KR20140068547A - Organic light emitting display device and method for manufacturing of the same - Google Patents

Abstract

According to an embodiment of the present invention, an organic electroluminescent light emitting display device includes: a substrate; an organic light emitting diode which is located on the substrate and includes a first electrode, an organic film layer, and a second electrode; and a barrier which covers the organic light emitting diode. The barrier is a silicon oxide film formed with polysilazane mixed with inorganic nanoparticles.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent display device,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to an organic light emitting display device and a method of manufacturing the same, and more particularly, to an organic light emitting display device and a method of manufacturing the same.

2. Description of the Related Art In recent years, the importance of flat panel displays (FPDs) has been increasing with the development of multimedia. In accordance with this, a liquid crystal display (LCD), a plasma display panel (PDP), a field emission display (FED), an organic light emitting display device Various flat-panel displays have been put into practical use.

Particularly, the organic light emitting display device has a response speed of 1 ms or less, a high response speed, low power consumption, and self light emission. In addition, there is no problem in the viewing angle, which is advantageous as a moving picture display medium regardless of the size of the apparatus. In addition, since it can be manufactured at a low temperature and the manufacturing process is simple based on the existing semiconductor process technology, it is attracting attention as a next generation flat panel display device.

Conventionally, an organic light emitting display has been manufactured by forming an organic light emitting diode including a first electrode, an organic layer, and a second electrode on a substrate, sealing the sealing substrate made of glass or metal and the substrate with an adhesive. However, the organic electroluminescent display device is difficult to realize a thin shape by use of an encapsulating substrate, and has a problem of poor durability.

Recently, organic light emitting display devices are manufactured by stacking a plurality of thin films such as an inorganic film and an organic film on an organic light emitting diode and sealing them. However, it takes a long time to laminate the inorganic film and the organic film alternately, and the structure becomes complicated. Further, there is a problem that particles are generated in the process of vapor deposition of an inorganic film using a low-temperature PECVD method, thereby providing a moisture infiltration path by the particles.

The present invention provides an organic electroluminescent display device and a method of manufacturing the same that prevent deterioration of devices due to moisture permeation and are easy to process.

According to an aspect of the present invention, there is provided an organic light emitting display including a substrate, an organic light emitting diode (OLED) disposed on the substrate and including a first electrode, an organic layer, and a second electrode, And a barrier covering the light emitting diode, wherein the barrier is a silicon oxide film formed of polysilazane mixed with inorganic nanoparticles.

Wherein the polysilazane is a perhydro polysilazane.

The inorganic nanoparticles may be at least one selected from the group consisting of metal oxide, silica, and clay.

And the inorganic nanoparticles are surface-treated with a coupling agent.

And the inorganic nanoparticles are contained in an amount of 0.1 to 10 wt% based on 100 wt% of the polysilazane.

And the distance from the side surface of the organic light emitting diode to the barrier is longer than the distance from the top surface of the organic light emitting diode to the barrier.

The distance from the side of the organic light emitting diode to the barrier is equal to the distance from the top surface of the organic light emitting diode to the barrier.

According to another aspect of the present invention, there is provided a method of fabricating an organic light emitting display, including: forming an organic light emitting diode including a first electrode, an organic layer, and a second electrode on a substrate; And oxidizing the polysilazane mixed with the inorganic nanoparticles on the substrate to form a barrier which is a silicon oxide film.

And the barrier is formed by applying a solution in which the polysilazane and the inorganic nanoparticles are mixed on the substrate.

And aligning the mask on the substrate on which the organic light emitting diode is formed, before applying the mixed solution of the polysilazane and the inorganic nanoparticles.

The mask may have an opening exposing an area where the organic light emitting diode is formed.

And the inorganic nanoparticles are surface-treated with a coupling agent.

And the inorganic nanoparticles are contained in an amount of 0.1 to 10 wt% based on 100 wt% of the polysilazane.

An organic light emitting display device and a method of manufacturing the same according to an exemplary embodiment of the present invention can form a barrier using a polysilazane mixed with inorganic nanoparticles on an organic light emitting diode, Can be manufactured.

In addition, by forming the barrier including the inorganic nanoparticles, it is possible to prevent the external moisture and oxygen from penetrating into the organic light emitting diode. Furthermore, by applying a barrier by a solution process, and by forming a longer length on the side surface of the organic light emitting diode, there is an advantage that the penetration of moisture and oxygen on the side of the organic light emitting diode can be further prevented.

1 is a plan view showing an organic light emitting display according to an embodiment of the present invention.
2 is a sectional view of an organic light emitting display according to an embodiment of the present invention, taken along line I-I 'of FIG.
3 and 4 are cross-sectional views illustrating an organic light emitting display device according to another embodiment of the present invention.
5A to 5D are cross-sectional views illustrating a method of manufacturing an organic light emitting display according to an exemplary embodiment of the present invention.
6 is a graph showing the measurement of the moisture permeability of a barrier fabricated according to an embodiment of the present invention.
7 is a diagram illustrating the surface of a barrier fabricated in accordance with an embodiment of the present invention.
8 is a cross-sectional view of a barrier fabricated in accordance with an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a plan view showing an organic light emitting display according to an embodiment of the present invention, FIG. 2 is a cross-sectional view illustrating an organic light emitting display according to an embodiment of the present invention, taken along line I-I ' And FIGS. 3 and 4 are cross-sectional views illustrating an organic light emitting display device according to another embodiment of the present invention.

1 and 2, an organic light emitting display device 10 according to an embodiment of the present invention includes an organic light emitting diode 200 disposed on a substrate 100, a barrier 200 covering the organic light emitting diode 200, (300).

More specifically, the organic light emitting diode 200 is located on the substrate 100. The substrate 100 may be made of glass, plastic, or a transparent substrate made of a conductive material. An organic light emitting diode 200 including a first electrode 210, an organic layer 230 and a second electrode 240 is disposed on the substrate 100.

The first electrode 210 may be an anode, and may be a transparent electrode or a reflective electrode. When the first electrode 210 is a transparent electrode, the first electrode 210 may be one of indium tin oxide (ITO), indium zinc oxide (IZO), and zinc oxide (ZnO). When the first electrode 210 is a reflective electrode, the first electrode 210 may be formed of one of aluminum (Al), silver (Ag), and nickel (Ni) under the layer of any one of ITO, IZO, And may further include a reflective layer made of any one of them and may include the reflective layer between two layers made of any one of ITO, IZO and ZnO.

The first electrode 210 may be formed using a sputtering method, an evaporation method, a vapor phase deposition method, or an electron beam deposition method.

An insulating layer 220 is formed on the substrate 100 on which the first electrode 210 is formed to expose a part of the first electrode 210. The insulating layer 220 may include organic materials such as benzocyclobutene (BCB) resin, acrylic resin or polyimide resin, but is not limited thereto.

The organic layer 230 is positioned on the first electrode 210 exposed by the insulating layer 220. The organic layer 230 may include at least a light emitting layer and may further include a hole injecting layer, a hole transporting layer, an electron transporting layer, or an electron injecting layer on the upper or lower portion of the light emitting layer.

The hole injection layer may function to smoothly inject holes from the first electrode 210 into the light emitting layer, and may be formed of at least one of cupper phthalocyanine, PEDOT (poly (3,4) -ethylenedioxythiophene), PANI (polyaniline) And NPD (N, N-dinaphthyl-N, N'-diphenyl benzidine), but the present invention is not limited thereto.

The hole transport layer plays a role of facilitating the transport of holes, and it is preferable to use a hole transport layer such as NPD (N-dinaphthyl-N, N'-diphenyl benzidine), TPD (N, N'- -bis- (phenyl) -benzidine), s-TAD and 4,4 ', 4 "-tris (N-3-methylphenyl-N- phenylamino) -triphenylamine But is not limited thereto.

The light emitting layer may be formed of a material that emits red, green, and blue light, and may be formed using phosphorescent or fluorescent materials.

When the light emitting layer is red, it includes a host material including CBP (carbazole biphenyl) or mCP (1,3-bis (carbazol-9-yl) , PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium) and PtOEP (octaethylporphyrin platinum) Alternatively, it may be made of a fluorescent material including PBD: Eu (DBM) ₃ (Phen) or Perylene, but not limited thereto.

And a phosphorescent material including a dopant material including Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium), which includes a host material including CBP or mCP when the light emitting layer is green, Alternatively, it may include, but is not limited to, a fluorescent material containing Alq3 (tris (8-hydroxyquinolino) aluminum).

(4,6-F ₂ ppy) ₂ Irpic when the emissive layer is blue, and a host material comprising CBP or mCP. Alternatively, the phosphorescent material may comprise a spiro- But is not limited to, a fluorescent material including any one selected from the group consisting of DPVBi, spiro-6P, distyrylbenzene (DSB), distyrylarylene (DSA), PFO polymer and PPV polymer.

The electron transport layer plays a role of facilitating transport of electrons and may be composed of at least one selected from the group consisting of Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq and SAlq It is not limited.

The electron transport layer may also prevent holes injected from the first electrode from passing through the light emitting layer to the second electrode. In other words, it plays a role of a hole blocking layer and plays a role of efficient bonding of holes and electrons in the light emitting layer.

The electron injection layer plays a role of injecting electrons smoothly. Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq or SAlq may be used.

The electron injection layer may further include an inorganic material, and the inorganic material may further include a metal compound. The metal compound may include an alkali metal or an alkaline earth metal. Metal compound containing the alkali metal or alkaline earth metal is LiQ, LiF, NaF, KF, RbF, CsF, FrF, BeF 2, MgF 2, CaF 2, SrF 2, BaF any one selected from ₂ the group consisting of RaF ₂ But is not limited thereto.

The second electrode 240 may be a cathode electrode and may be made of magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), or an alloy thereof having a low work function. Here, the second electrode 240 may be formed to have a thickness thin enough to transmit light when the organic light emitting display device has a front or both-side light emitting structure. When the organic light emitting display device has a back light emitting structure, It can be formed thick enough to reflect light.

A barrier 300 covering the organic light emitting diode 200 is located. The barrier 300 may prevent external moisture or air from penetrating and may protect the organic light emitting diode 200 from external impact. The barrier 300 may be a silicon oxide film formed by oxidizing the polysilazane mixed with the inorganic nanoparticles 310.

The polysilazane used in the present invention reacts with water and oxygen in the atmosphere to cause oxidation to form silicon oxide (SiO ₂ ). As the chain length bonded to the polysilazane becomes longer, the oxidation reaction proceeds slowly do. The polysilazane can be the most rapid perhydropolysilazane. When the polysilazane is formed of a silicon oxide film, it has a hydrophobic functional group to prevent water from penetrating into the silicon oxide film. Here, the hydrophobic functional group may be any one selected from the group consisting of an alkyl group, a vinyl group, a hydrocarbon group such as a cycloalkyl group, and a fluoro group.

In addition, the barrier 300 of the present invention includes inorganic nanoparticles 310 dispersed in a barrier 300, which is a silicon oxide film, formed by mixing inorganic nanoparticles 310 with polysilazane to form a silicon oxide film. The inorganic nanoparticles 310 are for preventing external moisture and oxygen from penetrating the barrier 300 and include at least one selected from the group consisting of metal oxide, silica, and clay. Here, aluminum oxide (Al ₂ O ₃ ) may be used as the metal oxide.

When the inorganic nanoparticles 310 are simply mixed with the polysilazane, the oxidation of the polysilazane is promoted by a hydroxyl group (-OH) present on the surface of the inorganic nanoparticles 310 and gas may be generated. Thus, inorganic nanoparticles 310 are surface treated with a coupling agent before mixing with the polysilazane. Here, as the coupling agent, a silane coupling agent such as an alkylalkoxy silane system, an amino silane system, or an epoxy silane may be used.

The inorganic nanoparticles 310 may be contained in a proportion of 0.1 to 10 wt% based on 100 wt% of the polysilazane. When inorganic nanoparticles 310 are contained in an amount of 0.1 wt% or more based on 100 wt% of polysilazane, the moisture permeability, which is a characteristic of blocking external moisture and oxygen, The inorganic nanoparticles 310 can prevent cracks from occurring in the thin film of the barrier film 300 and deterioration of the film quality.

As shown in FIG. 2, the barrier 300 of the present invention may be formed as a thin layer on the organic light emitting diode 200, and may be formed of passivation that protects the upper part from other structures or external impacts. 3, a passivation film 280 is separately formed on the organic light emitting diode 200, and a barrier 300 is formed to be thick, so that the sealing film 280, which encapsulates the organic light emitting diode 200, ≪ / RTI >

The barrier 300 of the present invention is formed such that the distance D1 from the side surface of the organic light emitting diode 200 to the barrier 300 is less than the distance D2 from the top surface of the organic light emitting diode 200 to the barrier 300 . The organic electroluminescent display device is vulnerable to penetration of moisture and oxygen in the lateral direction of the organic light emitting diode 200 than in the top surface direction. The distance D1 from the side of the organic light emitting diode 200 to the barrier 300 is greater than the distance D2 from the top surface of the organic light emitting diode 200 to the barrier 300. [ It is possible to prevent penetration of moisture and oxygen from the side surface of the organic light emitting diode 200. The distance D1 from the side surface of the organic light emitting diode 200 to the barrier 300 is greater than the distance D1 from the top surface of the organic light emitting diode 200 to the barrier 300. [ May be formed to be the same as the distance D2.

3, a sealant 410 is applied to an upper portion of the barrier 300 and a seal substrate 410 made of a glass substrate is formed. 400). ≪ / RTI > The present invention is not limited to the barriers of the structures shown in FIGS. 2 to 4, and any structure can be applied as long as it covers the organic light emitting diode.

Hereinafter, a method of manufacturing the organic light emitting display device will be described with reference to the accompanying drawings. Hereinafter, the manufacturing method of the structure of the organic light emitting display device described with reference to FIG. 4 will be described with the same reference numerals.

5A to 5D are cross-sectional views illustrating a method of manufacturing an organic light emitting display according to an exemplary embodiment of the present invention.

5A, one of indium tin oxide (ITO), indium zinc oxide (IZO), and zinc oxide (ZnO) is deposited on a transparent substrate 100 made of glass, plastic, 210 are formed. Next, a benzocyclobutene (BCB) resin, an acrylic resin, or a polyimide resin is applied on the first electrode 210 by a spin coating method or a screen pouring method and patterned by photolithography to form a first electrode The insulating layer 220 exposing a part of the insulating layer 220 is formed.

Next, a material emitting red, green or blue light is deposited on the first electrode 210 exposed by the insulating layer 220 to form an organic layer 230 including at least a light emitting layer. Further, a hole injecting layer, a hole transporting layer, an electron transporting layer, or an electron injecting layer may be further formed on the upper or lower part of the light emitting layer. Next, magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), or an alloy thereof is deposited on the substrate 100 including the organic layer 230 to form the second electrode 240 Thereby forming the organic light emitting diode 200.

The mask 450 having an opening OP exposing an area where the organic light emitting diode 200 is formed on the substrate 100 on which the organic light emitting diode 200 is formed is aligned. The mask 450 has a frame shape, and the opening OP exposes an area where the organic light emitting diode 200 is formed. The thickness of the barrier to be formed later is determined by adjusting the depth of the opening OP of the mask 450, and the width or length of the barrier is determined by adjusting the size of the opening OP.

Next, referring to FIG. 5B, a barrier solution 460 in which polysilazane and inorganic nanoparticles 310 are mixed with a solvent is coated on the substrate 100 on which the mask 450 is arranged. Here, as the solvent, commonly used organic solvents such as toluene, xylene, benzene or methyl benzoate can be used. The solution thus prepared can be coated by spin coating, screen printing, slit coating, or the like, and slit coating is shown in this embodiment. At this time, the barrier solution 460 can be prevented from escaping to the outside by the mask 450 and coated on the substrate 100. The applied barrier solution 460 may be applied to a thickness up to the top surface of the maximum mask 450.

Referring to FIG. 5C, polysilazane in the applied barrier solution 460 reacts with moisture and oxygen in the atmosphere to be oxidized to form a barrier 300 of the silicon oxide film. The inorganic nanoparticles 310 mixed in the barrier solution 460 are dispersed in the barrier 300. When the barrier 300 is formed, the mask 450 is removed.

5D, a sealant 410 is applied to an entire surface of an encapsulation substrate 400 made of a glass substrate, and the encapsulation substrate 400 is bonded to the substrate 100 on which the barrier 300 is formed, thereby fabricating an organic light emitting display device .

As described above, the organic light emitting display device and the method for fabricating the same according to the embodiment of the present invention can prevent the formation of the barrier by using the polysilazane on the organic light emitting diode, can do.

In addition, there is an advantage that foreign moisture and oxygen can be prevented from penetrating into the organic light emitting diode by forming a barrier using polysilazane mixed with inorganic nanoparticles. Furthermore, by applying a barrier by a solution process, and by forming a longer length on the side surface of the organic light emitting diode, there is an advantage that the penetration of moisture and oxygen on the side of the organic light emitting diode can be further prevented.

Hereinafter, the barrier of the present invention will be described in detail in the following experimental examples. However, the following experimental examples are merely illustrative of the present invention, and the present invention is not limited to the following experimental examples.

Example

Aluminum oxide particles having a particle size of about 100 nm were mixed at 4 wt% in a solution of perhydrosilazane (manufactured by Yuka Chemical Co., solid content 19%, amine catalyst 1.5 wt%) and ultrasonicated for about 5 minutes. Then, the solution was spin-coated on a polyether sulfone (PES) substrate at 1500 rpm for 20 seconds and heat-treated at about 100 ° C for 2 hours to prepare a barrier.

The barrier prepared according to the above example was measured for water vapor transmission rate (WVTR) using Aquatran (MOCON) equipment, and the barrier surface was observed through an optical microscope to be shown in FIG. And the cross section of the barrier measured by SEM is shown in Fig.

Referring to FIG. 6, the permeation amount per unit area with time is about 60 g / m 2day in the case of PES substrate, while the moisture permeability of the barrier according to the present invention is about 0.0056 g / m 2day, . Also, as shown in Figs. 7 and 8, it was confirmed that there was no crack-like surface on the surface of the barrier, and the section was very clean, and the barrier property was excellent.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be practiced. It is therefore to be understood that the embodiments described above are to be considered in all respects only as illustrative and not restrictive. In addition, the scope of the present invention is indicated by the following claims rather than the detailed description. Also, all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

10: organic electroluminescence display device 100: substrate
200: organic light emitting diode 210: first electrode
230: organic film layer 240: second electrode
300: Barrier

Claims (13)

Board;
An organic light emitting diode (OLED) disposed on the substrate, the organic light emitting diode including a first electrode, an organic layer, and a second electrode; And
And a barrier covering the organic light emitting diode,
Wherein the barrier is a silicon oxide film formed of polysilazane mixed with inorganic nanoparticles.
The method according to claim 1,
Wherein the polysilazane is a perhydro polysilazane.
The method according to claim 1,
Wherein the inorganic nanoparticles are composed of at least one selected from the group consisting of metal oxide, silica, and clay.
The method of claim 3,
Wherein the inorganic nanoparticles are surface-treated with a coupling agent.
The method according to claim 1,
Wherein the inorganic nanoparticles are contained in an amount of 0.1 to 10 wt% based on 100 wt% of the polysilazane.
The method according to claim 1,
Wherein a distance from a side surface of the organic light emitting diode to the barrier is longer than a distance from an upper surface of the organic light emitting diode to the barrier.
The method according to claim 1,
Wherein a distance from a side surface of the organic light emitting diode to the barrier is equal to a distance from an upper surface of the organic light emitting diode to the barrier.
Forming an organic light emitting diode including a first electrode, an organic film layer, and a second electrode on a substrate; And
And oxidizing the polysilazane mixed with the inorganic nanoparticles on the substrate on which the organic light emitting diode is formed to form a barrier which is a silicon oxide film.
9. The method of claim 8,
Wherein the barrier is formed by applying a solution in which the polysilazane and the inorganic nanoparticles are mixed on the substrate.
10. The method of claim 9,
Further comprising the step of aligning the mask on the substrate on which the organic light emitting diode is formed before applying the mixed solution of the polysilazane and the inorganic nanoparticles.
11. The method of claim 10,
Wherein the mask has an opening exposing an area where the organic light emitting diode is formed.

9. The method of claim 8,
Wherein the inorganic nanoparticles are surface-treated with a coupling agent.
9. The method of claim 8,
Wherein the inorganic nanoparticles are contained in an amount of 0.1 to 10 wt% based on 100 wt% of the polysilazane.

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