KR101588298B1 - Organic light emitting display apparatus and the method for manufacturing the same - Google Patents

Abstract

An organic light emitting display device including a hybrid protective film is provided. The organic light emitting display includes a substrate, a display portion including the organic light emitting element on the substrate, and a sealing portion sealing the display portion and including a hybrid protective film. Wherein the hybrid protective film comprises a carbon-free inorganic partial layer, an organic partial layer having a constant carbon content, and a gradient portion interposed between the inorganic partial layer and the organic partial layer, Layer.

Description

[0001] The present invention relates to an organic light emitting display device and a method of manufacturing the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an organic light emitting display, and more particularly, to an organic light emitting display including a hybrid protective layer and a method of manufacturing the same.

The organic light emitting display includes a hole injecting electrode, an electron injecting electrode, and an organic light emitting device including an organic light emitting layer interposed therebetween, wherein holes injected from the hole injecting electrode and electrons injected from the electron injecting electrode Emitting display device in which an exciton generated by coupling in an organic light emitting layer falls from an excited state to a ground state to generate light.

Since an organic light emitting display device which is a self-emission type display device does not require a separate light source, it can be driven at a low voltage and can be configured as a light and thin type. Due to its high quality characteristics such as wide viewing angle, high contrast, And has been used in various products such as smart phones, touch panels, TVs, and aircraft displays.

However, since the organic light emitting display has a characteristic of being deteriorated by external moisture or oxygen, it is necessary to seal the organic light emitting element to prevent permeation of moisture or oxygen from the outside.

2. Description of the Related Art In recent years, in order to make the organic light emitting display thinner and / or flexible, it is necessary to use a plurality of inorganic films, a plurality of organic films or alternately stacked inorganic films and organic films Thin film encapsulation (TFE) composed of a plurality of layers is used. However, since the thin film encapsulation is formed of a plurality of layers, there is a problem in that, in order to increase the water or oxygen barrier performance, the thickness becomes thick and the manufacturing process is added to increase the manufacturing cost.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an organic light emitting diode (OLED) display device including a hybrid passivation layer exhibiting high moisture and oxygen barrier performance by applying a simple manufacturing process.

It is another object of the present invention to provide a method of manufacturing such an OLED display.

According to another aspect of the present invention, there is provided an organic light emitting display including a substrate, a display unit including the organic light emitting device on the substrate, and a sealing unit sealing the display unit and including a hybrid protection film. Wherein the hybrid protective film comprises a carbon-free inorganic partial layer, an organic partial layer having a constant carbon content, and a gradient portion interposed between the inorganic partial layer and the organic partial layer, Layer.

According to an embodiment of the present invention, the display unit includes a thin film transistor on the substrate, a pixel electrode connected to the thin film transistor, a pixel defining layer exposing at least a part of the pixel electrode and defining a light emitting region, An organic light emitting layer disposed on at least a part of the pixel electrode exposed by the film, and an opposing electrode disposed on the organic light emitting layer and the pixel defining layer.

According to another example of the OLED display device, the inorganic partial layer and the gradient partial layer may each have a constant thickness. The thickness of the organic partial layer may be thicker on the organic emission layer than on the pixel defining layer.

According to another example of the OLED display device, the sealing portion may further include an inorganic barrier layer disposed on the hybrid protective layer and including an inorganic material.

According to another example of the OLED display device, the sealing portion may further include an organic-inorganic hybrid layer disposed on the hybrid protective layer. The hybrid protective film may be formed by performing a plasma surface treatment on a layer of the same material as the organic-inorganic hybrid layer.

According to another example of the OLED display device, the sealing portion may further include an inorganic barrier layer disposed on the organic-inorganic hybrid layer and including an inorganic material.

According to another example of the OLED display device, the sealing portion may further include an upper hybrid passivation layer disposed on the inorganic barrier layer and having the same partial layer structure as the hybrid passivation layer.

According to another example of the organic light emitting display, the sealing portion may further include an inorganic barrier layer interposed between the display portion and the hybrid protective film and including an inorganic material.

According to another example of the OLED display device, the sealing portion may further include an organic-inorganic hybrid layer interposed between the display portion and the inorganic barrier layer. The hybrid protective film may be formed by performing a plasma surface treatment on a layer of the same material as the organic-inorganic hybrid layer.

According to another example of the OLED display device, the sealing portion may include an upper organic-inorganic hybrid layer disposed on the hybrid protective layer and made of the same material as the organic-inorganic hybrid layer, And an upper inorganic barrier layer disposed on the upper inorganic barrier layer and including an inorganic material.

According to another example of the organic light emitting diode display, the skeleton of the hybrid passivation layer may have a network structure having a linkage of -O-Si-O-. The network may contain silicon, oxygen, hydrogen, and carbon, and some of the silicones may be directly connected to a covalent bond with the carbon that forms part of the organic functional group.

According to another example of the OLED display device, the network structure may further include at least one other element. The other element may be at least one element selected from alkali metals, alkaline earth metals, transition metals, transition metals, metalloids, boron and phosphorus. The other element may be placed in the form of an oxide at an interstitial location in the network structure or may be connected to a silicon atom constituting the skeleton of the network by the covalent bond of the other element-oxygen-silicon.

According to another example of the organic light emitting diode display, the content of silicon and other elements in the hybrid passivation layer may vary within a range of ± 10% by weight or less along the thickness direction.

According to another example of the OLED display device, the moisture permeability of the sealing portion may be less than 0.015 g / m ² / day at 37.8 ° C and a relative humidity of 100%. The light transmittance of the sealing portion may be 85% or more with respect to light at a wavelength of 550 nm at 25 캜.

According to another aspect of the present invention, there is provided an organic light emitting display including a flexible substrate, a display unit including the organic light emitting element on the flexible substrate, and a sealing unit sealing the upper surface and the side surface of the display unit. . Wherein the sealing portion comprises an inorganic partial layer from which carbon has been removed, an organic partial layer having a constant carbon content, and a gradient portion interposed between the inorganic partial layer and the organic partial layer, And an organic-inorganic hybrid layer including the same material as the organic partial layer of the hybrid protective film. The moisture permeability of the sealing portion is 0.009 g / m ² / day or less at 37.8 캜 and 100% relative humidity.

According to another aspect of the present invention, there is provided a method of manufacturing an organic light emitting diode display, comprising: forming a display unit including an organic light emitting diode on a substrate; In the organic-inorganic mixed solution containing the organic material and the inorganic material, sol-gel hydrolysis and condensation proceed to prepare an organic-inorganic hybrid coating liquid. In order to seal the display portion, the organic-inorganic hybrid coating liquid is coated on the display portion to form an organic-inorganic hybrid layer. Treating the organic-inorganic hybrid layer with a plasma containing a reactive gas to form a carbon-removed inorganic partial layer, an organic partial layer having a constant carbon content, and an inorganic organic layer interposed between the inorganic partial layer and the organic partial layer, A hybrid protective film is formed which includes a gradient partial layer whose carbon content is increased as the layer is adjacent to the partial layer. The plasma treatment is continued until the inorganic partial layer having a predetermined thickness is formed in the hybrid protective film.

According to an embodiment of the present invention, the organic-inorganic mixed solution comprises at least one organic silane of formula (1), water, and at least one silicate ester of formula (2) ).

[Chemical Formula 1]

A ¹ _l A ² _m A ³ _n Si (OE ¹ ) _p (OE ² ) _q (OE ³ ) _r

(2)

Si (OG ¹ ) _? (OG ² ) _? (OG ³ ) _? (OG ⁴ ) _?

A ¹ , A ² and A ³ each independently represent an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a vinyl group, an acrylic group, a methacrylic group or an epoxy group, 1, m, and n are each independently 0 or a natural number, 1? l + m + n? 3, and E ¹ , E ² , and E ³ are each independently an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 10 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxyalkyl group having 1 to 20 carbon atoms, a fluoroalkyloxyalkyl group having 1 to 20 carbon atoms, an alkyloxyaryl group having 1 to 20 carbon atoms, An aryloxyalkyl group having 6 to 20 carbon atoms or an aryloxyaryl group having 6 to 20 carbon atoms, p, q and r are each independently 0 or a natural number of 1 to 3, 1? P + q + + m + n + p + q + r = 4.

G ¹ , G ² , G ³ and G ⁴ in the formula (2) each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms in the fluoroalkyl group and 10 to 20 carbon atoms, A fluoroalkyloxyalkyl group having 1 to 20 carbon atoms, an alkyloxyaryl group having 1 to 20 carbon atoms, an aryloxyalkyl group having 6 to 20 carbon atoms, or an aryloxyaryl group having 6 to 20 carbon atoms, ?,?,?, and? are independently 0 or a natural number of 1 to 4, and? +? +? +? = 4.

According to another example of the manufacturing method of the OLED display device, the organic-inorganic mixed solution may further include at least one kind of oxide precursor. The oxide precursor may include at least one other element selected from alkali metals, alkaline earth metals, transition metals, transition metals, metalloids, boron and phosphorus, and may be a precursor capable of forming oxides of the other elements with oxygen have.

According to another example of the manufacturing method of the OLED display device, at least one of the organic-inorganic hybrid layer and the inorganic barrier layer including the inorganic material may be further formed on the hybrid protective layer.

According to another example of the manufacturing method of the OLED display device, at least one of the organic-inorganic hybrid layer and the inorganic barrier layer including the inorganic material may be additionally formed between the display portion and the hybrid protective layer.

According to the organic light emitting display device and the method of manufacturing an organic light emitting display device of the present invention, an organic light emitting display device including a hybrid protective film exhibiting high moisture and oxygen barrier performance through a simple manufacturing process can be achieved. In addition, the overall thickness can be minimized, and the manufacturing cost can be reduced.

1 is a cross-sectional view schematically illustrating an organic light emitting display according to various embodiments of the present invention.
2 is a cross-sectional view illustrating one pixel region of an OLED display according to an exemplary embodiment of the present invention.
3 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.
4 is a cross-sectional view illustrating one pixel region of an OLED display according to another exemplary embodiment of the present invention.
5 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.
6 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.
7 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.
8 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.

Various embodiments of the present invention will now be described in detail with reference to the accompanying drawings. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. It is to be understood that the embodiments shown below may be modified in various ways and that the scope of the present invention is not limited to the following embodiments and that all changes, Should be understood to include.

BRIEF DESCRIPTION OF THE DRAWINGS [0027] Reference will now be made, by way of example, to the accompanying drawings, in which: In the attached drawings, the dimensions of the structures may be shown enlarged or reduced in size to facilitate a clear understanding of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention. The singular < RTI ID = 0.0 > expressions < / RTI > include plural expressions, unless the context clearly dictates otherwise. As used herein, the terms "comprises" or "having", etc., are to be understood as specifying the presence of listed features, and not precluding the presence or addition of one or more other features. In this specification, the term "and / or" is used to include any and all combinations of one or more of the listed features. In this specification, terms such as " first ", "second ", and the like are used only to intend to distinguish one feature from another to describe various features, and these features are not limited by these terms. In the following description, when the first characteristic is described as being connected, coupled or connected to the second characteristic, it does not exclude that the third characteristic may be interposed between the first characteristic and the second characteristic. Further, when it is described that the first element is disposed on the second element, it does not exclude that the third element is interposed between the first element and the second element. However, when it is stated that the first element is disposed directly on the second element, the third element is not interposed between the first element and the second element.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

1 is a cross-sectional view schematically illustrating an organic light emitting display according to various embodiments of the present invention.

1, an OLED display 1000 according to various embodiments of the present invention includes a display unit 200 formed on one side of a substrate 100, a sealing unit 300 sealing the display unit 200, .

The display unit 200 may include an organic light emitting diode (OLED) and a thin film transistor (TFT) array for driving the same.

The sealing portion 300 may include a hybrid protective film. Wherein the hybrid protective film comprises a carbon-free inorganic partial layer, an organic partial layer having a constant carbon content, and a gradient portion interposed between the inorganic partial layer and the organic partial layer, Layer. By forming the sealing portion 300 including the hybrid protective film on the display portion 200, the display portion 200 can be protected from moisture and oxygen of the outside air.

2 is a cross-sectional view illustrating one pixel region of an OLED display according to an exemplary embodiment of the present invention.

Referring to FIG. 2, the OLED display 1000 includes a substrate 100, a display unit 200, and a sealing unit 300.

The substrate 100 may be a flexible substrate. The substrate 110 may be formed of a material such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, Heat-resistant and durable plastic materials such as polyetherimide (PEI), polyethersulphone (PES) and fiber reinforced plastic (PLP), and the like. However, the present invention is not limited thereto, and various materials having flexible characteristics such as a metal foil or a thin glass may be used. Alternatively, the substrate 100 may be a rigid substrate, and the substrate 100 may be made of a glass material containing SiO ₂ as a main component.

When the image is a bottom emission type in which the image is realized in the direction of the substrate 100, the substrate 100 should be formed of a transparent material. However, when the image is a top emission type in which the image is formed in the direction opposite to the substrate 100, the substrate 100 need not necessarily be formed of a transparent material. In this case, the substrate 100 can be formed of metal. When the substrate 100 is formed of metal, the substrate 100 may include at least one selected from the group consisting of carbon, iron, chromium, manganese, nickel, titanium, molybdenum, and stainless steel It is not.

The display unit 200 may be disposed on the upper surface of the substrate 100. The term display unit 200 referred to in the present specification collectively refers to an organic light emitting diode (OLED) and a thin film transistor (TFT) array for driving the organic light emitting diode OLED, and means a display portion for displaying an image and a driving portion for displaying an image together .

The display unit 200 includes a plurality of pixels arranged in a matrix form when viewed on a plane. Each pixel includes an organic light emitting element OLED and an electronic element electrically connected to the organic light emitting element OLED. The electronic device may include at least two thin film transistors (TFT) including a driving thin film transistor and a switching thin film transistor, a storage capacitor, and the like. The electronic device is electrically connected to the wirings and receives an electrical signal from a driving unit outside the display unit 200 to drive the organic light emitting device OLED. The array of electronic elements and wirings electrically connected to the organic light emitting element OLED is referred to as a thin film transistor (TFT) array.

The display portion 200 includes a device / wiring layer 210 including a thin film transistor (TFT) array, and an organic light emitting device layer 220 including an organic light emitting diode (OLED) array.

The device / wiring layer 210 may include a driving thin film transistor (TFT), a switching thin film transistor (not shown), a capacitor (not shown) driving the organic light emitting diode OLED, wirings connected to the thin film transistors or the capacitor (Not shown) may be included. FIG. 2 shows only the organic thin film transistor (TFT) for driving the organic light emitting device OLED and the organic light emitting device OLED. However, the present invention is not limited thereto. It is apparent to those skilled in the art that a thin film transistor (TFT) of a storage capacitor, a storage capacitor, and various wirings may be further included.

A buffer layer 217 may be disposed on the upper surface of the substrate 100 to provide smoothness and prevent penetration of impurities. The buffer layer 217 may be made of an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, titanium oxide, or titanium nitride, or may be made of organic materials such as polyimide, polyester, acrylic, Or a stack of a plurality of materials selected from among the plurality of materials. When the buffer layer 217 contains an inorganic material, the buffer layer 217 can be deposited by various deposition methods such as plasma enhanced chemical vapor deposition (PECVD), atmospheric pressure CVD (APCVD), and low pressure CVD (LPCVD). The buffer layer 217 may be omitted.

The active layer 211 may be disposed on a predetermined region of the buffer layer 217. The active layer 211 is formed by forming an inorganic semiconductor or an organic semiconductor such as silicon or an oxide semiconductor on the entire surface of the flexible substrate 100 on the buffer layer 217 and patterning the substrate using a photolithography process and an etching process .

When the active layer 211 is formed of a silicon material, a polycrystalline silicon layer may be formed by forming an amorphous silicon layer entirely on the buffer layer 217 and then crystallizing the amorphous silicon layer. The amorphous silicon may be formed by a rapid thermal annealing (RTA) process, a solid phase crystallization (SPC) process, an excimer laser annealing (ELA) process, a metal induced crystallization (MIC) process, a metal induced lateral crystallization (MILC) process, ) Method and the like. The polycrystalline silicon layer may be patterned using a photolithography process and an etching process. An active layer 211 including a source region, a drain region, and a channel region defined therebetween is formed by doping impurities such as boron (B) ions or phosphorus (P) ions in some regions of the active layer 211 .

According to another example, after the amorphous silicon layer is first patterned, the polycrystalline silicon patterns may be formed by crystallizing the patterned amorphous silicon pattern.

The first insulating film 219a may be disposed on the active layer 211. [ The first insulating film 219a may include an insulating material such as silicon oxide, silicon nitride, and / or silicon oxynitride, and may be formed by a method such as PECVD, APCVD, or LPCVD.

The first insulating film 219a is interposed between the active layer 211 and the gate electrode 213 of the thin film transistor TFT and can function as a gate insulating film of the thin film transistor TFT. Also, the first insulating film 219a may function as a dielectric layer of the storage capacitor between the lower electrode and the upper electrode of the storage capacitor (not shown). In this case, in order to increase the capacitance of the storage capacitor, the first insulating film 219a may include an insulating material having a high dielectric constant. For example, the first insulating film 219a may have a laminated structure in which silicon nitride having a higher dielectric constant than silicon oxide is interposed between the lower silicon oxide and the upper silicon oxide.

A gate electrode 213 may be disposed on a predetermined region of the first insulating film 219a. The gate electrode 213 may be connected to a gate line (not shown) to which a control signal for controlling the thin film transistor TFT is applied. The thin film transistor TFT may be electrically conducted according to a signal applied to the gate electrode 213 through the gate line.

The gate electrode 213 is formed of a metal such as aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), or the like in consideration of adhesion with the adjacent layer, surface flatness of the layer to be laminated, (Au), Ni, Ni, Ir, Cr, Li, Ca, Mo, Ti, , Copper (Cu), or the like. For example, the gate electrode 213 may have a laminated structure of molybdenum (Mo) / aluminum (Al) / molybdenum (Mo).

A second insulating film 219b including an insulating material such as silicon oxide, silicon nitride, and / or silicon oxide may be disposed on the gate electrode 213, for example. The second insulating film 219b may have a multilayer structure.

The first insulating layer 219a and the second insulating layer 219b may include a contact hole exposing a source region and a drain region of the active layer 211. [ The source electrode 215a and the drain electrode 215b may be electrically connected to the source region and the drain region of the active layer 211 through the contact holes of the first insulating layer 219a and the second insulating layer 219b, respectively.

The source electrode 215a and the drain electrode 215b may be formed of a metal such as aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg) At least one of Ni, Ni, Ir, Cr, Li, Ca, Mo, Ti, W, Or may be formed as a single layer or multiple layers.

For the protection of the thin film transistor (TFT) formed in this way, the third insulating film 219c covering the thin film transistor (TFT) can be arranged.

The third insulating film 219c may include an inorganic insulating film and / or an organic insulating film. The examples of the inorganic insulating films that can be used for the third insulating film (219c) is a silicon oxide (SiO _2), silicon nitride (SiN _x), silicon oxynitride (SiON), aluminum oxide (Al ₂ O _3), titanium oxide (TiO ₂₎ , Tantalum oxide (Ta ₂ O ₅ ), hafnium oxide (HfO ₂ ), zirconium oxide (ZrO ₂ ), Barium Strontium Titanate (BST), Lead Zirconate-Titanate (PZT), and the like. Examples of the organic insulating film that can be used for the third insulating film 219c include a general general polymer (PMMA, PS), a polymer derivative having a phenolic group, an acrylic polymer, an imide polymer, an aryl ether polymer, A fluorine-based polymer, a p-xylene-based polymer, a vinyl alcohol-based polymer, and blends thereof.

The third insulating film 219c may have a composite laminated structure of an inorganic insulating film and an organic insulating film. In this case, the organic insulating film may function as a planarization film for planarizing the upper surface of the inorganic insulating film covering the thin film transistor (TFT), for example, when the organic light emitting device OLED is disposed on the thin film transistor TFT have.

The organic light emitting device layer 220 including the organic light emitting device OLED may be disposed in the light emitting region above the third insulating film 219c.

The organic light emitting device layer 220 may include a pixel electrode 221 formed on the third insulating film 219c, an opposing electrode 225 disposed to face the pixel electrode 221, and an intermediate layer 223 interposed therebetween. When a voltage is applied between the pixel electrode 221 and the counter electrode 225, the intermediate layer 223 can emit light. The intermediate layer 223 may emit blue light, green light, red light, or white light.

The third insulating layer 219c may include a contact hole exposing at least one of the source electrode 215a and the drain electrode 215b and the pixel electrode 221 may be connected to the source electrode 215a and the drain electrode 215b through the contact hole. And the drain electrode 215b, thereby being electrically connected to the thin film transistor TFT.

The organic light emitting display may be classified into a bottom emission type, a top emission type, and a dual emission type depending on a light emitting direction. In the bottom emission type organic light emitting display, the pixel electrode 221 is provided as a light transmitting electrode and the counter electrode 225 is provided as a reflective electrode. In the organic light emitting display of the front emission type, the pixel electrode 221 is provided as a reflective electrode and the counter electrode 225 is provided as a transflective electrode. In the present invention, the organic electroluminescent device OLED emits light in the direction of the sealing part 300 will be described.

The pixel electrode 221 may be a reflective electrode. The pixel electrode 221 may include a laminated structure of a reflective layer and a transparent electrode layer having a high work function. The reflective layer may be formed of at least one selected from the group consisting of Ag, Mg, Al, Pt, Pd, Au, Ni, Ne, Ir, ), Or an alloy thereof. A transparent electrode layer is indium tin oxide (ITO; indium tin oxide), indium zinc oxide (IZO; indium zinc oxide), zinc oxide (ZnO; zinc oxide), indium oxide _{(In 2 O 3; indium oxide} ), indium gallium oxide ( And at least one material selected from transparent conductive oxide materials such as indium gallium oxide (IGO) and aluminum zinc oxide (AZO). The present invention is not limited thereto, and it can be formed of various materials, and its structure can also be a single layer or a multilayer, and various modifications are possible. The pixel electrode 221 may function as an anode electrode.

A pixel defining layer 230 may be disposed on the pixel electrode 221 to cover the edge of the pixel electrode 221 and include a predetermined opening exposing the center of the pixel electrode 221. The pixel defining layer 230 may be formed of an organic material such as polyimide or the like.

An intermediate layer 223 including an organic light emitting layer that emits light may be disposed on an area defined by the opening. The region where the intermediate layer 223 is disposed may be defined as a light emitting region. Meanwhile, when the light emitting region is formed in the opening of the pixel defining layer 230, a region protruded by the pixel defining layer 230 is disposed between the light emitting regions, and no organic light emitting layer is formed in the protruded region Non-emission region.

The counter electrode 225 may be formed as a transmissive electrode. The counter electrode 225 may be a semi-transparent film having a thin metal such as Li, Ca, LiF / Ca, LiF / Al, Al, Mg, or Ag with a small work function. In order to overcome the problem of high resistance of the thin metal semi-transparent film, a transparent conductive film made of a transparent conductive oxide may be laminated on the metal semi-transparent film. The counter electrode 225 may be formed over the entire surface of the flexible substrate 100 in the form of a common electrode. The counter electrode 225 may function as a cathode electrode.

The polarities of the pixel electrode 221 and the counter electrode 225 may be opposite to each other.

The intermediate layer 223 may include an organic light emitting layer that emits light, and the organic light emitting layer may include a low molecular organic material or a polymer organic material. A hole transport layer (HTL) and a hole injection layer (HIL) are arranged in the direction of the pixel electrode 221 with the organic emission layer as a center, An electron transport layer (ETL) and an electron injection layer (EIL) may be disposed in the direction of the counter electrode 225. Of course, other functional layers besides the hole injecting layer, the hole transporting layer, the electron transporting layer, and the electron injecting layer may be laminated.

On the other hand, in the case of a polymer organic layer in which the organic light emitting layer is formed of a polymer organic material, only a hole transport layer may be provided in the direction of the pixel electrode 221 with the organic light emitting layer as a center. The polymeric hole transport layer may be formed by a method such as inkjet printing or spin coating using a polyethylene dihydroxythiophene (PEDOT: poly- (2,4) -ethylene-dihydroxy thiophene) or polyaniline (PANI: 221).

In this embodiment, a structure in which the organic light emitting element layer 220 is disposed on the element / wiring layer 210 on which the driving thin film transistor (TFT) is disposed is described, but the present invention is not limited thereto, The pixel electrode 221 of the organic light emitting diode OLED is formed on the same layer as the active layer 211 of the thin film transistor TFT or the pixel electrode 221 is formed on the same layer as the gate electrode 213 of the thin film transistor TFT Or a structure in which the pixel electrode 221 is formed on the same layer as the source and drain electrodes 215a and 215b.

Although the gate electrode 213 is disposed on the active layer 211 in the present embodiment, the present invention is not limited thereto, and the gate electrode 213 may be disposed under the active layer 211 It is possible.

The sealing portion 300 may be disposed on the substrate 100 so as to cover the display portion 200. The organic light emitting device OLED included in the display unit 200 may be made of an organic material and easily deteriorated by external moisture or oxygen. Therefore, in order to protect the display unit 200, the display unit 200 must be sealed. The sealing portion 300 may include a hybrid protective film 310 as a means for sealing the display portion 200. [ The hybrid protective film 310 includes an inorganic partial layer 313 with carbon removed therefrom, an organic partial layer 311 having a constant carbon content, and an inorganic partial layer 313 interposed between the organic partial layer 311, And a gradient partial layer 312 in which the content of carbon is increased toward the center portion 311.

The hybrid protective film 310 is divided into the organic partial layer 311, the gradient partial layer 312 and the inorganic partial layer 313 but is formed by a single coating and a plasma treatment process, Layer structure. That is, in the structure in which the organic material layer and the inorganic material layer are laminated, since the inorganic material layer must be laminated after the organic material layers are laminated, the hybrid protective film 310 must be formed in the organic- The carbon content is removed from the exposed upper surface through the plasma treatment so that the content of carbon in the inorganic partial layer 313 in which the carbon is removed and the content of carbon in the vicinity of the inorganic partial layer 313 And a organic partial layer 311 in which carbon is not removed and carbon content is constant.

The inorganic partial layer 313 and the gradient partial layer 312 can be formed to have a uniform thickness by a plasma treatment. On the other hand, since the organic partial layer 311 is not affected by the plasma treatment, the organic partial layer 311 may be thick on the organic light emitting device OLED and thin on the pixel defining layer 230.

In addition, since the hybrid protective film 310 is formed by the plasma treatment, it is easy to protect the side surface of the display portion 200. The hybrid protective film 310 disposed on the side of the display portion 200 may include an organic portion layer 311, a gradient partial layer 312 and an inorganic partial layer 313 disposed substantially parallel to the side surface .

The boundary between the organic partial layer 311 and the gradient partial layer 312 and the boundary between the gradient partial layer 312 and the inorganic partial layer 313 may not be clearly distinguished. Unclear boundaries contribute to increased water and oxygen barrier rates. In the structure in which the organic material layer and the inorganic material layer are laminated, the boundary between the organic material layer and the inorganic material layer is clear, and moisture or oxygen can permeate through this boundary.

Although not shown, a halogenated metal layer including LiF may be further interposed between the display portion 200 and the sealing portion 300. The metal halide layer can prevent the display unit 200 from being damaged when the sealing unit 300 is formed of an inorganic material by a sputtering method or a plasma deposition method. Further, an intermediate layer may be interposed between the display portion 200 and the sealing portion 300. Suitable materials for the intermediate layer include, for example, organic materials such as polyimide, polynorbornene, polycarbonate, polyparaxylene, or parylene, or organic materials such as silicon oxide, Silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, titanium oxide, or titanium nitride.

The hybrid protective film 310 including the organic partial layer 311, the gradient partial layer 312, and the inorganic partial layer 313 will be described in detail.

The hybrid protective film 310 has an inclined-type interface structure including silicon and at least one other inorganic element, and the concentration of the organic functional group gradually changes depending on the thickness (or depth).

The hybrid protective film 310 has an "inclined compositional interface structure" when the hybrid protective film 310 is made of an organic-inorganic composite material and is observed along the thickness (depth) direction of the hybrid protective film 310, (I.e., the surface in the direction away from the substrate 100) from the lower surface (i.e., the surface in the direction of the substrate 100) of the hybrid protective film 310, , It means that there is a region where the ratio of carbon gradually decreases when the composition according to the thickness is observed. Therefore, as described above, the hybrid protective film 310 is composed of three partial layers of the organic partial layer 311, the gradient partial layer 312, and the inorganic partial layer 313, and the composition This does not change rapidly.

The skeleton of the hybrid protective film 310 is a network structure having a linkage of -O-Si-O-, which is a structure seen in a silicate. The network may comprise silicon, oxygen, hydrogen, and carbon. Some of the silicones may be directly connected to covalent bonds with the carbon that forms part of the organic functional group. For example, in the network structure, some silicon atoms are bonded to four oxygen atoms, while some silicon atoms are bonded to an organic group such as an alkyl group, an aryl group, a fluoroalkyl group, a vinyl group, an acrylic group, a methacrylic group, Functional groups and Si-C bonds. A silicon atom in which an organic functional group of the silicon atom of the network structure is connected by an Si-C bond can be bonded to one organic functional group.

The network structure may further include at least one other element. Other elements that can be included in the network structure of the hybrid protective film 310 may be at least one element selected from alkali metals, alkaline earth metals, transition metals, transition metals, metalloids, boron and phosphorus (P). In the hybrid protective film 310, the other element may be placed in the form of oxide at an interstitial location in the network structure, or may be connected to a silicon atom constituting the skeleton of the network structure by covalent bonding with other elements-oxygen-silicon . When the symbol of the other element is represented by M, a part of the other element is directly bonded to the -O-Si-O- skeleton of the network in an oxide form of M _m O _n , or a hydroxide form or an oxide form containing a hydroxyl group It can exist in the gap. Other parts of the other elements may be linked directly to the framework of the network structure, such as -MO-Si- by chemical bonding. In both cases, since the other element is bonded to the oxygen atom, other elements present in the hybrid protective film 310 can be regarded as a wide range of oxides.

As described above, the hybrid protective film 310 has a graded-composition type interface structure and consists of three layers of an organic partial layer 311, a gradient partial layer 312 and an inorganic partial layer 313 sequentially from the lower surface.

In the following description, the direction of travel from the inorganic partial layer 313 to the organic partial layer 311, or vice versa, is referred to as the "thickness" direction or "depth" direction of the hybrid protective film 310. The term "inorganic partial layer 313" refers to a partial layer of the hybrid protective film 310, which is located near the upper surface of the hybrid protective film 310 and in which carbon is substantially not detected. The fact that the carbon is not substantially detected in the inorganic partial layer 313 from the viewpoint of the operation of the measuring instrument is actually measured by, for example, X-ray photoelectron spectroscopy (XPS) . ≪ / RTI > The main signal used to measure the mole fraction of carbon atoms in XPS is a spectroscopic signal originating from the 1s level of carbon atoms. The fact that the carbon atoms are not substantially detected in the inorganic part layer 313 on the basis of XPS means that the intensity of the carbon atom signal is not statistically significantly larger than that of the noise signal.

The inorganic partial layer 313 is, for example, composed mainly of silicon and oxygen at a mole fraction of 99% or more of the atoms. When further other elements are further included, the inorganic partial layer 313 may be composed mainly of silicon, oxygen, and other elements not described below. From the fact that carbon is not substantially detected in the inorganic partial layer 313, it can be seen that there is no carbon bearing the Si-C bond in the silicon atom of the inorganic partial layer 313. However, the inorganic partial layer 313 contains silicon atoms which are bonded to four oxygen atoms and constitute the -O-Si-O- linkage which is the skeleton of the network structure. In the hybrid protective film 310, the inorganic partial layer 313 mainly plays a role of blocking oxygen and moisture due to the dense composition.

The term "organic partial layer 311" refers to a partial layer of the hybrid protective film 310 which is located near the lower surface of the hybrid protective film 310 and in which carbon is detected in a predetermined amount. Some of the silicon atoms in the organic partial layer 311 are bonded directly to the carbon atom constituting the organic functional group while forming the -O-Si-O- linkage which is the skeleton of the network structure and the other part is bonded to the four oxygen atoms At the same time, it can be connected to the skeleton of the network structure. And, the organic partial layer 311 may include the above-mentioned other metal elements. The organic part layer 311 has affinity for the surface of the display part 200 positioned below (i.e., the counter electrode 225), and can function to bring the display part 200 and the sealing part 300 into close contact with each other .

The term "gradient partial layer 312" is a partial layer positioned between the inorganic partial layer 313 and the organic partial layer 311, wherein the content of carbon is from the inorganic partial layer 313 to the organic partial layer 313, Refers to a region that gradually monotonously increases in the thickness along the thickness direction toward the base 311. That is, the carbon content of the gradient partial layer 312 is substantially not detected at the interface with the inorganic partial layer 313 as in the inorganic partial layer 313, the carbon content gradually increases along the thickness direction, And reaches the carbon content value of the organic partial layer 311 at the interface with the layer 311.

Since carbon is not substantially detected in the "inorganic partial layer 313 ", the inorganic partial layer 313 can be regarded as an inorganic material layer containing silicon and oxygen as main components. Although the organic partial layer 311 is referred to as an organic partial layer, the organic partial layer 311 may have a skeleton of silicon and oxygen, and some of the silicon may not be bonded to an organic functional group, The organic partial layer 311 has a structure of an organic-inorganic composite material in which an organic functional group and an inorganic material are combined. The gradient partial layer 312 also has the structure of an organic-inorganic composite material. Therefore, the hybrid protective film 310 composed of the inorganic partial layer 313, the gradient partial layer 312, and the organic partial layer 311 can be referred to as an organic-inorganic composite layer.

The inorganic partial layer 313 can be regarded as an inorganic material layer and the gaseous partial layer 312 and the organic partial layer 311 can be regarded as organic - inorganic composite material.

The sloping composition type interface structure is a structure in which the content of carbon atoms changes in accordance with the thickness (depth) direction of the hybrid protective film 310, and the content of silicon and other elements does not change as much as carbon atoms depending on the thickness. In particular, the content of silicon and other elements in the hybrid protective film 310 may be substantially uniform throughout the hybrid protective film 310. For example, the fluctuation range of the content of silicon and other elements is at most ± 10% by weight or at most ± 7% by weight in the thickness direction.

The hybrid protective film 310 is characterized in that the interface between the inorganic partial layer 313, the gradient partial layer 312 and the organic partial layer 311 is not clearly distinguished. The hybrid protective film 310 is an organic-inorganic composite layer having a graded-composition type interface structure whose composition gradually changes. Therefore, the hybrid protective film 310 has excellent moisture blocking effect, oxygen blocking effect and mechanical strength due to the dense composition of the inorganic partial layer 313 And at the same time, the abrupt change in physical properties is buffered through the gradient partial layer 312 to ensure flexibility and high affinity with the upper surface of the display portion 200 can be obtained due to the organic partial layer 311. The inorganic partial layer 313 is not peeled off from the gradient partial layer 312 because the composition is gradually changed in the single hybrid protective film 310 integrated with the chemical bond. (Not shown). The hybrid protective film 310 has a function of preventing cracks and peeling due to the difference in physical properties between the layers when compared with the thin film encapsulation of the prior art in which the inorganic material layers are laminated separately on the organic material layer by chemical vapor deposition or sputtering And flexibility and strength can be obtained at the same time.

Further, the hybrid protective layer 310 of the present invention may be formed by directly connecting other elements other than carbon to the -O-Si-O- backbone of the barrier layer through oxygen or by being present in the interstices of the network structure, And the refractive index of the hybrid protective film 310 can be adjusted by appropriately selecting the kind and amount of the other elements. For example, when the hybrid protective film 310 has a target refractive index, it is selected as an oxide of another element having a refractive index that is closer to the target refractive index than the refractive index of the organic-inorganic hybrid layer formed without other elements, Can be brought close to the target refractive index by injecting it into the organic-inorganic hybrid layer.

Since the hybrid protective film 310 is a network structure having a skeleton of -O-Si-O- linkages, the hybrid protective film 310 may have a transparent characteristic depending on the selection of other elements. The hybrid protective film 310 has a refractive index of 1.4 to 2.5 with respect to light having a wavelength of 632 nm at 25 DEG C and a content of other elements such as other elements is selected so that the light transmittance is 80% or more with respect to light having a wavelength of 550 nm . When the refractive index is 1.4 to 2.5, it is easy to match the refractive indexes with each other when layers having different materials on the hybrid protective film 310 are required to be laminated. Therefore, the light transmittance of the final OLED display 1000 is excellent Level. If the light transmittance is 80% or more, the sharpness of the organic light emitting display 1000 can be improved. The light transmittance of the hybrid passivation film 310 is 85% or more, and the light transmittance of the hybrid passivation film 310 is 90% in the practical application in consideration of the cost and the physical properties of the raw material, Beyond that, light transmittance is also possible.

The hybrid protective film 310 may further include other elements such as Li, Na, K, Rb, Cs, Ber, , Mg, Ca, Sr, Ba, Ti, Zr, Hf, V, Nb, Mo, ), Tungsten (W), tellurium (Te), rhenium (Re), nickel (Ni), zinc (Zn), aluminum (Al), gallium Sn), boron (B), phosphorus (P), and combinations thereof. The ratio of the number of atoms of the other element to silicon in the hybrid protective film 310 may be selected in the range of 1:20 to 20: 1, or in the range of 1:10 to 10: 1. In this case, 310 may have a more dense structure. Therefore, the moisture barrier property and the oxygen barrier property can be further improved.

The content of carbon atoms in the inorganic partial layer 313 may be 1% or less by mol. In other words, this 1% content corresponds to the noise signal level of the XPS and is a level at which carbon is not substantially detected.

When the hybrid protective film 310 further includes other elements, when the number of carbon atoms is N _carbon , the number of silicon atoms is N _silicon , the number of oxygen atoms is N _oxygen , and the number of atoms of _{other elements} is N _{other elements} , And the carbon content of the inorganic partial layer 313 may be N _carbon / (N _carbon + N _silicon + N _oxygen + N _{other element} )? 0.01. -Si-O-Si- or -MO-Si- is to achieve a dense network structure, but contribute, Si-CH _x Si- or alkyl, such as carbon-functional terminal group having a binding hydrogen (CH) (end functionality) are those It can act as a defect in the network structure and degrade the gas barrier property. When the content of the carbon atoms is within the above range, internal defects generated by functional groups having a carbon-hydrogen bond are minimized, so that the inorganic partial layer 313 has excellent gas barrier properties.

The surface hardness of the inorganic part layer 313 may be 6H or more as measured by a pencil hardness meter.

The network structure of the hybrid protective film 310 may include both silicon atoms (inorganic silicon) that are not directly bonded to the carbon forming the organic functional group and silicon atoms (organic silicon) that is bonded directly to the carbon that forms the organic functional group . At this time, the organic partial layer 311 of the hybrid protective film 310 may be composed of only organic silicon, or may include both organic silicon and inorganic silicon. When the network structure of the organic partial layer 311 contains a silicon atom (inorganic silicon) which is not directly bonded to carbon, the silicon atom directly bonded to the carbon forming the organic functional group in the organic partial layer 311 Silicon) may be less than 10. If the ratio of the number of atoms of inorganic silicon to organosilicon in the composition of the organic partial layer 311 is smaller than the above value, the hybrid protective film 310 can have appropriate flexibility without being easily cracked by external stress.

* In the hybrid protective film 310, an organic functional group is directly connected to a silicon atom by a Si-C bond, and may not be bonded to an oxygen atom. That is, if the organic functional group is R, it can be connected with R-Si, but not with RO-Si. The hybrid protective film 310 having no organic functional group bonded to oxygen atoms can further increase the light transmittance and can make the density more dense as compared with the case where organic functional groups bonded to oxygen atoms such as RO-Si are present, The blocking performance is better.

The average number of organic functional groups of the silicon atom (organosilicon) to which the organic functional group is directly bonded may be 3 or less. Preferably, the number of organic functional groups bonded to the organosilicon may be 2 or less. More preferably, the number of organic functional groups is one.

The organic functional groups may be crosslinked to each other. The crosslinking may be a carbon-carbon single bond.

The thickness of the hybrid protective film 310 may be selected in the range of 0.1 mu m to 10 mu m.

The hybrid protective film 310 has a water permeability of 37.8 DEG C and a relative humidity of 100% to 0.015 g / m < ² > / day or less. Particularly, the water permeability of 0.015 g / m ² / day, which can be realized with the hybrid protective film 310 according to the present invention, is lower than the water permeability of the inorganic film obtained by the typical prior art sputtering process of 10 ^-1 g / m ² / day An order of magnitude improved. In terms of light transmittance, the hybrid protective film 310 exhibits a light transmittance of 88.5% with respect to a wavelength of 550 nm and a light transmittance similar to that of a conventional inorganic film of 91.1%.

Hybrid protective film 310 is in the oxygen transmission rate 35 ℃, relative humidity 0% 10 ^- excellent 1cm ³ / m ² / il ^{~ 10 -2 cm 3 / m 2} / day. Particularly, the oxygen permeability of 10 ^-2 cm ³ / m ² / day, which can be realized with the hybrid protective layer 310 according to the present invention, can be measured by using a typical barrier layer obtained by plasma enhanced chemical vapor deposition (PECVD) It is an order of magnitude improvement over the minimum oxygen permeability of 10 ^-1 cm ³ / m ² / day level.

A method of manufacturing the hybrid protective film 310 according to an embodiment of the present invention will be described in detail.

The method for manufacturing the hybrid protective film 310 is,

A process for preparing an organic-inorganic mixed solution comprising at least one organosilane of formula (1), at least one oxide precursor, water, and at least one silicate ester of formula (2) Hydrolyzing and condensing the sol-gel to produce an organic-inorganic hybrid coating liquid,

b) coating the organic-inorganic hybrid coating liquid on the display portion 200 formed on the substrate 100 and curing the organic-inorganic hybrid coating liquid to form an organic-inorganic hybrid layer, and

c) treating the surface of the organic-inorganic hybrid layer with a plasma containing a reactive gas to form a hybrid protective layer 310. [

At this time, the plasma treatment in step c) of forming the hybrid protective film 310 can proceed until the inorganic partial layer 313 in which no carbon is detected is formed in the hybrid protective film 310 to a predetermined thickness.

In step a), the organic-inorganic mixed solution is prepared by mixing at least one kind of organosilane, at least one kind of oxide precursor, water and at least one kind of silicate ester as an optional component .

According to another example, the organic-inorganic mixed solution may comprise at least one kind of organosilane, water, and at least one silicate ester as an optional component, without an oxide precursor. In this case, the hybrid protective film 310 does not contain any other element.

The organosilane and the silicate ester may contain hydrolyzable functional groups such as an alkoxy group and an aryloxy group in all stoichiometrically possible ratios as shown in the following Formulas 1 and 2, respectively. The organosilane may further include a non-hydrolyzable organic functional group in addition to an alkoxy group and / or an aryloxy group. The combination of the organic functional group and the hydrolyzable functional group in the organosilane may comprise any combination stoichiometrically possible.

[Chemical Formula 1]

A ¹ _l A ² _m A ³ _n Si (OE ¹ ) _p (OE ² ) _q (OE ³ ) _r

(2)

Si (OG ¹ ) _? (OG ² ) _? (OG ³ ) _? (OG ⁴ ) _?

At this time, A ¹ , A ² and A ³ each independently represent an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a vinyl group, an acrylic group, a methacrylic group or an epoxy group. l, m and n are each independently 0 or a natural number, and 1? l + m + n? 3. E ^1, E ^2, E ³ are each independently of each other in carbon number from 1 to 10 alkyl group, carbon number 1 to 10 with an alkyl group the number of carbon-fluoro 6-20 aryl group, carbon 1 to 20 of the alkyloxy group, the carbon A fluoroalkyloxyalkyl group of 1 to 20 carbon atoms, an alkyloxyaryl group of 1 to 20 carbon atoms, an aryloxyalkyl group of 6 to 20 carbon atoms, or an aryloxyaryl group of 6 to 20 carbon atoms. p, q, and r are each independently 0 or a natural number of 1 to 3, and 1? p + q + r? 3 and 1 + m + n + p + q + r = 4.

G ¹ , G ² , G ³ and G ⁴ in the formula (2) each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms in the fluoroalkyl group and 10 to 20 carbon atoms, A fluoroalkyloxyalkyl group having 1 to 20 carbon atoms, an alkyloxyaryl group having 1 to 20 carbon atoms, an aryloxyalkyl group having 6 to 20 carbon atoms, or an aryloxyaryl group having 6 to 20 carbon atoms. ?,?,?, and? are independently 0 or a natural number of 1 to 4, and? +? +? +? = 4.

The oxide precursor may include at least one other element selected from alkali metals, alkaline earth metals, transition metals, transition metals, metalloids, boron and phosphorus. In addition, the oxide precursor may form a binary oxide of the other element and oxygen through a sol-gel hydrolysis process.

The sol-gel synthesis process for preparing the organic-inorganic composite coating liquid from the organic-inorganic mixed solution is a technology familiar to the average person skilled in the art and is not described in detail herein. Organic silanes, silicate esters, and hydrolyzable oxide precursors are all starting materials that are widely used for sol-gel hydrolysis and condensation reactions. Briefly, an organic-inorganic mixed solution can be prepared by mixing an organosilane, an oxide precursor to provide an oxide of another element other than carbon, water and optionally a silicate ester. At this time, the organic-inorganic mixed solution may include a solvent and a catalyst. As described above, the oxide precursor for supplying the oxide of the other element other than carbon may be optionally not included in the organic-inorganic mixed solution.

As the sol-gel hydrolysis of the organic-inorganic mixed solution proceeds, the hydrolyzable functional groups such as alkoxy groups and aryloxy groups in the silane components are hydrolyzed to form Si-OH, and then the Si-OH removes water And condensed to form a network structure in which -O-Si-O- connecting portions are connected. At this time, if the oxide precursor of the other element also has a hydrolyzable functional group, it can be hydrolyzed together, and the condensation reaction can proceed further to be connected to the -O-Si-O- It can be settled. The oxide precursor may be partially converted into an oxide in the subsequent plasma treatment step c). As a result of such hydrolysis and condensation, an organic-inorganic hybrid coating liquid can be produced.

The organic-inorganic mixed solution is prepared by mixing one or more organosilanes and one or more oxide precursors, water and, if necessary, one or more silicate esters, so that a wide variety of organic-inorganic mixed solutions can be prepared . In one embodiment of the present invention, a hydrolysis reaction and a condensation reaction can be carried out while adding silicate ester and a polar solvent and stirring the organosilane to this solution. By removing water, an alcohol component, or a catalyst from the organic-inorganic mixed solution by using extraction or dialysis, finally the organic-inorganic hybrid coating solution can be obtained.

In one embodiment of the present invention, the organosilane and the silicate ester used to prepare the organic-inorganic mixed solution in the step a) may be represented by the formulas (3) and (4), respectively.

(3)

R ¹ _x Si (OR ² ) _(4-x)

[Chemical Formula 4]

Si (OR ³⁾ ₄

In Formula (3), R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms including a vinyl group, an acrylic group, a methacrylic group, and an epoxy group. R ² is an alkyl group having 1 to 10 carbon atoms or an alkyloxyalkyl group having 1 to 10 carbon atoms. x is an integer of 1 to 3; Preferably, x is 1 or 2.

In Formula 4, R ³ is an alkyl group having 1 to 10 carbon atoms or an alkyloxyalkyl group having 1 to 10 carbon atoms.

When organotrialkoxysilane and tetra-alkyl silicate are used as organosilanes and silicate esters, respectively, as in formulas (3) and (4), it is convenient in terms of cost, availability, and reactivity of raw materials.

In one embodiment of the invention, the organosilane of the formula 1, x is 1, trialkoxysilane ^{(R 2 Si (OR 3)} 3) , or x is 2, dialkoxysilane _{^{((R 2) 2 Si (}} OR 3) ₂ ) may be used.

Exemplary compounds of trialkoxysilane (R ² Si (OR ³ ) ₃ ) include, but are not limited to, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, vinyltripropoxysilane, phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like.

Exemplary compounds of dialkoxysilane ((R ² ) ₂ Si (OR ³ ) ₂ ) include, but are not limited to, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane May be included.

Examples of silicate esters of formula (2) include tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate, tetraisopropoxysilicate, tetrabutoxysilicate, tetraethoxyethyl silicate, and the like. Other silicate esters other than the above exemplified materials can also be used.

When the silicate ester is included in the preparation of the organic-inorganic mixed solution according to an embodiment of the present invention, the molar ratio of the silicate ester to the organosilane may be 1: 10 to 10: 1 have. In this case, the organic-inorganic hybrid layer of step b) and the hybrid protective film 310 of step c) can have appropriate flexibility without cracking the external stress. By controlling the ratio of the organic silane to the silicate ester, the carbon content in the final hybrid protective film 310 can be determined.

The other element which is the central atom of the oxide precursor that can be contained in the organic-inorganic mixed solution is hydrolyzed to form a non-carbon metallic element, which can form other element-oxygen-other element and other element-oxygen- Any metal element can be used, and some nonmetallic elements are possible. Here, 'metal' refers to a group of alkali metals, alkaline earth metals, transition metals, transition metals, metalloids and nonmetals.

Examples of oxide precursors that may be included in the organic-inorganic mixed solution are given below. Of course, the oxide precursor is not limited to the examples listed here.

As an example of a precursor of a nonmetal other element, if the other element is boron (III), the oxide precursor may be boric acid, trimethylborate, and the like. (P), the oxide precursor is selected from the group consisting of phosphoric acid, phosphorus oxychloride, phosphorus pentoxide, and alkylphosphates having 1 to 6 carbon atoms. (For example, methyl phosphate, ethyl phosphate, dimethyl phosphate, trimethyl phosphate, triethyl phosphate) and the like.

According to one embodiment of the present invention, the oxide precursor may be a metal oxide precursor. The precursor of the metal oxide may be represented by the following chemical formula (5).

[Chemical Formula 5]

ML _n

(I), R (I), Cs (I), Be (II), Mg (II) and Ca (II) (III), Ga (III), In (III), Ti (IV), Ta (V), Zr (IV), Hf , Tl (III), Ge (IV), Sn (IV), Sb (III) and the like. L is (singer) a decomposable functional group, for example, a halogen (F ^-, Cl ^-, Br ^- and I ^-, especially Cl ^- and Br ^-), nitrate (NO ₃ ^-), alkoxy group of carbon number 1 to 6 (in particular, Butoxy, sec-butoxy or tert-butoxy, n-pentyloxy, n-hexyloxy), the number of carbon atoms Acyloxy (particularly acetoxy and propionyloxy), alkylcarbonyl (e.g., acetyl), acetylacetone, and the like, having from 1 to 4 carbon atoms, . In the case of Li (I), Na (I), K (I), Rb (I) and Cs (I), n = 1 and Be (II) , III (III), III (III), B (III), Sb (III), Mg (II), Ca (II) (V), Mo (V), and W (V) for n = 3, Ti (IV), Zr (IV), Hf N = 5.

Some examples of precursors of alkali metals are as follows.

Examples of Li (I) include lithium acetate, lithium bromide, lithium carbonate, lithium chloride, lithium nitrate, lithium iodide,

In the case of Na (I), sodium acetate, sodium bromide, sodium carbonate, sodium chloride, sodium nitrate, sodium iodide, sodium ethoxide, sodium methoxide

In the case of K (I), potassium acetate, potassium bromide, potassium carbonate, potassium chloride, potassium nitrate, potassium iodide

In the case of Rb (I), rubidium acetate, rubidium bromide, rubidium carbonate, rubidium chloride, rubidium nitrate, rubidium iodide

In the case of Cs (I), cesium acetic acid, cesium bromide, cesium carbonate, cesium chloride, cesium nitrate, cesium iodide

Some examples of precursors of alkaline earth metals are as follows.

In the case of Be (II), beryllium acetylacetonate, beryllium chloride, beryllium nitrate

In the case of Mg (II), magnesium acetate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium ethoxide, magnesium fluoride, magnesium formate, magnesium iodide)

In the case of Ca (II), calcium acetate, calcium bromide, calcium carbonate, calcium chloride, calcium fluoride, calcium formate, calcium iodide

Some examples of precursors of transition metals are as follows.

In the case of Ti (IV), titanium chloride dihydrate, titanium tert-butoxide, titanium n -butoxide, titanium 2-ethylhexyl titanium 2-ethylhexyloxide), ethoxylated titanium, titanium methoxide, isopropoxylated titanium, titanium iodide

In the case of Ta (V), tantalum butoxide, tantalum chloride, tantalum ethoxide, tantalum methoxide

In the case of Zr (IV), zirconium butoxide, zirconium ethoxide, isopropoxylated zirconium, propoxylated zirconium, tributoxybutyl zirconium, zirconium acetylacetonate

In the case of Hf (IV), normal butoxide hafnium, tert-butoxy hafnium

In the case of Mo (V), isopropoxylated molybdenum, molybdenum trichloride isopropoxide,

In the case of W (V), tungsten ethoxide

In the case of Zn (II), zinc citrate, zinc acetate, zinc acetylacetonate hydrate, zinc chloride, zinc nitrate

In the case of Sn (IV), tin (IV) acetate, tin (II) chloride dihydrate and tin (III)

Some of the precursors of post-transition metals are as follows.

In the case of Al (III), aluminum ethoxide, aluminum isopropoxide, aluminum phenoxide, tributoxy titanium aluminum, tributoxyaluminum, aluminum tri-sec-butoxide, , Aluminum chloride, aluminum nitrate

In the case of Ga (III), gallium acetylacetonate, gallium chloride, gallium fluoride, gallium nitrate hydrate

In the case of In (III), indium chloride, indium chloride hexahydrate, indium fluoride, indium fluoride trihydrate, indium hydroxide, indium nitrate hydrate, indium acetylacetonate, indium acetylacetonate,

In the case of Tl (III), thallium acetylacetonate, thallium acetylacetonate, thallium chloride, thallium tetrachloride hydrate, thallium nitrate, thallium nitrate trihydrate

Some precursors of metalloids are as follows.

In the case of Ge (IV), germanium ethoxide, isopropoxylated germanium, germanium methoxide, germanium (IV) chloride, germanium (IV)

In the case of Sb (III), antimony butoxide, antimony ethoxide, antimony methoxide, antimony pentoxide

A variety of organic reaction by using a gel-sol from the organic silane and silicic acid ester and the above-mentioned inorganic oxide precursor composite material, for _{example, CaO-SiO 2, ZrO-} SiO 2, MgO-SiO 2, Al 2 O 3 -SiO 2 _{, TiO 2 -SiO 2, ZnO 2} -SiO 2, ZrO 2 -SiO 2, Ga 2 O 3 -SiO 2, P 2 O 5 -SiO 2, P 2 O 5 -Na 2 O-SiO 2, P 2 O ₅ -Na ₂ O-Al ₂ O 3 -SiO ₂ , P ₂ O ₅ -Al ₂ O ₃ -SiO ₂ , P ₂ O ₅ -CaO-Na ₂ O-SiO ₂ , B ₂ O ₃ -SiO ₂ , Na ₂ An organic-inorganic hybrid coating layer composed of OB ₂ O ₃ -SiO ₂ , GeO ₂ -SiO ₂ and MoO ₂ -SiO ₂ can be produced. The principles and means of this sol-gel preparation process are already well known (see, for example, J. Am . Ceram. Soc . 71, 666-672 (1988), J. Am . Chem . Soc . 133, 1917-1934 (2011), Journal of Left - Gel Science and Technology , 3, 219-227 (1994), J. Mater . Chem., 15, 2134-2140 (2005), Journal of Left - Gel Science and Technology 13, 103-107 (1998), J Sol - Gel Sci Techn (2006) 39: 79-83 , Journal of Non- Crystalline Soiids 100 (1988) 409-412, Journal of Left - Gel Science and Technology 37, 63 ~ 68, 2006, J. Phys . Chem . B 1998, 102, 6465-6470, Catal Lett (2008) 126: 286-292 .

The addition amount of the organosilane in the organic-inorganic mixed solution may be determined depending on the number of carbon atoms of the silane organic functional moiety and the type of the functional group in order to suppress cracking of the organic-inorganic hybrid coating layer and impart flexibility. In one embodiment of the present invention, when the molar number of the _organosilane is M _silicate , the number of moles of the _{silicate ester} is M _{silicic acid ester} , and the number of moles of the other elements of the oxide precursor is M _{other element} , M _organosilane / (M _{silicate ester} + M _{miscellaneous element} )? 10, the organic-inorganic mixed solution can be prepared. The content of _organosilane may satisfy 0.1? M _organosilane / (M _{silicate ester} + M _{other element} )? 5.

Since the hybrid protective film 310 may have a protective function even when it does not contain inorganic silicon, the M _{silicate ester} may be 0 in the above formula. In this case, an organic-inorganic mixed solution can be prepared with only organosilane and other elements and water.

The number of other element moles (M _{other elements} ) is often equal to the number of moles of oxide precursor. However, when the number of atoms of the other element in the one mole of the oxide precursor is an integer multiple of 1 (for example, when the oxide precursor is a non-stoichiometric compound, such as Li ₂ CO ₃ ), the number of moles of the oxide precursor ). For example, if the added oxide precursor is 2.5 moles of Li ₂ CO _3, then the M _{other element} = 5. Similarly, when several kinds of organosilanes, silicate esters and oxide precursors are used together, the values of M _organosilane , M _{silicate ester} , and M _{other elements} are the sum of all the chemical species.

If the addition amount of the organosilane is within the above range, flexibility can be imparted to the organic-inorganic hybrid coating layer, and then the plasma treatment time can be controlled within an appropriate range in step c).

The amount of the oxide precursor added to the other elements in the organic-inorganic mixed solution can be determined according to the desired level of moisture and oxygen barrier properties and mechanical properties. In accordance with one embodiment of the present invention, the organic-to the molar number of the organic silane in the manufacture of the inorganic mixed solution M molar number of the _{organic silane,} silicate ester can be other elements of moles of M _{Silicate esters} oxide precursor M _{other elements} , The organic-inorganic mixed solution may be prepared by mixing the components so that the content of the oxide precursor satisfies 0.05? M _{other element} / (M _organosilane + M _{silicate ester} )? 20. The content of the oxide precursor may satisfy 0.1? M _{other element} / (M _organosilane + M _{silicate ester} )? 10.

The values of M _organosilane , M _{silicate ester} , and M _{other elements} are determined in the same manner as in the above-described equation. Addition of oxide precursors of other elements to the silane components at this ratio can provide excellent moisture barrier properties, gas barrier properties and mechanical strength while preventing cracking of the hybrid protective film 310.

In the organic-inorganic mixed solution, water is a reactant for hydrolysis. Water is suitable if it is water of sufficient purity, for example, distilled water, ultrapure water and the like can be used.

In one embodiment of the present invention, the organic-inorganic mixed solution contains 100 parts by weight of the total amount of the organosilane and the oxide precursor (when the silicate ester is contained in the organic-inorganic mixed solution, the amount of the organosilane, the oxide precursor and the silicate ester (The total weight of 100 parts by weight), 5 to 350 parts by weight of water, or 10 to 250 parts by weight of water.

In one embodiment of the present invention, the number of moles of water to be added to the organic-inorganic mixed solution is equal to or more than the total number of moles of hydrolyzable functional groups such as alkoxy group and aryloxy group which can be hydrolyzed in the organic- Lt; / RTI >

In one embodiment of the present invention, when the amount of water in the production of the organic-inorganic mixed solution is less than the molar amount of water relative to the total number of moles of the hydrolyzable functional groups of the organosilane and the siloxane ester combined with hydrolyzable functional groups such as aryloxy groups The number of moles of water to the total number of moles of hydrolyzable functional groups can be selected within the range of 1: 5 to 5: 1, or in the range of 1: 3 to 3: 1. When the oxide precursor also contains a hydrolyzable functional group such as an alkoxy group or an aryloxy group, the number of mols of the hydrolyzable functional group is preferably in a range of from 1 to 500 moles per mole of the hydrolyzable functional group of the organic silane and the silicate ester, And the number of moles of the functional group.

In order to proceed with the sol-gel hydrolysis reaction in the step a), the organic-inorganic mixed solution may further contain a solvent in addition to water as a reactant. A polar solvent may be used as a solvent that can be included in the organic-inorganic mixed solution. Some examples of suitable polar solvents are methanol, ethanol, isopropanol, butanol, 2-methoxy-ethanol, 2-ethoxy-ethanol, 2-butoxyethanol, 1-methoxy- -2-propanol and the like; Ketone systems such as methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate, butyl acetate and 2-methoxy-ethyl acetate, 2-ethoxy-ethyl acetate and 2-butoxy-ethyl acetate; Aromatic hydrocarbons such as toluene and xylene, and N, N-dimethylmethanamide as a polar solvent. It goes without saying that the respective solvents may be used alone or in the form of a mixture in the organic-inorganic mixed solution of the present invention.

In order to accelerate the sol-gel hydrolysis reaction and the condensation reaction, an acid or base catalyst may be used. As a catalyst for promoting hydrolysis, an acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, hydrofluoric acid (HF) May be added to a polar solvent. The reaction time and temperature depend on the silane components, the type of oxide precursor, and the concentration on the solvent, but the general sol-gel hydrolysis and condensation conditions of the silane components and the oxide precursor are not limited.

The solid solids content of the finally produced organic-inorganic hybrid solution may be 1 to 50% by weight based on the solvent and distilled water. Preferably, it may be an amount of 5 to 30% by weight. When the silica sol is used in an amount of 5% by weight or less, the thickness may become too thin, and even if a subsequent treatment step is performed, desired barrier properties may not be obtained. When the silica sol is used in an amount of 50% by weight or more, the surface of the silica sol may be rough and easily cracked due to external impact.

The organic-inorganic composite coating liquid, which is the thus obtained organic-inorganic composite material sol, can be applied on the display portion 200 on the substrate 100 by various coating methods. In one embodiment of the present invention, a spin coating process, a dip coating process, a roll coating process, a screen coating process, a spray coating process, a spin casting process, A method such as flow coating, screen printing or ink-jetting may be used.

According to an embodiment of the present invention, after the organic-inorganic hybrid coating liquid is coated on the display portion 200 on the substrate 100, the organic-inorganic hybrid coating liquid is cured by thermal curing or photo curing to form a cured An organic-inorganic hybrid layer may be formed. For example, the organic-inorganic hybrid coating liquid may be coated to a thickness of 0.1 to 10 占 퐉, or a thickness of 0.1 to 5 占 퐉.

The thermal curing may be performed within a temperature range in which the organic light emitting device OLED of the display unit 200 and the substrate 100 are not deteriorated and the heat treatment conditions may vary depending on the organic light emitting device OLED and the substrate 100 . The thermal curing can be carried out, for example, within a temperature range of 50 to 200 캜.

In the organic silane of the above formula (1), A ¹ , A ² and A ³ are unsaturated functional groups such as a vinyl group, an acryl group, a methacryl group and the like as a raw material for a sol-gel hydrolysis reaction. Organosilane having such a functional group can form an organic-inorganic hybrid layer in which radicals are formed by light and unsaturated functional groups form a crosslinking, so that irradiation of light causes crosslinking of organic functional groups. Examples of suitable photoinitiators include, but are not limited to, 1-hydroxycyclohexyl phenyl ketone (trade name Irgacure 184), benzophenone, 2-hydroxy-2-methylpropiophenone , 2,2-diethoxyacetophenone, 3,3 ', 4,4'-tetrakis- ( t- butylperoxycarbonyl) benzophenone [3,3,4,4-tetra- ( t -butylperoxycarbonyl) benzophenone ], And the like. In this case, the photoinitiator may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the organic-inorganic composite layer solution.

In this step c), the organic-inorganic hybrid layer is subjected to plasma treatment only on the upper surface of the organic-inorganic hybrid layer coated on the display portion 200 without performing chemical vapor deposition or sputtering under high vacuum, ). ≪ / RTI > The inorganic partial layer 313 may be formed on the upper surface of the organic-inorganic hybrid layer by the plasma treatment in the step c), and the gradient partial layer 312 may be formed below the inorganic partial layer 313. That is, by treating the upper surface of the organic-inorganic hybrid layer containing the silane-derived organic functional group with a plasma using a reactive gas to remove the organic functional groups from the upper surface of the organic-inorganic hybrid layer, It is possible to change the upper surface portion into a layer of pure inorganic material and further form an inclined composition of the organic functional group along the depth direction in the region corresponding to the gradient partial layer 312. Accordingly, the organic-inorganic hybrid layer can be converted into the hybrid protective layer 310 including the inorganic partial layer 313, the gradient partial layer 312, and the organic partial layer 311. [

The process of converting the upper surface of the organic-inorganic hybrid layer into the partial layer of the inorganic material by the plasma treatment in the step c) is performed by simultaneous physical and chemical effects of the particles formed by the plasma. It is not intended to be bound by any particular theory as to the working principle of the process of the present invention, but for the sake of clarity, a brief description is given of the use of a reactive gas (for example, oxygen) - inorganic composite layer is thought to be removed by the gas form (CO, CO ₂ ) through the decomposition process of the organic functional groups present in the silicon chain near the upper surface of the inorganic composite layer. At the same time, the light energy of various wavelengths (soft X-ray, ultraviolet ray, visible ray, infrared ray) generated in the excitation-relaxation process of the gas molecules induced by the plasma induces a photochemical reaction at the surface of the organic- . Especially, when high-energy light such as soft X-ray and vacuum ultraviolet (100 ~ 190 nm) is emitted in the plasma treatment process, Si-C, Si-O and MO bonds are dissociated and radicals are generated, And it is believed that the crosslinking reaction can be actively induced. At the same time, the high energy ions generated by the plasma will generate pressure and heat in the process of ion bombardment, leading to the molecular structure of the surface area of the precursor layer being treated to have a dense structure.

As a result, the organic functional groups are efficiently removed from the surface of the organic-inorganic hybrid layer by the plasma treatment using the reactive gas to form the dense inorganic partial layer 313. The inorganic partial layer 313 thus formed is dense in structure, and is excellent in the effect of blocking oxygen and moisture. This dense structure can be further strengthened by the oxides of the other elements. The inorganic partial layer 313 having such a dense structure is characterized in that the surface hardness is increased.

On the other hand, in the lower region of the inorganic partial layer 313, the organic functional group is not completely removed, and the gradient partial layer 312 (the organic partial layer 313), which gradually increases in carbon concentration along the thickness direction toward the organic partial layer 311 .

In one embodiment of the present invention, the plasma treatment of step c) may consist of a continuous, single number of treatments that do not change the plasma treatment conditions during treatment. That is, it is not necessary to adjust the plasma treatment conditions for the formation of the gradient partial layer 312, and only by treating the organic-inorganic hybrid layer one time and without interruption in one fixed processing condition, A hybrid protective film 310 having an interface structure may be formed. Of course, if it is an average technician in the field, it is possible to change the plasma treatment condition to a variable condition that varies with time, rather than a fixed condition, depending on the performance of the hybrid protective film 310 to be obtained, Can be changed.

In the plasma surface treatment in the step c), the substrate 100 on which the organic-inorganic hybrid layer is formed on the display unit 200 is put into the plasma reaction chamber in step b), and the pressure is lowered. Then, O ₂ , N ₂ O Inorganic composite layer by supplying a reactive gas such as N ₂ , NH ₃ , H ₂ , H ₂ O, etc. (that is, a plasma raw material gas) and applying power to the electrode to generate plasma. In this case, the plasma raw material gas supplied into the reaction chamber as well as the single gas _{O 2 / N 2 O, O} 2 / N 2, O 2 / NH 3, O 2 / H 2, Ar / O 2, He / O 2 , A mixed gas of these gases such as Ar / N ₂ O, He / N ₂ O, Ar / NH ₃ and He / NH ₃ , an inert gas such as helium (He) Can also be used. As the power source for generating the plasma, there are a plasma power source type such as a radio frequency (RF) power source, a medium frequency (MF) power source, a direct current (DC) power source, and a microwave power source All are available without.

In the plasma surface treatment in the step c), the thicknesses of the inorganic partial layer 313 and the gradient partial layer 312 may vary depending on the plasma output, the processing pressure, the processing time, the distance between the electrode and the substrate, And as a result, moisture and oxygen barrier properties can be controlled. Generally, the higher the plasma output, the lower the process pressure, and the longer the treatment time, the more the hydrocarbon component is removed to increase the thickness of the inorganic partial layer 313 and the gradient partial layer 312, Is improved. However, if the plasma output is high, the blocking performance may be increased by only a short time of processing. However, since the temperature of the organic light emitting device OLED may deteriorate due to the plasma treatment or the substrate 100 may be deformed, It needs to be adjusted appropriately. Also, depending on the kind of the reactive gas, M-O and M-N (M is silicon and metal) can be bonded and the blocking characteristics can be controlled.

According to one embodiment of the present invention, the inorganic partial layer 313 may be formed to a thickness of 10 to 100 nm, or 10 to 50 nm, in order to realize excellent blocking characteristics. In addition, the sum of the thicknesses of the inorganic partial layer 313 and the gradient partial layer 312 formed by the plasma treatment may be 50 to 250 nm, or 100 to 200 nm.

Since the hybrid protective film 310 thus formed has intermediate characteristics between the organic and inorganic materials according to the ratio of the organic functional groups, the organic partial layer 311 is formed by the lower display portion 200 and the inorganic partial layer 313 ). ≪ / RTI > Through this buffering function, when an external force acts on the hybrid protective film 310 or when the resin shrinks or expands due to temperature, the stress generated at the interface is reduced to cause cracking or peeling of the hybrid protective film 310 from the display portion 200 Can be suppressed.

According to an embodiment of the present invention, when a radio frequency (RF) power source is used as a plasma power source, the output is 0.3 W / cm 2 to 4 W / cm 2, the processing time is 5 seconds to 10 minutes, Plasma processing can be performed while maintaining mtorr. If the plasma output is less than 0.3 W / cm 2, desired blocking performance can not be obtained with a processing time of less than 10 minutes, and if it exceeds 4 W / cm 2, the organic light emitting device OLED or the substrate 100 may be damaged . Also, if the plasma processing pressure is greater than 500 mtorr or the treatment time is less than 5 seconds, it is difficult to obtain the desired level of barrier performance.

The hybrid protective film 310 can be formed on the counter electrode 225 by the above-described method. Compared with the conventional thin film encapsulation method, the hybrid shielding layer 311 including the organic partial layer 311, the gradient partial layer 312 and the inorganic partial layer 313 is formed by performing the plasma surface treatment after forming the organic- The process is simpler than the thin film encapsulation method in which a plurality of deposition processes must be performed. In addition, in the thin film encapsulation method, the peeling phenomenon may occur between the films, and cracks may be caused by a sudden temperature change or an external impact due to the difference in characteristics between the films. However, since the hybrid protective film 310 according to the present invention does not clearly distinguish the boundaries between the partial layers, peeling does not occur between the partial layers, and since the characteristics of the hybrid protective film 310 gradually change with thickness, Cracks do not occur even when the impact or temperature of the substrate is changed. Further, the characteristics of the hybrid protective film 310 can be easily controlled by changing plasma treatment conditions as necessary.

3 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.

Referring to FIG. 3, an organic light emitting display 1000a in which a hybrid protective layer 310 and an inorganic barrier layer 320 are disposed on a display portion 200 is shown.

The organic light emitting display 1000a is substantially similar to the organic light emitting display 1000 shown in FIG. 2, except that an inorganic barrier layer 320 is further disposed on the hybrid protective film 310. FIG. The description of the substrate 100, the display portion 200, and the hybrid protective film 310 of the organic light emitting display 1000a has been described above with reference to FIG. 2, and therefore is not repeated.

The inorganic barrier layer 320 may be disposed on the inorganic partial layer 313 of the hybrid protective film 310. [ The inorganic barrier layer 320 may include at least one inorganic material selected from the group consisting of silicon oxide, silicon nitride, silicon oxides, aluminum oxides, aluminum nitrides, titanium oxides, titanium nitrides, and zirconium oxides. For example, the inorganic barrier layers 320 may comprise any one of a silicon nitride (SiNx), aluminum oxide (Al ₂ O _3), silicon oxide (SiO _2), titanium oxide (TiO _2), zirconium oxide (ZrO ₂₎ . The material of the inorganic barrier layer 320 can be selected in consideration of the adhesive force with the underlying inorganic part layer 313.

In Figure 3, the inorganic barrier layer 320 is shown as being a single layer, but this is exemplary and may have a stacked structure in which a plurality of layers are stacked. For example, the inorganic barrier layer 320 may have a laminated structure of silicon oxide (SiO ₂ ) / aluminum oxide (Al ₂ O ₃ ) / silicon oxide (SiO ₂ ).

The inorganic barrier layer 320 may be formed by a chemical vapor deposition (CVD) method, a plasma enhanced CVD (PECVD) method, a high density plasma CVD (HDP-CVD) method, a sputtering method, ), And the like.

4 is a cross-sectional view illustrating one pixel region of an OLED display according to another exemplary embodiment of the present invention.

4, an organic light emitting diode display 1000b having a hybrid protective layer 310, an organic-inorganic hybrid layer 330, and an inorganic barrier layer 320 disposed on a display portion 200 is illustrated.

The OLED display 1000b is similar to the OLED display 1000 shown in FIG. 3 except that an organic-inorganic hybrid layer 330 is further disposed between the hybrid protective layer 310 and the inorganic barrier layer 320 1000a. The description of the substrate 100, the display portion 200, the hybrid protective layer 310, and the inorganic barrier layer 320 of the organic light emitting display 1000b is not repeated because it has been described above with reference to FIGS. 2 and 3 .

The organic-inorganic hybrid layer 330 may be disposed between the hybrid protective layer 310 and the inorganic barrier layer 320. As described above, the hybrid protective film 310 is formed by performing a plasma treatment on the surface of the organic-inorganic hybrid layer. The organic-inorganic hybrid layer 330 is formed by applying a plasma surface treatment to form the hybrid protective film 310 Organic composite layer described above. In other words, the organic-inorganic hybrid layer 330 is formed by applying the organic-inorganic hybrid coating solution prepared by proceeding the sol-gel hydrolysis and condensation reaction to the organic-inorganic hybrid solution on the hybrid protective layer 310, And then curing it. The organic portion layer 311 of the hybrid protective film 310 has properties and composition substantially similar to those of the organic-inorganic composite layer 330, because it is not affected by the plasma surface treatment.

The organic-inorganic hybrid layer 330 is disposed on the inorganic partial layer 313 of the hybrid passivation layer 310 to relieve the internal stress of the inorganic partial layer 313, Defects such as cracks can be compensated.

4, the sealing portion 300b is shown to include the hybrid protective layer 310, the organic-inorganic hybrid layer 330, and the inorganic barrier layer 320, but the inorganic barrier layer 320, Inorganic hybrid layer 310 and the organic-inorganic hybrid layer 330 only.

5 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.

Referring to FIG. 5, an organic light emitting display 1000c having an inorganic barrier layer 320c and a hybrid passivation layer 310 disposed on a display 200 is illustrated.

The organic light emitting display 1000c shown in FIG. 2 is substantially identical to the organic light emitting display 1000 shown in FIG. 2 except that an inorganic barrier layer 320c is further disposed between the hybrid protective film 310 and the display portion 200. [ . The description of the substrate 100, the display portion 200, and the hybrid protective film 310 of the organic light emitting display 1000c is not repeated because it has been described above with reference to FIG. In addition, the inorganic barrier layer 320c is substantially similar to the inorganic barrier layer 320 of the organic light emitting diode display 1000a shown in Fig. 3 except for the position where the inorganic barrier layer 320c is disposed.

The inorganic barrier layer 320c may be disposed on the counter electrode 225 of the display portion 200. [ Inorganic barrier layer (320c), for example, including at least one of a silicon nitride (SiNx), aluminum oxide (Al ₂ O _3), silicon oxide (SiO _2), titanium oxide (TiO _2), zirconium oxide (ZrO ₂₎ And may be formed in a single layer or a multilayer structure and may be formed by a chemical vapor deposition (CVD) method, a plasma enhanced CVD (PECVD) method, a high density plasma CVD (HDP-CVD) method, a sputtering method, (ALD), and the like.

Although not shown in FIG. 5, a halogenated metal layer including LiF may further be interposed between the inorganic barrier layer 320c and the counter electrode 225. FIG. The metal halide layer can prevent the display portion 200 from being damaged when the inorganic barrier layer 320c is formed.

6 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.

Referring to FIG. 6, an organic light emitting diode display 1000d having an organic-inorganic hybrid layer 330d, an inorganic barrier layer 320c, and a hybrid passivation layer 310 is disposed on a display 200.

The organic light emitting diode display 1000d shown in FIG. 5 is similar to the organic light emitting display 1000c shown in FIG. 5 except that an organic-inorganic hybrid layer 330d is further disposed between the inorganic barrier layer 320c and the display portion 200. FIG. ). The description of the substrate 100, the display portion 200, and the hybrid protective film 310 of the organic light emitting display 1000d is not repeated because it has been described above with reference to Fig. In addition, the inorganic barrier layer 320c is substantially similar to the inorganic barrier layer 320 of the organic light emitting diode display 1000a shown in Fig. 3 except for the position where the inorganic barrier layer 320c is disposed. In addition, the organic-inorganic hybrid layer 330d is substantially similar to the organic-inorganic hybrid layer 330d of the organic light emitting display 1000b shown in Fig.

The organic-inorganic hybrid layer 330d may be disposed on the counter electrode 225 of the display unit 200. The organic-inorganic hybrid layer 330d is formed by applying sol-gel hydrolysis to the organic-inorganic mixed solution and applying the organic-inorganic hybrid coating solution to the counter electrode 225 of the display unit 200, And then curing it.

The inorganic barrier layer 320c may be disposed on the organic-inorganic hybrid layer 330d. Inorganic barrier layer (320c), for example, including at least one of a silicon nitride (SiNx), aluminum oxide (Al ₂ O _3), silicon oxide (SiO _2), titanium oxide (TiO _2), zirconium oxide (ZrO ₂₎ And may be formed in a single layer or a multilayer structure and may be formed by a chemical vapor deposition (CVD) method, a plasma enhanced CVD (PECVD) method, a high density plasma CVD (HDP-CVD) method, a sputtering method, (ALD), and the like.

7 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.

7, an organic light emitting diode display (OLED) display device (OLED display) 300 in which a lower hybrid passivation layer 310, an organic-inorganic hybrid layer 330, an inorganic barrier layer 320, and an upper hybrid passivation layer 310e are disposed on a display 200 1000b are shown.

The organic light emitting display 1000e is substantially similar to the organic light emitting display 1000b shown in Fig. 4, except that the upper hybrid passivation layer 310e is further disposed. Description of the substrate 100, the display portion 200, the lower hybrid passivation layer 310, the organic-inorganic hybrid layer 330, and the inorganic barrier layer 320 of the organic light emitting diode display 1000e will be described with reference to FIGS. Since it is described above by reference, it is not repeated. The lower hybrid protective film 310 of FIG. 7 is substantially the same as the hybrid protective film 310 of FIG.

The upper hybrid passivation layer 310e may be disposed on the inorganic barrier layer 320. [ The upper hybrid passivation film 310e has substantially the same characteristics and composition, only at the position where it is disposed with the lower hybrid passivation film 310. [

The upper hybrid passivation layer 310e is formed by applying sol-gel hydrolysis to the organic-inorganic mixed solution, coating the organic-inorganic hybrid coating solution on the inorganic barrier layer 320, curing the inorganic barrier layer 320, And then performing a treatment. By the plasma surface treatment, the upper hybrid passivation film 310e may also include the organic partial layer 311e, the gradient partial layer 312e, and the inorganic partial layer 313e.

The organic partial layer 311e is not affected by the plasma surface treatment and the content of carbon is constant and the inorganic partial layer 313e is removed from the carbon by the plasma surface treatment and substantially no carbon is detected. Since the gradient partial layer 312e is partially subjected to the plasma surface treatment, the content of carbon is decreased as it is adjacent to the inorganic partial layer 313e. As shown, the organic partial layer 311e, the gradient partial layer 312e, and the inorganic partial layer 313e may have substantially the same thickness.

8 is a cross-sectional view illustrating one pixel region of an OLED display according to another embodiment of the present invention.

8, a lower organic-inorganic hybrid layer 330d, a lower inorganic barrier layer 320c, a hybrid protective layer 310, an upper organic-inorganic hybrid layer 330f, and an upper inorganic barrier layer 330d are formed on a display 200, An organic light emitting display 1000f in which the layer 320f is disposed is shown.

The organic light emitting diode display 1000d includes the organic light emitting display shown in FIG. 6 except that the upper organic-inorganic hybrid layer 330f and the upper inorganic barrier layer 320f are further disposed on the hybrid protective layer 310. [ Which is substantially similar to device 1000d. The description of the substrate 100, the display portion 200, the lower organic-inorganic hybrid layer 330d, the lower inorganic barrier layer 320c, and the hybrid protective layer 310 of the organic light emitting diode display 1000f will be described with reference to FIGS. 6, so it is not repeated. The lower organic-inorganic hybrid layer 330d and the lower inorganic barrier layer 320c of FIG. 8 are only different from each other and have substantially the same structure as the organic-inorganic hybrid layer 330d and the inorganic barrier layer 320c of FIG. 6 can do.

The upper organic-inorganic hybrid layer 330f and the upper inorganic barrier layer 320f are substantially similar to the lower organic-inorganic hybrid layer 330d and the lower inorganic barrier layer 320c, except where the upper organic-inorganic hybrid layer 330f and the upper inorganic barrier layer 320f are disposed, respectively.

The upper organic-inorganic hybrid layer 330f may be disposed on the hybrid protective layer 310. [ The upper organic-inorganic hybrid layer 330f is formed by applying the organic-inorganic hybrid coating liquid prepared by proceeding sol-gel hydrolysis with respect to the organic-inorganic mixed solution onto the hybrid protective layer 310, . The material of the upper organic-inorganic hybrid layer 330f and the material of the lower organic-inorganic hybrid layer 330d may be the same or different.

The upper inorganic barrier layer 320f may be disposed on the organic-inorganic hybrid layer 330f. Inorganic barrier layer (320f) are, for example, including at least one of a silicon nitride (SiNx), aluminum oxide (Al ₂ O _3), silicon oxide (SiO _2), titanium oxide (TiO _2), zirconium oxide (ZrO ₂₎ And may be formed in a single layer or a multilayer structure and may be formed by a chemical vapor deposition (CVD) method, a plasma enhanced CVD (PECVD) method, a high density plasma CVD (HDP-CVD) method, a sputtering method, (ALD), and the like. The material of the upper inorganic barrier layer 320f may be the same as or different from the material of the lower inorganic barrier layer 320c.

The inventors of the present invention manufactured the organic light emitting diode display 1000 shown in FIG. 2 as follows.

(A) The display portion 200 was formed on the substrate 100.

As the substrate 100, a polyethylene terephthalate (PET) film having a thickness of 125 탆 which is transparent plastic was used.

The display unit 200 includes a thin film transistor TFT on the substrate 100, a pixel electrode 221 connected to the thin film transistor TFT, a pixel defining layer 230 exposing a part of the pixel electrode 221, An intermediate layer 223 including an organic light emitting layer disposed on a part of the pixel electrode 221 and an opposite electrode 225 disposed on the intermediate layer 223. [

An organic-inorganic mixed solution was prepared, and an organic-inorganic hybrid layer was formed on the display portion 200.

An organic-inorganic mixed solution was prepared by adding 1.25 g (6 mmol) of tetraethylorthosilicate (TEOS) and 1.07 g (6 mmol) of methyltriethoxysilane (MTES) to 12 mL of an isopropanol solvent. The organic - inorganic mixed solution was sol - gel hydrolyzed and condensed to prepare a sol - like organic - inorganic composite coating liquid.

Inorganic composite coating liquid was spin-coated to a thickness of about 2 to 3 탆 so as to cover the display portion 200 on the substrate 100 and then cured to form an organic-inorganic hybrid layer.

The surface of the organic-inorganic hybrid layer was subjected to plasma treatment to form a hybrid protective film 310.

The substrate 100 having the organic-inorganic hybrid layer formed on the display unit 200 is placed in a plasma reaction chamber, the pressure inside the vessel is dropped to 10 ^-3 torr or less by using a vacuum pump, and the vacuum pump is continuously operated And the surface of the organic-inorganic hybrid layer was treated for 1 minute by generating plasma at an RF output of 2 W / cm < 2 > at a pressure of 50 mtorr to form hydrocarbons on the surface of the organic- .

The organic-inorganic hybrid layer includes a carbon-free inorganic partial layer 313, an organic partial layer 311 having a constant carbon content, and an organic partial layer 311 interposed between the inorganic partial layer 313 and the organic partial layer 311, And a gradient partial layer 312 in which the content of carbon is increased as the layer 311 is closer to the hybrid protective film 310.

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The moisture permeability of the sealing portion 300 of the organic light emitting diode display 1000 including the hybrid protective layer 310 measured by Model 3/33 was 15 x 10 ^-3 g / m ² / day, and the UV-Vis Spectrometer HP 8453 , And the light transmittance measured for light of 550 nm was 88.5%.

The inventors of the present invention manufactured the organic light emitting diode display 1000a shown in FIG. 3 as follows.

The above steps a) to c) were performed.

(D) An inorganic barrier layer 320 is formed on the hybrid protective film 310.

The substrate 100 having the hybrid protective film 310 formed on the display unit 200 is placed in a plasma chamber and the pressure inside the vessel is lowered to 10 ^-6 torr or less by using a vacuum pump and then the vacuum pump is continuously operated Argon gas was introduced and the plasma was generated at an RF output of 5 W / cm 2 at a pressure of 1 mtorr. The argon gas ionized by the plasma generation accelerated toward the electrode, collided with the silicon oxide target, and the silicon oxide (SiO _x ) was ejected. An inorganic barrier layer 320 made of the ejected silicon oxide (SiO _x ) was deposited on the hybrid protective film 310. The thickness of the inorganic barrier layer 320 was about 30 to 120 nm.

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The moisture permeability of the sealing portion 300a of the organic light emitting diode display 1000a including the hybrid protective layer 310 and the inorganic barrier layer 320 measured by Model 3/33 was 9x10 ^-3 g / m ² / day , And a light transmittance of 88.7% as measured with a UV-Vis Spectrometer HP 8453 at a wavelength of 550 nm.

The inventors of the present invention manufactured the organic light emitting diode display 1000b shown in FIG. 4 as follows.

The above steps a) to c) were performed.

E) Before the d) step, the organic-inorganic hybrid layer 330 is formed on the hybrid protective layer 310. [

The organic-inorganic hybrid layer 330 is obtained by curing the organic-inorganic hybrid coating solution prepared in step (b). The organic-inorganic hybrid coating solution was spin-coated on the hybrid protective layer 310 and cured to form an organic-inorganic hybrid layer 330.

Inorganic barrier layer 320 was formed on the organic-inorganic hybrid layer 330 in the same manner as in the step d).

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The moisture permeability of the sealing portion 300b of the organic light emitting diode display 1000b including the hybrid protective film 310, the organic-inorganic hybrid layer 330, and the inorganic barrier layer 320, as measured by Model 3/33, 5 × 10 ^-3 g / m ² / day, and the light transmittance of the UV-Vis spectrometer HP 8453 measured at 550 nm was 88.5%. Mocon Permatran-W; The measurement limit of Model 3/33 was 5 x 10 ^-3 g / m ² / day and the moisture permeability of the seal 330 b was below the measurement limit.

It was determined that the barrier performance was improved by filling the organic-inorganic hybrid layer 330 with microcracks that may have occurred in the inorganic barrier layer 320.

The inventors of the present invention manufactured the organic light emitting diode display 1000c shown in FIG. 5 as follows.

The above step a) was performed.

Before performing the above step b), the above step d) was performed.

The sealing portion 300c including the inorganic barrier layer 320c and the hybrid protective film 310 is formed on the display portion 200 by performing the above step b)

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The water permeability of the sealing portion 300c of the organic light emitting display 1000c measured by Model 3/33 was less than 5 x 10 ^-3 g / m ² / day and measured with a UV-Vis Spectrometer HP 8453 for light of 550 nm The light transmittance was 86.3%. Mocon Permatran-W; The measurement limit of Model 3/33 was 5 x 10 ^-3 g / m ² / day, and the moisture permeability of the seal portion 330 c was below the measurement limit.

The inventors of the present invention fabricated the organic light emitting diode display 1000d shown in FIG. 6 as follows.

The above a) step, the ㅁ) step, and the d) step were performed in this order.

A sealing portion 300d including the organic-inorganic hybrid layer 330d, the inorganic barrier layer 320c, and the hybrid protective layer 310 is formed on the display portion 200 by performing the above-described steps b) and d) .

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The moisture permeability of the sealing portion 300d of the organic light emitting display 1000d measured by Model 3/33 was less than 5 x 10 ^-3 g / m ² / day and measured with a UV-Vis Spectrometer HP 8453 for light of 550 nm The light transmittance was 87.5%. Mocon Permatran-W; The measurement limit of Model 3/33 was 5 x 10 ^-3 g / m ² / day and the moisture permeability of the seal 330 d was below the measurement limit.

The inventors of the present invention manufactured the organic light emitting diode display 1000e shown in FIG. 7 as follows.

The above steps a) through c), step e), and step d) were performed in this order.

Inorganic composite layer 330d, the inorganic barrier layer 320c, and the upper hybrid passivation layer 310e are formed on the display unit 200 by repeating the above-described steps b) and c) To form a sealing portion 300e.

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The moisture permeability of the sealing portion 300e of the organic light emitting display 1000e measured by Model 3/33 was less than 5 x 10 ^-3 g / m ² / day and measured with a UV-Vis Spectrometer HP 8453 for light of 550 nm The light transmittance was 85.2%. Mocon Permatran-W; The measurement limit of Model 3/33 was 5 x 10 ^-3 g / m ² / day and the moisture permeability of the seal 330 d was below the measurement limit.

The inventors of the present invention manufactured the organic light emitting diode display 1000f shown in FIG. 8 as follows.

The above a) step, the ㅁ) step, and the d) step were performed in this order.

Inorganic composite layer 330d, the lower inorganic barrier layer 320c, and the hybrid organic-inorganic hybrid layer 330c are formed on the display unit 200 by performing the above-described steps b) and d) A sealing portion 300f including a protective film 310, an upper organic-inorganic hybrid layer 330f, and an upper inorganic barrier layer 320f was formed.

Mocon Permatran-W at 37.8 [deg.] C, 100% relative humidity; The moisture permeability of the sealing portion 300f of the organic light emitting display 1000f measured by Model 3/33 was less than 5 x ^10-3 g / m ² / day and measured with a UV-Vis Spectrometer HP 8453 for light of 550 nm The light transmittance was 85.5%. Mocon Permatran-W; The measurement limit of Model 3/33 was 5 x 10 ^-3 g / m ² / day and the moisture permeability of the seal 330 d was below the measurement limit.

The results of moisture permeability and light transmittance of the organic light emitting display devices 1000 to 1000f are as follows.

Seal structure Water permeability
(g / m 2 / day) Light transmittance
(%, 550 nm) MOCON limit
(g / m 2 / day) 300 (HP) 15x10 ^-3 88.5 5x10 ^-3 300a (IB / HP) 9x10 ^-3 88.7 5x10 ^-3 300b (IB / OIC / HP) Less than the measurement limit 88.5 5x10 ^-3 300c (HP / IB) Less than the measurement limit 86.3 5x10 ^-3 300d (HP / IB / OIC) Less than the measurement limit 87.5 5x10 ^-3 300e (HP / IB / OIC / HP) Less than the measurement limit 85.2 5x10 ^-3 300f (IB / OIC / HP / IB / OIC) Less than the measurement limit 85.5 5x10 ^-3 300b '(OIC / HP) Less than the measurement limit 89.3 5x10 ^-3

Here, HP denotes a hybrid protective film 310, IB denotes an inorganic barrier layer, and OIC denotes an organic-inorganic composite layer. The sealing portion 300b 'has a structure in which the sealing portion 300b is deformed and the inorganic barrier layer is omitted in the sealing portion 300b. The water permeability was measured at 37.8 ° C and a relative humidity of 100%. Measuring instruments were Mocon Permatran-W; Model 3/33 was used, and the measurement limit of this measuring instrument was 5 × 10 ^-3 g / ㎡ / day.

As a comparative example, the water permeability was also measured for a structure in which the sealing portion did not include the hybrid protective film.

The water permeability exceeded 10 ^-1 g / m 2 / day when the sealing portion is composed of an organic-inorganic composite layer or when it is composed of an inorganic barrier layer and an organic-inorganic composite layer.

When the sealing portion was composed of an inorganic barrier layer having a thickness of 25 nm, the water permeability was 0.59 g / m 2 / day.

When the sealing portion was composed of an inorganic barrier layer having a thickness of 60 nm, the water permeability was 0.27 g / m 2 / day.

When the sealing portion was composed of an inorganic barrier layer having a thickness of 115 nm, the water permeability was 0.35 g / m 2 / day.

When the sealing portion is composed of the inorganic barrier layer having a thickness of 60 nm and the organic-inorganic composite layer, the water permeability was 0.37 g / m 2 / day.

Although the present invention has been described with reference to the limited embodiments, various embodiments are possible within the scope of the present invention. It will also be understood that, although not described, equivalent means are also incorporated into the present invention. Therefore, the true scope of protection of the present invention should be defined by the following claims.

100: substrate 200: display portion
210: element / wiring layer 220: organic light emitting element layer
300: sealing part 310: hybrid shielding
311: organic partial layer 312: gradient partial layer
313: inorganic partial layer 320: inorganic barrier layer
330: Organic-inorganic composite layer

Claims (20)

Board;
A display unit including an organic light emitting element on the substrate; And
And a hybrid protective film sealing the display portion,
The hybrid protective film may be formed,
Preparing an organic-inorganic hybrid coating solution by proceeding sol-gel hydrolysis and condensation on an organic-inorganic mixed solution containing an organic material and an inorganic material;
Coating the organic-inorganic hybrid coating solution on the display unit and curing the organic-inorganic hybrid coating layer to form the organic-inorganic hybrid layer; And
Wherein the organic-inorganic hybrid layer comprises an organic partial layer having a constant carbon content, an inorganic partial layer disposed on the organic partial layer and having carbon removed therefrom, and an inorganic partial layer interposed between the organic partial layer and the inorganic partial layer, Inorganic composite layer to a plasma containing a reactive gas until the inorganic partial layer is formed on the upper surface to have a predetermined thickness so as to be deformed into the hybrid protective film including a gradient partial layer having a decreasing carbon content as the distance from the organic partial- Wherein the organic light emitting display device is formed by a method including the steps of: The method according to claim 1,
The display unit includes:
A thin film transistor on the substrate;
A pixel electrode connected to the thin film transistor;
A pixel defining layer exposing at least a part of the pixel electrode and defining a light emitting region;
An organic emission layer disposed on at least a part of the pixel electrode exposed by the pixel defining layer; And
And a counter electrode disposed on the organic emission layer and the pixel defining layer. 3. The method of claim 2,
The inorganic partial layer and the gradient partial layer each have a constant thickness,
Wherein the thickness of the organic partial layer is thicker on the organic light emitting layer than on the pixel defining layer. The method according to claim 1,
Further comprising an inorganic barrier layer disposed on the inorganic partial layer of the hybrid protective film and formed of an inorganic material. The method according to claim 1,
Further comprising an upper organic-inorganic composite layer disposed on the inorganic partial layer of the hybrid protective film,
The content of carbon discontinuously changes at the boundary of the inorganic partial layer and the upper organic-inorganic composite layer of the hybrid protective film,
Wherein the upper organic-inorganic hybrid layer is formed of the same material as the organic-inorganic hybrid layer by the same method. 6. The method of claim 5,
And an inorganic barrier layer disposed on the upper organic-inorganic hybrid layer and formed of an inorganic material. The method according to claim 6,
Further comprising an upper hybrid passivation layer disposed on the inorganic barrier layer and having the same partial layer structure as the hybrid passivation layer,
Wherein an amount of carbon discontinuously changes at a boundary between the inorganic barrier layer and the organic partial layer of the upper hybrid passivation layer. The method according to claim 1,
Further comprising an inorganic barrier layer interposed between the display portion and the organic portion layer of the hybrid protective film and formed of an inorganic material,
Wherein a content of carbon discontinuously changes at a boundary between the inorganic barrier layer and the organic partial layer of the hybrid protective film. 9. The method of claim 8,
And a lower organic-inorganic hybrid layer interposed between the display part and the inorganic barrier layer,
The content of carbon discontinuously changes at the boundary between the inorganic barrier layer and the lower organic-inorganic composite layer,
Wherein the lower organic-inorganic hybrid layer is formed of the same material as the organic-inorganic hybrid layer by the same method. 10. The method of claim 9,
An upper organic-inorganic composite layer disposed on the inorganic partial layer of the hybrid protective film and formed in the same manner as the organic-inorganic composite layer in the same manner; And
Further comprising an upper inorganic barrier layer disposed on the upper organic-inorganic hybrid layer and formed of an inorganic material. The method according to claim 1,
The skeleton of the hybrid protective film is a network structure having a linkage of -O-Si-O-,
Wherein the network comprises silicon, oxygen, hydrogen, and carbon,
Wherein some of the silicon atoms are directly connected to a covalent bond with a carbon forming part of an organic functional group. 12. The method of claim 11,
Wherein said network further comprises at least one other element,
The other element is at least one element selected from alkali metals, alkaline earth metals, transition metals, transition metal, metalloid, boron and phosphorus,
Wherein the other element is positioned in the form of an oxide at an interstitial location in the network structure or is connected to a silicon atom constituting the skeleton of the network with the covalent bond of the other element-oxygen-silicon. Emitting display device. 13. The method of claim 12,
Wherein the content of silicon and other elements in the hybrid passivation layer has a variation width within a range of up to +/- 10% by weight along the thickness direction. The method according to claim 1,
The moisture permeability of the hybrid protective film is 0.015 g / m ² / day or less at 37.8 캜 and a relative humidity of 100%
Wherein the hybrid passivation layer has a light transmittance of 85% or more with respect to light having a wavelength of 550 nm at 25 캜. delete Forming a display portion including an organic light emitting element on a substrate;
Preparing an organic-inorganic hybrid coating solution by proceeding sol-gel hydrolysis and condensation on an organic-inorganic mixed solution containing an organic material and an inorganic material;
Coating the organic-inorganic hybrid coating solution on the display unit and curing the organic-inorganic hybrid coating layer to form the organic-inorganic hybrid layer; And
Treating the organic-inorganic hybrid layer with a plasma containing a reactive gas to form a carbon-removed inorganic partial layer, an organic partial layer having a constant carbon content, and an inorganic organic layer interposed between the inorganic partial layer and the organic partial layer, And forming a hybrid protective film including a gradient partial layer whose content of carbon increases as it is adjacent to the partial layer,
Wherein the plasma treatment is performed until the inorganic partial layer having a predetermined thickness is formed in the hybrid passivation layer. 17. The method of claim 16,
Wherein the organic-inorganic mixed solution comprises at least one organosilane of formula (1), water, and at least one silicate ester of formula (2) as an optional component. Way:
[Chemical Formula 1]
A ¹ _l A ² _m A ³ _n Si (OE ¹ ) _p (OE ² ) _q (OE ³ ) _r
(2)
Si (OG ¹ ) _? (OG ² ) _? (OG ³ ) _? (OG ⁴ ) _?
At this time, A ¹ , A ² and A ³ each independently represent an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a vinyl group, an acrylic group, a methacrylic group or an epoxy group, 1, m, and n are each independently 0 or a natural number, 1? l + m + n? 3, and E ¹ , E ² , and E ³ are each independently an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 10 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxyalkyl group having 1 to 20 carbon atoms, a fluoroalkyloxyalkyl group having 1 to 20 carbon atoms, an alkyloxyaryl group having 1 to 20 carbon atoms, An aryloxyalkyl group having 6 to 20 carbon atoms or an aryloxyaryl group having 6 to 20 carbon atoms, p, q and r are each independently 0 or a natural number of 1 to 3, 1? P + q + + m + n + p + q + r = 4,
G ¹ , G ² , G ³ and G ⁴ in the formula (2) each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms in the fluoroalkyl group and 10 to 20 carbon atoms, A fluoroalkyloxyalkyl group having 1 to 20 carbon atoms, an alkyloxyaryl group having 1 to 20 carbon atoms, an aryloxyalkyl group having 6 to 20 carbon atoms, or an aryloxyaryl group having 6 to 20 carbon atoms, ?,?,?, and? are independently 0 or a natural number of 1 to 4, and? +? +? +? = 4. 18. The method of claim 17,
Wherein the organic-inorganic mixed solution further comprises at least one kind of oxide precursor,
The oxide precursor is at least one other element selected from an alkali metal, an alkaline earth metal, a transition metal, a transition metal, a metalloid, boron and phosphorus, and is a precursor capable of forming an oxide of the other element with oxygen Wherein the organic light emitting display device comprises a light emitting diode. 17. The method of claim 16,
Further comprising forming at least one of the organic-inorganic hybrid layer and the inorganic barrier layer including an inorganic material on the hybrid protective layer. 17. The method of claim 16,
Further comprising forming at least one of the organic-inorganic hybrid layer and the inorganic barrier layer including the inorganic material between the display portion and the hybrid protective layer.

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