, Korean Laid-Open Patent Publication No. 2018-0014073 discloses a metal electrode for OLED lighting, but the above-described improvement of characteristics is not recognized.

Korean Patent Application Publication No. 2018-0014073

An object of the present invention is to provide a transparent electrode structure having improved optical, chemical, and mechanical properties.

An object of the present invention is to provide an electrical device such as a lighting device and a solar cell including the transparent electrode stack.

1. Transparent substrate; A lower insulating layer formed on the transparent substrate; A transparent electrode layer stacked on the lower insulating layer; And a point-adhesive layer formed between the transparent substrate and the lower insulating layer and including bubbles, and a ratio of the area of the area where the bubbles are distributed when projected in a plane direction is 2 to 35% of the transparent electrode structure.

2. The transparent electrode structure according to the above 1, wherein the air bubbles are distributed on at least one of a lower interface of an adhesive layer adjacent to the transparent substrate and an upper interface of an adhesive layer adjacent to the lower insulating layer.

3. The transparent electrode structure according to the above 2, wherein the air bubbles are distributed together at a lower interface of the adhesive layer adjacent to the transparent substrate and an upper interface of the adhesive layer adjacent to the lower insulating layer.

4. In the above 1, each diameter of the bubbles is 0.025 to 2.5㎛, the transparent electrode structure.

5. In the above 1, the haze value of the adhesive layer measured according to JIS K7136 is 5 to 60%, the transparent electrode structure.

6. In the above 1, the absolute value of the difference between the surface energy of the lower insulating layer and the adhesive layer is 4 to 50mN/m, the transparent electrode structure.

7. The transparent electrode structure according to the above 1, wherein the absolute value of the difference in surface energy between the transparent substrate and the adhesive layer is 17 to 30 mN/m.

8. The transparent electrode structure according to the above 1, further comprising a barrier layer disposed between the lower insulating layer and the transparent electrode layer.

9. In the above 8, the barrier layer is indium-tin oxide (ITO), aluminum oxide, zinc oxide, aluminum oxide-zinc oxide composite (AZO) material, silazane, siloxane, and silicon-containing inorganic A transparent electrode structure comprising at least one barrier material selected from the group consisting of materials.

10. The transparent electrode structure according to the above 8, wherein the barrier layer has a moisture permeability of 10 ^-3 g/m ^{2 24hr or less under a condition of 40°C and 90% relative humidity.}

11. The transparent electrode structure according to the above 1, wherein the lower insulating layer includes an intermediary layer and a protective layer sequentially stacked from the adhesive layer.

12. The transparent electrode structure according to the above 1, wherein the transparent electrode layer includes a first transparent oxide electrode layer, a metal layer, and a second transparent oxide electrode layer sequentially stacked.

13. The transparent electrode structure of 1 above; An organic emission layer disposed on the transparent electrode structure; And an upper electrode disposed on the organic emission layer.

14. The transparent electrode structure of 1 above; A photoactive layer disposed on the transparent electrode structure; And an upper electrode disposed on the photoactive layer.

The transparent electrode structure according to embodiments of the present invention may include an adhesive layer including air bubbles. The bubbles promote scattering or dispersion of light passing through the transparent electrode structure, thereby preventing total reflection of light. Accordingly, the light efficiency of the transparent electrode structure may be improved.

In some embodiments, the area of the area in which the air bubbles included in the adhesive layer are distributed may be adjusted through a difference value in surface energy of the lower insulating layer and the adhesive layer or a difference value in surface energy between the transparent substrate and the adhesive layer. Accordingly, the light efficiency of the transparent electrode structure may be further improved.

In some embodiments, by inserting a barrier layer between the transparent electrode layer and the lower insulating layer, oxidation of the transparent electrode layer may be prevented and chemical stability may be further improved.

By using the transparent electrode structure, it is possible to manufacture a lighting device and a battery device having improved optical, chemical, and mechanical stability.

1 is a schematic cross-sectional view illustrating a transparent electrode structure according to exemplary embodiments.
2 and 3 are schematic cross-sectional views illustrating an electric device to which a transparent electrode structure according to exemplary embodiments is applied.
4 is a microscope observation photograph of an adhesive layer according to exemplary embodiments.

Embodiments of the present invention provide a transparent electrode structure having improved optical properties, including an adhesive layer in which bubbles are formed. In addition, it provides an electric device such as a lighting device, a battery device, etc. to which the transparent electrode structure is applied.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings. However, the following drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the contents of the present invention, so that the present invention is described in such drawings. It is limited to the matters and should not be interpreted.

1 is a schematic cross-sectional view illustrating a transparent electrode structure according to exemplary embodiments.

Referring to FIG. 1, the transparent electrode structure 100 is a transparent substrate 110. Including the lower insulating layer 130 formed on the transparent substrate, the transparent electrode layer 150 stacked on the lower insulating layer 130, the air bubbles 122 formed between the transparent substrate 110 and the lower insulating layer 130 It may include a pressure-sensitive adhesive layer 120.

In some embodiments, a barrier layer 140 formed between the lower insulating layer 130 and the transparent electrode layer 150 may be further included. In some embodiments, the lower insulating layer 130 may include an intermediary layer 132 and a protective layer 134 sequentially stacked on the adhesive layer 120. In some embodiments, an upper protective layer 136 may be included between the barrier layer 140 and the transparent electrode layer 150.

The transparent substrate 110 may include glass or a transparent resin material having high light transmittance. Examples of the transparent resin material include cyclic olefin polymer (COP), polyethylene terephthalate (PET), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), Polyallylate, polyimide (PI), cellulose acetate propionate (CAP), polyethersulfone (PES), cellulose triacetate (TAC), polycarbonate (PC), cyclic olefin copolymer (COC), And polymethyl methacrylate (PMMA).

The lower insulating layer 130 may include an intermediary layer 132 and a protective layer 134 sequentially stacked from the adhesive layer 120.

The intermediate layer 132 may transfer the transparent electrode layer 150 to the transparent substrate 110 while protecting the transparent electrode layer 150.

The intermediate layer 132 may include an organic polymer film, and as non-limiting examples, a polyimide polymer, a polyvinyl alcohol polymer, a polyamic acid polymer, a polyamide ( polyamide) polymer, polyethylene polymer, polystylene polymer, polynorbornene polymer, phenylmaleimide copolymer polymer, polyazobenzene polymer, polyphenyl Polyphenylenephthalamide polymer, polyester polymer, polymethyl methacrylate polymer, polyarylate polymer, cinnamate polymer, coumarin It may include polymers, phthalimidine polymers, chalcone polymers, aromatic acetylene polymers, and the like. These may be used alone or in combination of two or more.

For example, after forming the lower insulating layer 130 and the transparent electrode layer 150 including the intermediary layer 132 and the protective layer 134 on a carrier substrate (not shown), the carrier substrate is an intermediary layer ( 132). Thereafter, the transparent substrate 110 may be bonded to the peeling surface of the intermediate layer 132 through the adhesive layer 120.

For example, the thickness of the intermediate layer 132 may be about 5 to 1,000 nm, preferably about 50 to 500 nm, as a non-limiting example. For example, the refractive index of the lower insulating layer 130 may be about 1.48 to 1.58.

For example, the intermediate layer 132 is easily peeled off from the carrier substrate, so that cracks in the transparent electrode structure 100 do not occur during peeling, the peeling force on the carrier substrate is about 0.01 to 0.2 N/25 mm Can be

As described above, after forming the lower insulating layer 130 and the transparent electrode layer 150 on the carrier substrate, the transparent electrode structure ( 100) can be obtained. Accordingly, it is possible to prevent the transparent substrate 110 from being damaged by a high-temperature deposition process such as a sputtering process performed when the transparent electrode layer 150 is formed, and a thinner transparent substrate 110 can be used, so that the thin transparent The electrode structure 100 and the electric device can be easily implemented.

The protective layer 134 may include, for example, an organic insulating material. For example, the protective layer 134 may cover at least a part of the side of the intermediate layer 132 to minimize exposure of the side of the intermediate layer 132 to an etchant during a process such as patterning of electrode patterns. . In terms of completely blocking exposure of the side surfaces of the mediation layer 132, the protective layer 134 may cover all sides of the mediation layer 132.

For example, the thickness of the protective layer 134 is preferably about 1 to 10 μm, preferably 1 to 3 μm, in terms of securing chemical resistance and flexibility. For example, the refractive index of the protective layer 134 may be about 1.48 to 1.58.

The surface energy of the lower insulating layer 130 may be about 30 to 80 mN/m, preferably about 40 to 70 mN/m. For example, the surface energy of the intermediate layer 132 to which the adhesive agent is applied may be about 30 to 80 mN/m, preferably about 40 to 70 mN/m.

When the surface energy of the lower insulating layer 130 is less than about 30 mN/m, the wettability is low, and the adhesive is not applied smoothly when the adhesive layer 120 is formed, so that the thickness of the adhesive layer 120 may be increased, and the surface energy is reduced. When it exceeds about 80 mN/m, the wettability is high, and the adhesive strength of the pressure-sensitive adhesive layer 120 may be lowered.

For example, as a non-limiting example, the surface energy value of the lower insulating layer 130 may be adjusted to the above range through a surface treatment method such as plasma, corona, saponification, or adjusting the content of the composition included in the lower insulating layer 120. Can be adjusted.

The adhesive layer 120 may adhere the transparent substrate 110 and the lower insulating layer 130, and may include air bubbles 122. The area ratio of the area in which the air bubbles 122 formed in the adhesive layer 120 are distributed may be about 2 to 35% of the area of the upper surface of the adhesive layer 120 when projected in the planar direction.

For example, in the above range, the adhesive layer 120 can improve the light efficiency of the transparent electrode structure 100 while maintaining excellent adhesion between the lower insulating layer 130 and the transparent substrate 110.

For example, when the area ratio of the area in which the air bubbles 122 are distributed is less than about 2% of the upper surface area of the adhesive layer 120, the total reflection prevention effect is insignificant, and when it exceeds about 35%, the adhesive layer 20 The adhesion of the may be deteriorated.

According to exemplary embodiments, the air bubbles 122 are at least one of the lower interface of the adhesive layer 120 adjacent to the transparent substrate 110 and the upper interface of the adhesive layer 120 adjacent to the lower insulating layer 130. Can be formed in In this case, since the air bubbles 122 are formed at the upper or lower interface of the adhesive layer 120, not inside the adhesive layer 120, the durability of the adhesive layer 120 due to the air bubbles 122 can be effectively prevented from deteriorating. have.

For example, the air bubbles 122 may be formed only at the lower interface of the adhesive layer 120 adjacent to the transparent substrate 110. For example, the air bubbles 122 may be formed only at the upper interface of the adhesive layer 120 adjacent to the lower insulating layer 130. In this case, bubbles 122 may be finely present on the interface where the bubbles 122 are not formed. When the area ratio of the area to the area of the upper surface of the adhesive layer of the bubbles 122 is 0.2% or less, the bubbles 122 are not formed. I don't see it.

According to some embodiments, the air bubbles 122 may be distributed together at a lower interface of the adhesive layer 120 adjacent to the transparent substrate 110 and an upper interface of the adhesive layer 120 adjacent to the lower insulating layer 130. . In this case, the air bubbles 122 are dispersed at each interface of the adhesive layer 120 to minimize a decrease in adhesion force due to the formation of the air bubbles 122.

According to exemplary embodiments, the diameter of the air bubbles 122 may be about 0.025 to 2.5 μm. Within the above range, the adhesive layer 120 may improve the light efficiency of the transparent electrode structure 100 while maintaining excellent adhesion.

For example, when the diameter of the bubble 122 is less than about 0.025 μm, the total reflection prevention effect may be insignificant, and when it exceeds about 2.5 μm, the adhesive strength of the adhesive layer 120 by the large bubble 122 and Due to the decrease in durability, the defect rate of the transparent electrode structure 100 may increase.

According to exemplary embodiments, the haze value of the adhesive layer 120 measured according to JIS K7136 may be about 5 to 60%. In the above range, total reflection of light passing through the transparent electrode structure 100 may be suppressed, so that the light efficiency of the transparent electrode structure 100 may be further improved.

For example, the thickness of the adhesive layer 120 may be about 0.1 to 5 μm. In the above range, the durability of the transparent electrode structure may be excellent. For example, the refractive index of the adhesive layer 120 may be about 1.49 to 1.54.

According to exemplary embodiments, the surface energy value of the adhesive layer 120 may be, for example, about 20 to 70 mN/m, and preferably about 20 to 60 mN/m. If the surface energy value of the adhesive layer 120 is less than about 20 mN/m, the adhesive may not be applied smoothly, so the thickness of the adhesive layer 120 may become thick, and if it exceeds about 70 mN/m, the wettability of the adhesive agent This is high, so the adhesive force of the adhesive layer 120 may be lowered.

The surface energy value of the pressure-sensitive adhesive layer 120 may be implemented by controlling, for example, a component and content of the composition for forming the pressure-sensitive adhesive layer 120.

For example, the composition for forming the pressure-sensitive adhesive layer may include a pressure-sensitive adhesive composition including a photo-radical polymerizable compound, an acrylic oligomer, a photo-radical polymerization initiator, and the like.

Examples of the photo-radical polymerizable compound include ethyl acrylate, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl acrylate, isobutyl acrylate, allyl methacrylate, and 2-ethoxyethyl (meth)acrylate. )Acrylate, isodecyl (meth)acrylate, 2-dodecylthioethyl methacrylate, octyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, hydroxyethyl (meth)acrylate, hydroxy Propyl (meth)acrylate, hydroxybutyl (meth)acrylate, isooctyl (meth)acrylate, isodexyl (meth)acrylate, stearyl (meth)acrylate, tetrafurfuryl (meth)acrylate, phenoxy Monofunctional monomers such as cyethyl (meth)acrylate, octadecyl methacrylate, isobornyl (meth)acrylate, tetrahydrofuryl acrylate, and acryloylmorpholine; 1,3-butanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A-ethylene Glycol diacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid Di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, di(acryloxyethyl)isocyanurate, allylated cyclohexyldi(meth)acrylate, dimethyloldi Bifunctional monomers such as cyclopentane diacrylate, ethylene oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, and adamantane diacrylate; Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane Trifunctional monomers such as tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, and glycerol tri(meth)acrylate ; Tetrafunctional monomers such as diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; 5-functional monomers, such as propionic acid-modified dipentaerythritol penta (meth)acrylate; And hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipenta erythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

The acrylic oligomer may be an oligomer polymerized by including at least one kind of the photo-radical polymerizable compound.

As a non-limiting example of the photo-radical polymerization initiator, radical photoinitiators such as acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, and benzoinalkylether-based may be mentioned. These may be used alone or in combination of two or more.

For example, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, dimethoxy-2-phenylacetophenone, 3-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 4-chronolocetophenone, 4,4-dimethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-hydroxycyclophenylketone , 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl- 2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4-diaminobenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, anthraquinone, 2- Methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethyl Thioxanthone, 2,4-diethyl thioxanthone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzyl dimethyl ketal , Diphenyl ketone benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, fluorene, triphenylamine, carbazole, etc., but limited thereto. It does not become.

Commercially available products include Shiva's darocur 1173, darocur 4265, darocur BP, darocur TPO, darocur MBF, irgacure 184, irgacure 500, irgacure 2959, irgacure 754, irgacure 651, irgacure 369, irgacure 907, irgacure 819, irgacure 1300, irgacure 1300, irgacure 1300 irgacure 2022, irgacure 819DW, irgacure 2100, irgacure 784, irgacure 250, and the like. These may be used alone or in combination of two or more.

The photopolymerization initiator may be included in an amount of about 0.5 to 10 parts by weight based on 100 parts by weight of the photopolymerizable compound. When the content is within the above range, it has an appropriate curing speed and has excellent durability.

According to exemplary embodiments, an absolute value of the difference in surface energy between the lower insulating layer 130 and the adhesive layer 120 may be about 4 to 50 mN/m. According to exemplary embodiments, an absolute value of the difference in surface energy between the transparent substrate 110 and the adhesive layer 120 may be about 17 to 30 mN/m.

Within the above range, it is possible to more easily form bubbles of an appropriate number and size in the pressure-sensitive adhesive layer 120. Accordingly, the adhesive layer 120 can further improve the light efficiency of the transparent electrode structure 100 while maintaining excellent adhesive strength.

According to exemplary embodiments, the transparent electrode layer 150 includes a first transparent oxide electrode layer 152, a metal layer 154, and a second transparent oxide electrode layer 156 sequentially stacked on the lower insulating layer 130 It can contain structures.

The first transparent oxide electrode layer 152 and the second transparent oxide electrode layer 156 are indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), and aluminum-doped zinc oxide. Transparent conductive oxides such as (AZO), gallium-doped zinc oxide (GZO), zinc tin oxide (ZTO), indium gallium oxide (IGO), and tin oxide (SnO _{2) may be included.}

In some embodiments, the first transparent oxide electrode layer 152 and the second transparent oxide electrode layer 156 may include ITO or IZO.

The metal layer 154 is silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), palladium (Pd), chromium (Cr), titanium (Ti), tungsten (W), Niobium (Nb), tantalum (Ta), vanadium (V), iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), molybdenum (Mo), calcium (Ca) or Alloys thereof (eg, silver-palladium-copper (APC)). These may be used alone or in combination of two or more. The metal layer 154 may preferably include a silver alloy such as APC.

As described above, the metal layer 154 is included in the transparent electrode layer 150 to reduce resistance, so that, for example, the activation speed or reaction speed of the lighting device and the battery device may be improved. In addition, the overall flexibility of the transparent electrode layer 150 is secured through the metal layer 154 so that damage to the electrode can be prevented even when repeatedly folding or folding is applied.

By disposing the transparent oxide electrode layers 152 and 156 having relatively improved chemical resistance on the upper and lower surfaces of the metal layer 154, oxidation, corrosion, etc. due to external moisture and air penetration of the metal layer 154 can be prevented. . In addition, the transmittance of the transparent electrode layer 150 is improved by the transparent oxide electrode layers 152 and 156, so that the optical efficiency of the electric device may be improved.

According to exemplary embodiments, the refractive index of the transparent oxide electrode layers 152 and 156 may be adjusted in a range of about 1.7 to 2.2 to reduce reflection through refractive index matching with the metal layer 154. For example, in the case of ITO, the refractive index may be adjusted through a sputtering process using a target in which a weight ratio of _{indium oxide (In 2} O ₃ ) and tin oxide (SnO _{2) is adjusted.} For example, the refractive index of the metal layer 154 may be about 0.1 to 1.

The metal layer 154 may be formed to have a thickness smaller than the thickness of each of the first and second transparent oxide electrode layers 152 and 156 to improve transmittance.

In some embodiments, each of the first and second transparent oxide electrode layers 152 and 156 may have a thickness of about 200 to 800 Å, preferably about 300 to 500 Å. In some embodiments, the thickness of the metal layer 154 may be about 50 to 500 Å, preferably about 80 to 150 Å.

In the thickness range, the effect of suppressing reflectance and improving transmittance may be more effectively implemented by combining with the value of Equation 1 described above.

In one embodiment, a protective film such as an encapsulation film or a release film may be formed on the transparent electrode layer 150.

As described above, in the transparent electrode layer 150, by including the transparent oxide electrode layers 152 and 156 together with the metal layer 154, it is possible to prevent damage due to moisture and air while utilizing the low resistance characteristics of the metal layer 154. I can.

According to example embodiments, the barrier layer 140 may be disposed between the lower insulating layer 130 and the transparent electrode layer 150. The barrier layer 140 shields external moisture and external air penetrating the transparent electrode layer 150, thereby further improving mechanical and chemical stability of the transparent electrode layer 150.

In some embodiments, the moisture permeability of the barrier layer 140 may be in the range ^{of 10 -3} g/m ^{2 ·24 hr or less at 40 o} C and 90% relative humidity ^{, and preferably 10 -5} g/m ^It may be in the range of 2 · 24 hours or less. In the above range, the transparent electrode structure 100 can be more easily applied to an electrical device such as a solar cell or a lighting device.

For example, the barrier layer 140 may include a barrier material having improved moisture shielding ability.

According to exemplary embodiments, the barrier material is indium-tin oxide (ITO), aluminum oxide (eg, Al ₂ O ₃ ), zinc oxide (eg, ZnO), aluminum oxide (eg, Al ₂ O ₃ )-zinc oxide (eg, ZnO) composite (AZO) material, silazne, siloxane, and/or silicon-containing inorganic material.

"Silazane" is used as a term encompassing a compound or polymer comprising a "-Si-N-Si-" structure. "Siloxane" is used as a term encompassing a compound or polymer comprising a "-Si-O-Si-" structure.

Examples of the silicon-containing inorganic material include silicon oxide, silicon nitride and/or silicon oxynitride. These may be used alone or in combination of two or more. Preferably, at least two or more of silicon oxide, silicon nitride, or silicon oxynitride are used together, and more preferably, silicon oxide, silicon nitride, and silicon oxynitride may be used together.

The barrier layer 140 may have a single-layer or multi-layer structure including the above-described barrier material. For example, the thickness of the barrier layer 140 may be about 50 to 350 nm. For example, the refractive index of the barrier layer 140 may be about 1.6 to 2.2.

According to some exemplary embodiments, the transparent electrode structure 100 may further include an upper protective layer 136 positioned between the barrier layer 140 and the transparent electrode layer 150.

The upper protective layer 136 may itself serve as a substrate and a passivation layer. In addition, corrosion of the transparent pattern layer 150 can be prevented. In addition, it can serve as an adhesive layer.

The upper protective layer 136 may be formed of a single layer or a plurality of layers of two or more layers.

For example, when the upper protective layer 136 serves as a substrate, silicone-based polymers such as polydimethylsiloxane (PDMS) and polyorganosiloxane (POS); Polyimide polymer; It may be made of a polyurethane-based polymer, but is not limited thereto. These may be used alone or in combination of two or more.

For example, the upper protective layer 136 is a non-limiting example, and may be formed using a metal oxide such as silicon oxide, a photosensitive resin composition including an acrylic resin, a thermosetting resin composition, or an inorganic material such as silicon oxide (SiOx). In this case, it can be formed by vapor deposition or sputtering.

For example, when the upper protective layer 136 serves as an adhesive layer, for example, the upper protective layer 136 may include a thermosetting or photocurable adhesive. For example, it may include a heat-curable or photo-curable adhesive agent such as polyester-based, polyether-based, urethane-based, epoxy-based, silicone-based, and acrylic-based.

The thickness of the upper protective layer 136 is, for example, about 1 to 10 μm, preferably about 1 to 3 μm, in terms of securing corrosion, flatness, and flexibility.

2 is a schematic cross-sectional view illustrating an electric device to which a transparent electrode structure according to exemplary embodiments is applied. For example, FIG. 2 illustrates a lighting device including a transparent electrode structure according to the above-described exemplary embodiments.

Referring to FIG. 2, the lighting device 200 may include a light emitting layer 160 and an upper electrode 170 sequentially stacked on the above-described transparent electrode structure 100.

The light-emitting layer 160 may include, for example, an organic light-emitting material known in the art. In this case, the lighting device 200 may be provided as an OLED lighting device.

In one embodiment, a hole transport layer (HTL) may be further included between the transparent electrode layer 150 and the light emitting layer 160. In an embodiment, an electron transport layer (ETL) may be further included between the light emitting layer 160 and the upper electrode 170.

For example, the transparent electrode layer 150 may be provided as an anode of the lighting device 200, and the lighting device 200 may be a bottom-emission type that emits light through the transparent substrate 110. . In this case, the upper electrode 170 may be provided as a cathode and a reflective electrode of the lighting element 200.

3 is a schematic cross-sectional view illustrating an electric device to which a transparent electrode structure is applied according to example embodiments. For example, FIG. 3 shows a battery device such as a solar cell including a transparent electrode structure according to the above-described exemplary embodiments.

Referring to FIG. 3, the battery device 300 may include a photo-active layer 180 and an upper electrode 190 sequentially stacked on the above-described transparent electrode structure 100. The photoactive layer 180 may include, for example, a light absorbing layer including an organic polymer known in the art included in a solar cell.

In an embodiment, a hole transport layer may be further included between the transparent electrode layer 150 and the photoactive layer 180.

In one embodiment, the transparent electrode layer 150 may be provided as an anode of the battery element 300, and the upper electrode 190 may be provided as a cathode of the battery element 300.

Hereinafter, preferred embodiments are presented to aid in understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and examples within the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such modifications and modifications fall within the appended claims.

Examples and Comparative Examples

On a 700 µm-thick soda lime glass, the composition shown in Table 1 was applied and cured so that the dry thickness was the corresponding thickness to form a lower insulating layer.

Thereafter, 15 parts by weight of Soken Chemical Co., Ltd. ZAH-115 as a polymer resin, 4 parts by weight of urea hardener as a curing agent, 0.5 parts by weight of DIC company F-554 as an additive, and 0.5 parts by weight of Shin-Etsu Corporation KBM-403 as a solvent, propylene glycol monomethyl ether A protective layer-forming composition containing 60 parts by weight of acetate and 20 parts by weight of propylene glycol monomethyl ether was applied on the lower insulating layer and cured at 180 Ž for 30 minutes to form a 2 µm-thick first protective layer. I did.

Thereafter, an ITO layer was formed to a thickness of 0.05 μm on the first protective layer by a vacuum deposition method, and then a photosensitive photoresist was applied on the ITO layer, exposed, developed, and etched to form an electrode pattern layer.

Thereafter, the glass substrate was peeled from the lower insulating layer and the upper stacked material in a temperature environment of 25°C, and an adhesive layer of Table 1 was formed under the lower insulating layer, and the transparent substrate of Table 1 was bonded to the lower portion of the adhesive layer Thus, a transparent electrode structure was manufactured.

The transparent substrate was treated with a KOH concentration of 4.5N, a liquid temperature of 45°C, and a treatment time of 65 seconds to make the surface energy 74mN/m, a KOH concentration of 4.5N, a liquid temperature of 45°C, and a treatment time of 95 seconds to obtain a surface energy of 85mN/m. .

The surface energy values of the lower insulating layer (A), the adhesive layer (B), and the transparent substrate (C) were measured using a contact angle measuring instrument DSA 100, and then respectively described in Table 1.

division Lower insulating layer (A) Adhesive layer (B) Transparent substrate (C) ingredient thickness
(㎛) Surface energy
(mN/m) ingredient thickness
(㎛) Surface energy
(mN/m) Kinds thickness
(㎛) Surface energy
(mN/m) Example 1 A-4 0.3 33 B-1 7 57 TAC 20 74 Example 2 A-3 0.3 74 B-1 2 28 TAC 20 74 Example 3 A-2 0.1 45 B-1 One 57 TAC 20 74 Example 4 A-5 0.3 25 B-1 2 57 TAC 20 74 Example 5 A-1 0.3 53 B-2 2 85 TAC 20 74 Example 6 A-3 0.3 74 B-1 2 57 TAC 20 74 Example 7 A-2 0.1 45 B-1 2 57 TAC 20 74 Example 8 A-1 0.3 53 B-1 2 57 TAC 80 85 Example 9 A-4 0.3 33 B-1 2 28 TAC 20 74 Example 10 A-2 0.1 45 B-2 2 85 TAC 80 85 Comparative Example 1 A-1 0.3 53 B-1 2 57 TAC 20 74 Comparative Example 2 A-1 0.9 53 B-1 4 57 TAC 20 74 Comparative Example 3 A-3 0.5 91 B-1 4 43 TAC 20 74 Comparative Example 4 A-5 0.1 17 B-1 7 69 TAC 80 85 Comparative Example 5 A-2 0.2 46 B-1 4 43 TAC 20 74 Comparative Example 6 A-1 0.2 55 B-1 7 58 TAC 20 74 A-1: Polyarylate (Unitica, M-2000H) 5%, solvent cyclohexanone 95%
A-2: Polyarylate (Unitica, M-2040) 5%, solvent cyclohexanone 95%
A-3: Polyamic acid (Chemfield, T-100) 1%, solvent dimethylacetamide 99%
A-4: Polymethyl methacrylate (Microchem, 495 PMMA A4)
A-5: Polystyrene (Aldrich I, Mw35,000) 3%, solvent toluene 97%
B-1: UV-NS063 (Japanese synthetic)
B-2: MA21 (Meisho)
B-3: SKA-BL80 (Shinkwang Chemical Industry)

Experimental example. Evaluation of the brightness improvement rate according to the difference in surface energy

Bubble area ratio measurement

The transparent electrode structures of Examples and Comparative Examples were observed with an optical microscope with a magnification of 100 times, and the area of the area occupied by the bubbles was calculated, and then the area ratio of the bubbles was calculated by dividing the area by the total area of the adhesive layer. The calculation results are shown in Table 2, and FIG. 4 shows an optical micrograph of Example 4 having a bubble area of 12.6.

Haze evaluation

The Haze value of the adhesive layer included in the transparent electrode structures of Examples and Comparative Examples was measured according to JIS K7136. Table 2 shows the measurement results.

Evaluation of luminance improvement rate

Using the spectrometer CAS-140, the luminance of the transparent electrode structures of Examples and Comparative Examples was measured. Based on Comparative Example 1, the luminance improvement rates of Examples and Comparative Examples were calculated and shown in Table 2.

Adhesion evaluation

After the pressure-sensitive adhesive layer was allowed to stand at 23° C. and a relative humidity of 55% for 24 hours, the adhesiveness was evaluated to the extent that the blade entered when the blade of the cutter was pushed between the base films.

◎: The cutter blade does not fit between the bonded films

○: The cutter blade enters 2 mm or less between the bonded films

△: The cutter blade enters between the bonded films in a range of more than 2 mm to less than 5 mm

×: The blade of the cutter enters the bonded film to the end without difficulty

division Surface energy difference Evaluation results ｜Lower Insulation Layer- Adhesive Adhesive Layer｜ ｜Transparent materials-
Adhesive layer｜ bubble
area
ratio Haze
(%) Luminance
Improvement rate Adhesion Example 1 24 17 26.4 37 8.25 ○ Example 2 46 17 32.2 58.2 10.32 ○ Example 3 12 17 11.3 28.6 7.12 ◎ Example 4 32 17 12.6 31.2 9.67 ○ Example 5 32 17 9.24 33.3 8.05 ◎ Example 6 17 17 3.6 16.2 6.32 ◎ Example 7 12 17 2.12 8.3 3.21 ◎ Example 8 4 28 10.3 23.2 6.82 ◎ Example 9 5 47 14.1 40.1 10.01 ○ Example 10 40 0 12.1 38.4 9.96 ○ Comparative Example 1 4 17 0.5 0.2 0 ◎ Comparative Example 2 4 17 0.6 0.4 0 ◎ Comparative Example 3 51 31 50 78 2.01 X Comparative Example 4 51 16 40 71 5.21 X Comparative Example 5 3 31 36 61 7.02 X Comparative Example 6 3 16 0.2 0.3 0 ◎

Referring to Table 2, in the case of the examples having a bubble area ratio of 2 to 35%, the light efficiency of the transparent electrode structure was superior to that of the comparative examples having a bubble area of less than 2%.

100: transparent electrode structure 110: transparent substrate
120: adhesive layer 122: air bubbles
130: lower insulating layer 132: intermediate layer
134: protective layer 136: upper protective layer
140: barrier layer 150: transparent electrode layer
152: first transparent oxide electrode layer 154: metal layer
156: second transparent oxide electrode layer

Claims (14)

Transparent substrate;
A lower insulating layer formed on the transparent substrate;
A transparent electrode layer stacked on the lower insulating layer; And
It is formed between the transparent substrate and the lower insulating layer and includes a point-adhesive layer including bubbles, and when projected from a plane direction, the ratio of the area of the area where the bubbles are distributed is 2 to 35 compared to the area of the upper surface of the point-of-contact layer. %, the transparent electrode structure.
The transparent electrode structure of claim 1, wherein the air bubbles are distributed on at least one of a lower interface of an adhesive layer adjacent to the transparent substrate and an upper interface of an adhesive layer adjacent to the lower insulating layer.
The transparent electrode structure of claim 2, wherein the air bubbles are distributed together at a lower interface of an adhesive layer adjacent to the transparent substrate and an upper interface of an adhesive layer adjacent to the lower insulating layer.
The transparent electrode structure according to claim 1, wherein each diameter of the air bubbles is 0.025 to 2.5 μm.
The transparent electrode structure according to claim 1, wherein the haze value of the pressure-sensitive adhesive layer measured according to JIS K7136 is 5 to 60%.
The transparent electrode structure according to claim 1, wherein an absolute value of a difference in surface energy between the lower insulating layer and the adhesive layer is 4 to 50 mN/m.
The transparent electrode structure according to claim 1, wherein an absolute value of a difference in surface energy between the transparent substrate and the adhesive layer is 17 to 30 mN/m.
The transparent electrode structure of claim 1, further comprising a barrier layer disposed between the lower insulating layer and the transparent electrode layer.
The method according to claim 8, wherein the barrier layer is made of indium-tin oxide (ITO), aluminum oxide, zinc oxide, aluminum oxide-zinc oxide composite (AZO) material, silazane, siloxane, and silicon-containing inorganic material. A transparent electrode structure comprising at least one barrier material selected from the group consisting of.
The transparent electrode structure according to claim 8, wherein the barrier layer has a moisture permeability of 10 ^-3 g/m ^{2 24 hr or less under a condition of 40° C. and 90% relative humidity.}
The transparent electrode structure according to claim 1, wherein the lower insulating layer comprises an intermediary layer and a protective layer sequentially stacked from the adhesive layer.
The transparent electrode structure of claim 1, wherein the transparent electrode layer comprises a first transparent oxide electrode layer, a metal layer, and a second transparent oxide electrode layer sequentially stacked.
The transparent electrode structure of claim 1;
An organic emission layer disposed on the transparent electrode structure; And
A lighting device comprising an upper electrode disposed on the organic emission layer.
The transparent electrode structure of claim 1;
A photoactive layer disposed on the transparent electrode structure; And
A solar cell comprising an upper electrode disposed on the photoactive layer.

Images