KR102252416B1 - Organic light emitting device and method for manufacturing thin film encapsulation layer - Google Patents

Abstract

The present invention relates to an organic light-emitting device and a method of manufacturing a thin film encapsulation layer, and more particularly, to an organic light-emitting device in which an inorganic layer and a hydrocarbon compound layer are stacked on an organic light-emitting laminate, and a method of manufacturing a thin film encapsulation layer.
An organic light emitting device according to an embodiment of the present invention includes an organic light emitting laminate formed on a substrate; And a thin film encapsulation layer provided on the organic light emitting laminate and in which inorganic layers and hydrocarbon compound layers are alternately stacked.

Description

Organic light emitting device and method for manufacturing thin film encapsulation layer

The present invention relates to an organic light-emitting device and a method of manufacturing a thin film encapsulation layer, and more particularly, to an organic light-emitting device in which an inorganic layer and a hydrocarbon compound layer are stacked on an organic light-emitting laminate, and a method of manufacturing a thin film encapsulation layer.

An organic light emitting device (OLED) having an organic light emitting laminate including a cathode, an anode, and an emission layer made of an organic material interposed therebetween is a self-luminous device and does not require a separate light source, so low voltage driving is not required. It is not only possible, but also has a wide viewing angle and has the advantage of fast response speed. However, since the organic light-emitting laminate is very vulnerable to external moisture or oxygen and has poor durability against heat, a sealing process is required to protect the organic light-emitting laminate. In the encapsulation process, a cover method in which a getter is attached to the cover of glass or metal and then attached to the organic light-emitting laminate using an adhesive, or a thin film including an organic film and/or an inorganic film on the organic light-emitting laminate (Thin Film Encapsulation (TFE) is a thin film method that deposits.

In the case of manufacturing thin film encapsulation using a thin film method, in general, a process of forming an organic film at atmospheric pressure using a solution process such as screen printing or inkjet printing, and plasma enhanced chemical vapor deposition (PECVD) or atomic A process of forming an inorganic film using a vacuum process such as Atomic Layer Deposition (ALD) is repeated a plurality of times. At this time, when the organic film is formed by a solution process, a problem in which the thickness of the organic film is non-uniform due to the problem of non-uniform discharge of the solution from the nozzle occurs, and normal pressure (organic film)-vacuum (inorganic film)-normal pressure (organic film) ) As the deposition process proceeds in order, not only the deposition process becomes cumbersome, but also a problem in which particles are introduced occurs. In addition, when the organic layer is formed, damage to the organic light-emitting laminate occurs due to the use of a solvent, and as the thickness of the organic layer increases due to the solution process, the flexible property is deteriorated, making it difficult to apply to a flexible display.

Accordingly, a thin film encapsulation may be prepared by forming only an inorganic film without an organic film on the organic light-emitting laminate, but the inorganic film is formed in a state in which all particles present on the organic light-emitting laminate and/or the inorganic film are not removed. In the case of immediate formation, when the organic light-emitting device (OLED) is bent later, particles are desorbed and the inorganic film is peeled off. When the inorganic film is peeled off, a moisture transfer path is formed from the outside to a place where the inorganic film is peeled off as the particles are separated, and there is a problem in that the organic light emitting laminate is deteriorated and durability is deteriorated therefrom.

Korean Patent Application Publication No. 10-2017-0022624

The present invention provides an organic light-emitting device including a thin-film encapsulation layer in which inorganic layers and hydrocarbon compound layers are alternately stacked on an organic light-emitting laminate, and a thin-film encapsulation layer manufacturing method therefor.

An organic light emitting device according to an embodiment of the present invention includes an organic light emitting laminate formed on a substrate; And a thin film encapsulation layer provided on the organic light emitting laminate and in which inorganic layers and hydrocarbon compound layers are alternately stacked.

The hydrocarbon compound layer may include an oligomer containing carbon and hydrogen.

The hydrocarbon compound layer may have a thicker thickness than the inorganic layer.

It may further include a hydrocarbon planarization layer interposed between the organic light-emitting laminate and the thin film encapsulation layer.

A method of manufacturing a thin film encapsulation layer according to another embodiment of the present invention includes: carrying a substrate on which an organic light emitting laminate is formed into a chamber; Depositing an inorganic layer on the organic light emitting laminate; And a process of depositing a hydrocarbon compound layer on the inorganic layer, wherein the process of depositing the inorganic layer and the process of depositing the hydrocarbon compound layer may be performed by a vapor deposition method in a vacuum atmosphere.

It may further include a process of further depositing an inorganic layer on the hydrocarbon compound layer.

The process of depositing the hydrocarbon compound layer may include providing a vapor phase source material including carbon and hydrogen; Supplying a process gas including the source material and a carrier gas for transporting the source material into the chamber; And forming a plasma in the chamber to polymerize an oligomer containing carbon and hydrogen.

The source material may contain an aliphatic hydrocarbon.

The source material is methane, ethane, propane, butane, pentane, hexane, heptane, octane , Cetane, ethylene, propylene, butylene, amylene, hexene, isoprene, acetylene, cyclopropane , Cyclobutane, cyclopentane, cyclohexane, butylcyclohexane, isopropylcyclohexane, cycloheptane, cyclooctane cyclooctane), 1-hexene, 2-methyl-1-hexene, 5-methyl-1-hexene, butadiene It may include at least any one of.

The process of depositing the hydrocarbon compound layer may further include a process of supplying a discharge gas including hydrogen, helium, nitrogen, and an inert gas of two or more cycles into the chamber.

The ratio of the volume occupied by helium and nitrogen in the total of the carrier gas and the discharge gas supplied into the chamber may be 50% or more and less than 100%.

The organic light-emitting device according to an embodiment of the present invention forms a thin film encapsulation layer by alternately stacking an inorganic layer having moisture permeation prevention properties and a hydrocarbon compound layer having flexible properties on the organic light-emitting laminate, so that the thin film encapsulation layer is flexible and very excellent. It can have moisture permeation prevention efficiency. In addition, even when particles are present on the surface of the organic light-emitting laminate or the inorganic layer, the hydrocarbon compound layer does not form a space between the surface of the organic light-emitting laminate and particles or between the surface of the inorganic layer and the particles. Alternatively, it is possible to completely cover the surface of the inorganic layer. Accordingly, it is possible to prevent the inorganic layer (or thin film encapsulation layer) from being peeled off as particles fall off the surface of the organic light-emitting laminate or the surface of the inorganic layer, and deterioration and durability of the organic light-emitting laminate due to the peeling of the inorganic layer are prevented. Can be prevented.

In addition, since the hydrocarbon compound layer can be vapor-deposited in the same way as the inorganic layer, the overall thickness of the hydrocarbon compound layer can be made uniform and the thickness of the hydrocarbon compound layer can be reduced, as well as preventing the occurrence of damage to the organic light-emitting laminate due to the use of solvents. May be. In addition, since the deposition process of the hydrocarbon compound layer can be carried out in a vacuum atmosphere, it is possible to suppress the inflow of particles to the deposition surface on the organic light-emitting laminate at atmospheric pressure (or atmospheric pressure), and a vacuum and atmospheric pressure replacement chamber may not be required. , In a single chamber, an inorganic layer and a hydrocarbon compound layer may be stacked in-situ. Through this, the footprint of the entire equipment can be reduced, equipment manufacturing cost can be reduced, and space for a clean room can be easily secured.

On the other hand, by controlling the ratio of the volume occupied by helium (He) in the total of the carrier gas and the discharge gas supplied inside the chamber, the particle coating characteristics of the hydrocarbon compound layer can be controlled, and the particles can be completely covered even with a thin thickness. .

1 is a cross-sectional view showing an organic light emitting device according to an embodiment of the present invention.
2 is a cross-sectional view showing a thin film encapsulation layer in which particles are interposed on an inorganic layer according to an embodiment of the present invention.
3 is a cross-sectional view showing an organic light emitting device including a hydrocarbon planarization layer according to an embodiment of the present invention.
Figure 4 is a flow chart showing a thin film encapsulation layer manufacturing method according to another embodiment of the present invention.
5 is a conceptual diagram illustrating a process of depositing a hydrocarbon compound layer according to another embodiment of the present invention.
6 is a conceptual diagram illustrating particle coating characteristics according to a ratio of volumes occupied by helium and nitrogen in the entire carrier gas and discharge gas supplied into a chamber according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only the present embodiments make the disclosure of the present invention complete, and the scope of the invention to those of ordinary skill in the art It is provided to inform you. In the description, the same reference numerals are assigned to the same components, and the drawings may be partially exaggerated in size in order to accurately describe the embodiments of the present invention, and the same numerals refer to the same elements in the drawings.

1 is a cross-sectional view showing an organic light emitting device according to an embodiment of the present invention.

Referring to FIG. 1, an organic light emitting device 100 according to an embodiment of the present invention includes an organic light emitting laminate 110 formed on a substrate 10; And a thin film encapsulation layer 120 provided on the organic light-emitting laminate 110 and in which the inorganic layer 121 and the hydrocarbon compound layer 122 are alternately stacked.

The organic light emitting laminate 110 may be formed on the substrate 10, may be made of an organic light emitting layer made of an organic material provided between the cathode and the anode, and between the cathode and the anode, and additionally on a transparent cathode (or upper electrode). It may also include a formed capping layer (CPL). When electrons and holes are injected into the emission layer by applying voltage to the cathode and anode respectively, the excitons formed by bonding of electrons and holes to each other transition from the excited state to the ground state, resulting in energy difference. Corresponding photons are emitted, and the organic light emitting laminate 110 generates light according to this principle.

The organic light-emitting device 100 provided with the organic light-emitting laminate 110 does not require a separate light source, so it can be driven at a low voltage, has a wide viewing angle, and has a fast response speed. However, since it is very vulnerable to external moisture or oxygen and has low durability against heat, a thin film encapsulation layer 120 is required to protect the organic light-emitting laminate 110.

The thin film encapsulation layer 120 may seal the organic light-emitting laminate 110 provided on the substrate 10 to prevent the penetration of external moisture or oxygen, and may be provided on the organic light-emitting laminate 110. , The inorganic layer 121 and the hydrocarbon compound layer 122 may be alternately stacked. Here, the order of lamination of the inorganic layer 121 and the hydrocarbon compound layer 122 is not particularly limited, but it may be preferable that the inorganic layer 121 having excellent moisture permeation prevention properties is deposited in contact with the organic light-emitting laminate 110.

The inorganic layer 121 has a dense thin film so that the penetration of moisture or oxygen can be suppressed, and the penetration of most of the moisture and oxygen into the organic light-emitting laminate 110 by the inorganic layer 121 is blocked. I can. Here, the inorganic layer 121 may _{include a film having a composition of SiN x} , SiO _y or SiN _x O _y , and may have hydrophobic properties as the amount (x) of nitrogen (N) increases. . At this time, carbon (C) may be added (or doped) to the inorganic layer 121, through which it is possible to provide flexible properties to the inorganic layer 121, and the hydrocarbon compound layer due to material similarity to the hydrocarbon compound layer 122 It is also possible to enhance the adhesive property with (122).

The hydrocarbon compound layer 122 may include carbon (C) and hydrogen (H), and a vertical pinhole generated in the lower inorganic layer 121 deposited first is then deposited on the upper inorganic layer. Transition to the layer 121 may be suppressed or prevented. In addition, the hydrocarbon compound layer 122 may function as a buffer layer (or a stress relaxation layer) that reduces stress between the inorganic layer 121 and the inorganic layer 121 in addition to inhibiting moisture permeation. In addition, since the hydrocarbon compound layer 122 has a planarization characteristic, the top surface of the thin film encapsulation layer 120 may be flat, and may have ductility to provide ductility to the thin film encapsulation layer 120.

In general, an organic film is formed at atmospheric pressure (or atmospheric pressure) by using a solution process such as screen printing or inkjet printing to provide ductility to the thin film encapsulation. It is uniformly discharged to cause a problem in that the overall thickness of the organic film is uneven, and the organic light-emitting laminate 110 is damaged due to the solvent remaining in the solution. In addition, since the flexible property decreases as the thickness of the organic layer increases due to the solution process, it is difficult to apply a thin film encapsulation including the organic layer to a flexible display or the like.

However, the hydrocarbon compound layer 122 can be deposited by a vapor deposition method such as plasma enhanced chemical vapor deposition (PECVD), so that the overall thickness of the hydrocarbon compound layer 122 is uniform and the thickness of the hydrocarbon compound layer 122 is reduced. It can be made thin, and it is possible to prevent the occurrence of damage to the organic light-emitting laminate 110 due to the use of a solvent. In addition, since the deposition process of the hydrocarbon compound layer 122 can be carried out in a vacuum atmosphere, it is possible to suppress the inflow of particles 20 to the deposition surface on the organic light-emitting laminate 110 at normal pressure, and replace the vacuum and atmospheric pressure. A chamber may not be required, and the inorganic layer 121 and the hydrocarbon compound layer 122 may be stacked in-situ in a single chamber. Through this, the footprint of the entire equipment can be reduced, equipment manufacturing cost can be reduced, and space for a clean room can be easily secured.

In addition, the hydrocarbon compound layer 122 may include an oligomer containing carbon (C) and hydrogen (H). Here, the hydrocarbon compound layer 122 may contain a monomer that is not an oligomer due to less polymerization, but a polymer having a molecular weight greater than 1,400 or the number of monomers greater than 16 is not included. When a monomer containing carbon (C) and hydrogen (H) is polymerized and solidified into an oligomer having a molecular weight of 1,400 or less or the number of monomers bound by a carbon chain, 2 to 16, the hydrocarbon compound layer 122 is It can have moisture permeability.

If the hydrocarbon compound layer 122 is made of only monomers, the hydrocarbon compound layer 122 is not dense and the thin film is unstable, so it cannot have moisture permeability. On the contrary, if the hydrocarbon compound layer 122 is made of a polymer, Since the bonding force is too high and the bonding force with the lower layer such as the inorganic layer 121 is lowered, the entire hydrocarbon compound layer 122 may be easily separated (or peeled off) from the lower layer.

However, when the hydrocarbon compound layer 122 is composed of an oligomer containing carbon (C) and hydrogen (H), the hydrocarbon compound layer 122 is dense and may have high moisture permeability. Problems can be solved.

In addition, since the hydrocarbon compound layer 122 contains carbon (C), the stress is small compared to the inorganic layer 121, and functions as a stress relaxation layer interposed between the inorganic layer 121 and the inorganic layer 121 It may be suitable for: In addition, a thin film made of an oligomer containing carbon (C) and hydrogen (H) may have high mechanical strength and excellent light transmittance. On the other hand, the carbon nitride (CN) film, which was conventionally used in place of the organic film, has a property of absorbing light, but a thin film made of an oligomer containing carbon (C) and hydrogen (H) is Since it does not absorb the emitted light, it may be suitable for use in the thin film encapsulation layer 120 of the organic light emitting device 100. And the thin film made of oligomer containing carbon (C) and hydrogen (H) is hydrophobic, so it does not allow moisture to pass through, and hydrogen (H) retains oxygen (O) by reducing reaction with nearby oxygen (O). I can not do it. That is, if the hydrocarbon compound layer 122 includes an oligomer containing carbon (C) and hydrogen (H), moisture permeability, oxidation resistance, and light transmittance may be excellent, and the characteristics of the organic light-emitting laminate 110 may be improved. Since it is possible to relieve the stress between the inorganic layer 121 and the inorganic layer 121 while maintaining it in a good state, it may be one of the best materials for use in the thin film encapsulation layer 120 of the organic light emitting device 100. have.

Meanwhile, the hydrocarbon compound layer 122 may include an amorphous hydrocarbon. The hydrocarbon compound layer 122 containing an oligomer containing carbon (C) and hydrogen (H) and the hydrocarbon compound layer 122 containing an amorphous hydrocarbon secures a deposition rate of 100 nm/min or more while forming the hydrocarbon compound layer 122 Oligomers or amorphous hydrocarbons containing carbon (C) and hydrogen (H) can be deposited with a desired appropriate deposition rate. At this time, when the hydrocarbon compound layer 122 is formed by plasma chemical vapor deposition (PECVD), the deposition rate can be precisely controlled, so that the hydrocarbon compound layer 122 has a relatively thin thickness compared to the thickness of the organic film formed by the solution process. The formation of may be possible. In addition, when the hydrocarbon compound layer 122 is deposited using plasma, polymerization of the monomer may be well performed. In addition, the hydrocarbon compound layer 122 may have an unstable carbon chain structure passivated with hydrogen (H).

2 is a cross-sectional view showing a thin film encapsulation layer in which particles are interposed on an inorganic layer according to an embodiment of the present invention.

1 and 2, the hydrocarbon compound layer 122 may have a thicker thickness than the inorganic layer 121. Particles 20 that cannot be removed may exist on the surface of the organic light-emitting laminate 110 or the inorganic layer 121, and the inorganic layer 121 has poor ductility or wetting characteristics, so the organic light-emitting laminate 110 ) It cannot be deposited while evenly filling the space existing between the surface and the particle 20 or between the surface of the inorganic layer 121 and the particle 20 (hereinafter, between the surface and the particle of the lower layer), and organic light emission with the particle 20 The laminate 110 or the inorganic layer 121 cannot be completely covered. In this case, the probability that external moisture or oxygen will permeate through the uncoated gap may increase, and the particles 20 may be detached and the inorganic layer 121 may be peeled off.

On the other hand, the hydrocarbon compound layer 122 has excellent ductility and wetting characteristics, so even when the particles 20 are present on the surface of the organic light emitting laminate 110 or the inorganic layer 121, the surface and particles of the lower layer (110 or 121) (20) It is possible to completely cover the organic light-emitting laminate 110 or the inorganic layer 121 together with the particles 20 without forming a space therebetween. That is, when the particles 20 exist on the surface of the organic light-emitting laminate 110 or the inorganic layer 121, the area under the particles 20 on the surface of the organic light-emitting laminate 110 or the inorganic layer 121 An inverse taper-shaped space is generated, and by filling this space evenly with the hydrocarbon compound layer 122, the surface (or shape) of the hydrocarbon compound layer 122 on which the inorganic layer 121 is deposited is tapered. It can be made into shape. Through this, even when the particles 20 exist on the surface of the organic light-emitting laminate 110 or the inorganic layer 121, the inorganic layer 121 can be well deposited without being affected by the particles 20. In addition, it is possible to prevent a phenomenon in which the particles 20 existing on the surface of the organic light-emitting laminate 110 or the inorganic layer 121 fall off, and accordingly, the inorganic layer 121 Peeling (or thin film peeling) can be prevented, and deterioration and durability of the organic light-emitting laminate 110 resulting from peeling of the inorganic layer 121 can be prevented.

Here, the size (or diameter or width) of the particle 20 may be several micrometers (eg, about 3 μm), and exist on the surface of the organic light-emitting laminate 110 or the inorganic layer 121. In order to completely cover the particles 20 so that desorption of the particles 20 can be prevented, the hydrocarbon compound layer 122 must be deposited with a predetermined thickness or more, and the hydrocarbon compound layer 122 is thicker than the inorganic layer 121 Can have. In this case, the predetermined thickness may be determined according to the size of the particle 20. For example, the thickness of the hydrocarbon compound layer 122 may be 1/4 or more of the size of the particle 20, preferably 1/4 to 1/2 of the size of the particle 20, and more preferably, It may be 1/4 to 5 μm (eg, 0.5 to 5 μm) of the size of the particle 20. When the thickness of the hydrocarbon compound layer 122 becomes thicker than 5 µm, the overall thickness of the thin film encapsulation layer 120 becomes too thick, making it difficult to apply to a flexible display, etc., and the thickness of the hydrocarbon compound layer 122 becomes particles 20 If it becomes thinner than 1/4 of the size, it is impossible to completely cover the particle 20 without a gap. Meanwhile, the thickness of the inorganic layer 122 may be 1 μm or less, preferably 0.5 μm or less, more preferably greater than 0 μm, and less than or equal to 0.2 μm. When the thickness of the inorganic layer 122 becomes thicker than 1 µm, the flexibility decreases and cracks occur in the inorganic layer 122 when it is bent, and oxygen or moisture penetrates by such cracks and the organic light-emitting laminate ( 110). Accordingly, the hydrocarbon compound layer 122 may have a thickness of 5 µm or less, and the inorganic layer 122 may have a thickness of 1 µm or less to facilitate application to a flexible display, etc., through which the thin film encapsulation layer 120 While reducing the overall thickness, it is possible to prevent cracks of the inorganic layer 122 as well as secure moisture permeation prevention characteristics.

In addition, by appropriately controlling the deposition rate, the hydrocarbon compound layer 122 can be deposited while evenly filling the space between the surface of the lower layer 110 or 121 and the particle 20, and vapor deposition such as plasma chemical vapor deposition (PECVD) In the case of depositing a hydrocarbon compound layer 122 containing an oligomer containing carbon (C) and hydrogen (H) or a hydrocarbon compound layer 122 containing an amorphous hydrocarbon through the evaporation method, the deposition rate can be precisely controlled and thus hydrocarbons The compound layer 122 may more completely cover the organic light emitting laminate 110 without forming a space between the surface of the lower layer and the particles 20.

3 is a cross-sectional view showing an organic light emitting device including a hydrocarbon planarization layer according to an embodiment of the present invention.

Referring to FIG. 3, the organic light emitting device 100 according to the present invention may further include a hydrocarbon planarization layer 115 interposed between the organic light emitting laminate 110 and the thin film encapsulation layer 120. The hydrocarbon planarization layer 115 may be interposed between the organic light-emitting laminate 110 and the thin film encapsulation layer 120, and is provided to cover the organic light-emitting laminate 110 in contact with the organic light-emitting laminate 110. In addition, the particles 20 may be provided on the surface of the organic light-emitting laminate 110 in which particles 20 may be present, so that the deposition surface of the thin film encapsulation layer 120 may be planarized.

The hydrocarbon planarization layer 115 may include carbon (C), and may have less stress than the thin film encapsulation layer 120, and accordingly relieve the stress of the thin film encapsulation layer 120, thereby reducing the organic light-emitting laminate ( 110) can prevent excessive stress. Through this, stress is applied to the interface between the organic light-emitting laminate 110 and the thin film encapsulation layer 120 to prevent destruction near the interface of the organic light-emitting laminate 110 or the thin film encapsulation layer 120 from being peeled off.

In addition, the hydrocarbon planarization layer 115 does not form a space between the surface of the organic light-emitting laminate 110 and the particles 20 to remove the particles 20 remaining on the surface of the organic light-emitting laminate 110. By completely covering the light-emitting laminate 110, the deposition surface of the thin film encapsulation layer 120 can be flattened, and the particles 20 existing on the surface of the organic light-emitting laminate 110 fall off and the particles 20 By this, it is possible to prevent the thin film encapsulation layer 120 from being peeled off, and accordingly, it is possible to prevent the formation of a moisture transfer path from the outside where the encapsulation layer 120 is peeled and formed.

Here, the thickness of the hydrocarbon planarization layer 115 may be the same as the thickness of the hydrocarbon compound layer 122 or may be thicker than the thickness of the hydrocarbon compound layer 122. Since the hydrocarbon planarization layer 115 must also completely cover the particles 20 to provide a flat surface on which the thin film encapsulation layer 120 is deposited, a hydrocarbon that completely covers the particles 20 existing on the surface of the inorganic layer 121 It may be the same as or thicker than the thickness of the compound layer 122, and has excellent adhesion characteristics, and a hydrocarbon compound layer to planarize the deposition surface of the thin film encapsulation layer 120 so that the thin film encapsulation layer 120 can be deposited more stably. 122) can be thicker than the thickness.

4 is a flowchart showing a method of manufacturing a thin film encapsulation layer according to another embodiment of the present invention.

A method of manufacturing a thin film encapsulation layer according to another embodiment of the present invention will be described in more detail with reference to FIG. 4, and details that overlap with those previously described in relation to the organic light emitting device according to an embodiment of the present invention will be omitted. .

A method of manufacturing a thin film encapsulation layer according to another embodiment of the present invention includes the process of carrying the substrate 10 on which the organic light emitting laminate 110 is formed into the chamber 210 (S100); Depositing an inorganic layer 121 on the organic light emitting laminate 110 (S200); And a process of depositing a hydrocarbon compound layer on the inorganic layer 121 (S300), wherein the process of depositing the inorganic layer 121 (S200) and the process of depositing the hydrocarbon compound layer (S300) It can be carried out by vapor deposition in a vacuum atmosphere.

First, the substrate 10 on which the organic light emitting laminate 110 is formed is carried into the chamber 210 (S100). Since the organic light-emitting laminate 110 is very vulnerable to external moisture or oxygen, and has poor durability against heat, a thin film encapsulation (layer) to protect the organic light-emitting laminate 110 is formed (or deposited). To do this, the substrate 10 on which the organic light emitting laminate 110 is formed may be carried into the chamber 210. In this case, the substrate 10 carried into the chamber 210 may be supported by the substrate support unit 220. Here, the chamber 210 may be a vacuum chamber, and the method of manufacturing the thin film encapsulation layer of the present invention may further include a process of forming a vacuum in the chamber 210 (S150).

Next, an inorganic layer 121 is deposited on the organic light emitting laminate 110 (S200). When the substrate 10 on which the organic light-emitting laminate 110 is formed is introduced into the chamber 210, the inorganic layer 121 may be deposited by a vapor deposition method after forming a vacuum atmosphere in the chamber 210. . The inorganic layer 121 has a dense thin film so that the penetration of moisture or oxygen can be suppressed, and the penetration of most of the moisture and oxygen into the organic light-emitting laminate 110 by the inorganic layer 121 is blocked. I can.

Then, a hydrocarbon compound layer is deposited on the inorganic layer 121 (S300). After depositing the inorganic layer 121 on the organic light emitting laminate 110, a hydrocarbon compound layer may be deposited by vapor deposition in a vacuum atmosphere. The hydrocarbon compound layer may include carbon (C) and hydrogen (H), and a vertical pinhole generated in the lower inorganic layer 121 deposited first is then deposited on the upper inorganic layer ( 121 may be suppressed or prevented from being transferred, and a pinhole formed in the lower inorganic layer 121 may be prevented from communicating with the pinhole formed in the upper inorganic layer 121.

In this way, the process of depositing the inorganic layer 121 (S200) and the process of depositing the hydrocarbon compound layer (S300) may be performed by a vapor deposition method in a vacuum atmosphere, and the organic light emitting laminate ( 110) It is possible to suppress the inflow of particles to the deposition surface, and a vacuum and atmospheric pressure displacement chamber may not be required, and the inorganic layer 121 and the above-mentioned inorganic layer 121 and the above in a single chamber in-situ (in-situ) can be suppressed. A hydrocarbon compound layer can also be laminated. Through this, the footprint of the entire equipment can be reduced, equipment manufacturing cost can be reduced, and space for a clean room can be easily secured.

Here, the deposition order of the inorganic layer 121 and the hydrocarbon compound layer is not particularly limited, but it may be preferable that the inorganic layer 121 having excellent moisture permeation prevention properties is first deposited in contact with the organic light-emitting laminate 110.

The method of manufacturing a thin film encapsulation layer according to the present invention may further include a process of further depositing an inorganic layer 121 on the hydrocarbon compound layer (S400).

In addition, an inorganic layer 121 may be further deposited on the hydrocarbon compound layer (S400). Since the hydrocarbon compound layer does not have better moisture permeation prevention properties than the inorganic layer 121, an inorganic layer 121 is further deposited on the hydrocarbon compound layer to prevent the hydrocarbon compound layer from being exposed to the outside to allow for moisture permeation of the thin film encapsulation layer. The prevention properties can be further improved. In the present invention, the hydrocarbon compound layer 122 having ductility and moisture permeability including carbon (C) is interposed between the inorganic layer 121 and the inorganic layer 121, so that the inorganic layer 121/hydrocarbon compound layer / With only the three-layer structure of the inorganic layer 121, a thin film encapsulation layer having excellent moisture permeation prevention properties can be manufactured. That is, the hydrocarbon compound layer has moisture permeability while suppressing pinhole growth between the inorganic layers 121 and can effectively block the penetration of moisture or oxygen from the outside, so that the inorganic layer 121/hydrocarbon compound layer/inorganic layer 121 Even with a three-layer structure, it is possible to secure sufficiently excellent moisture permeation prevention properties. In addition, even when particles are present on the surface of the organic light-emitting laminate 110 or the inorganic layer 121, a reverse taper formed in the area under the particles on the surface of the organic light-emitting laminate 110 or the inorganic layer 121 By evenly filling the (taper)-shaped space with the hydrocarbon compound layer, the surface (or shape) of the hydrocarbon compound layer 122 on which the inorganic layer 121 is deposited may be tapered, and accordingly, the organic light-emitting laminate ( 110) or even when the particles 20 exist on the surface of the inorganic layer 121, the inorganic layer 121 can be deposited well without being affected by the particles 20, so the inorganic layer 121/hydrocarbon compound layer/inorganic It may not be necessary to laminate the inorganic layer 121 and the hydrocarbon compound layer a plurality of times in a more than three-layer structure of the layer 121. Accordingly, it is possible to reduce the manufacturing cost of the thin film encapsulation layer by reducing the number of laminations of the inorganic layer 121 and/or the hydrocarbon compound layer.

5 is a conceptual diagram illustrating a process of depositing a hydrocarbon compound layer according to another embodiment of the present invention.

Referring to FIG. 5, the process of depositing the hydrocarbon compound layer (S300) includes a process of providing a vaporous source material including carbon (C) and hydrogen (H) (S310); Supplying a process gas including the source material and a carrier gas for transporting the source material into the chamber 210 (S320); And forming a plasma 40 in the chamber 210 to polymerize an oligomer containing carbon (C) and hydrogen (H) (S330).

In the process of depositing the hydrocarbon compound layer (S300), a vapor source material including carbon (C) and hydrogen (H) may be first provided (S310). Here, the source material solution 30 including carbon (C) and hydrogen (H) may be bubbled to generate a vaporous source material. At this time, the temperature of the source material solution 30 accommodated in the source container 230 may be controlled and bubbled through a carrier gas to generate the vaporous source material. The vapor-like source material generated in this way is introduced into the supply pipe 242 connected to the chamber 210 and injected through an injection unit 241 such as a showerhead, and thus may be provided (or supplied) to the inside of the chamber 210. . Meanwhile, the method of supplying the vaporous source material is not limited thereto, and various vaporization methods may be used in addition to the bubbling method, and various types of vaporizers may be used to supply the vaporous source material.

Then, a process gas including the source material (ie, the vaporous source material) and a carrier gas for transporting the source material may be supplied into the chamber 210 (S320). The carrier gas may not only be used to bubble the source material solution 30, but may also serve to assist the movement of the vapor phase source material, and may transport the vapor phase source material. The vapor source material is in an unstable state that can be easily liquefied, and since it is heavier than a gaseous state, it does not move smoothly, and thus may be transported (or supplied) into the chamber 210 through the carrier gas. In this way, the hydrocarbon compound layer may be deposited by supplying the process gas including the vaporous source material and the carrier gas into the chamber 210.

In addition, a plasma 40 may be formed in the chamber 210 to polymerize an oligomer containing carbon (C) and hydrogen (H) (S330). The hydrocarbon compound layer can be deposited by forming a plasma 40 inside the chamber 210, and a monomer containing carbon (C) and hydrogen (H) is polymerized into an oligomer through the plasma 40 to solidify it. can do. When the oligomer is polymerized using the plasma 40, the polymerization is well performed and the hydrocarbon compound layer can be densely deposited, thereby ensuring the moisture permeability of the hydrocarbon compound layer. At this time, hydrogen (H) may passivate the molecular structure of an unstable carbon chain, the hydrocarbon compound layer may be stabilized in the form of a thin film, and reliability of the hydrocarbon compound layer may be secured.

The source material may contain an aliphatic hydrocarbon. Since the aliphatic hydrocarbon is composed of only carbon (C) and hydrogen (H), it may not damage the organic light-emitting stack 110 and may not affect the inorganic layer 121. In addition, since the aliphatic hydrocarbon has high chemical reactivity, it can be polymerized well into an oligomer, and it can be easy to deposit the dense hydrocarbon compound layer.

And the source material may be composed of only carbon (C) and hydrogen (H), methane (methane), ethane (ethane), propane (propane), butane (butane), pentane (pentane), heck Hexane, heptane, octane, cetane, ethylene, propylene, butylene, amylene, hexene, Isoprene, acetylene, cyclopropane, cyclobutane, cyclopentane, cyclohexane, butylcyclohexane, isopropylcyclohexane Isopropylcyclohexane, cycloheptane, cyclooctane, 1-hexene, 2-methyl-1-hexene, 5-methyl-1 -It may contain at least one of hexene (5-methyl-1-hexene) and butadiene. Since the source material is composed of only carbon (C) and hydrogen (H), there is no need to separate (or remove) unnecessary elements, and it is possible to prevent the separated unnecessary elements from acting as impurities or particles. In addition, the source material is composed of only carbon (C) and hydrogen (H), so that the polymerization of monomers containing carbon (C) and hydrogen (H) can be well performed, and can be well polymerized into a dense oligomer.

6 is a conceptual diagram illustrating particle coating characteristics according to a ratio of volumes occupied by helium and nitrogen in the entire carrier gas and discharge gas supplied into the chamber according to another embodiment of the present invention. FIG. 6(a) is It shows a case where the volume ratio of helium and nitrogen is less than 50%, FIG. 6(b) shows a case where the volume ratio of helium and nitrogen is 50%, and FIG. 6(c) shows a case where the volume ratio of helium and nitrogen is 50% It represents a larger case.

Referring to FIG. 6, the process of depositing the hydrocarbon compound layer (S300) is _{a discharge including hydrogen (H 2} ), helium (He), nitrogen (N ₂ ) and an inert gas of two or more cycles into the chamber 210 A process of supplying gas (S325) may be further included.

In the process of polymerizing the oligomer containing carbon (C) and hydrogen (H) (S330), while forming a plasma 40 in the chamber 210, the hydrogen ( H ₂ ), helium (He), nitrogen (N ₂ ) and an inert gas of 2 or more cycles (e.g., neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), Discharge gas containing organeson (Og)) can be supplied. That is, the plasma 40 may be generated by injecting a discharge gas into the chamber 210. Through this, the plasma 40 can be generated well, the oligomer containing carbon (C) and hydrogen (H) can be polymerized well, and the more dense hydrocarbon compound layer can be deposited. Here, the inert gas of two or more cycles may mean an inert gas of two or more cycles on the periodic table, and may be an element of Group 18 (inert gas) of two or more cycles of the periodic table.

In this case, hydrogen (H ₂ ) of the discharge gas may be used to passivate unstable carbon chain bonds in the hydrocarbon compound layer. Passivation of unstable carbon chain bonds with _{hydrogen (H 2} ) of the discharge gas to effectively passivate the molecular structure of the carbon chain because only hydrogen (H) contained in the vapor phase source material may not be sufficient. It can replenish the hydrogen atom (H) used for it. For example, since hydrogen (H) contained in the vapor phase source material may be in a state of being bonded with carbon (C), it may not be easy to passivate the carbon chain bond, and thus bond with carbon (C). Unstable hydrogen (H ₂ ) can be used as the discharge gas to supplement hydrogen atoms (H) that are insufficient to passivate unstable carbon chain bonds.

And helium (He) and nitrogen (N ₂ ) of the discharge gas are in the vapor phase between the surface of the organic light emitting laminate 110 and particles or between the surface of the inorganic layer 121 and particles (hereinafter, between the surface of the lower layer and particles). It can play a role in helping the source material to be filled. A detailed description of this will be described later.

Since the vapor phase source material has a directionality and is deposited on the organic light-emitting laminate 110 or the inorganic layer 121, it may not be well filled between the surface of the lower layer 110 or 121 and the particles, and the particle coating property ( Or wetting properties) may be poor.

_{Accordingly, the ratio of the volume occupied by helium (He) and nitrogen (N 2} ) in the total of the carrier gas and the discharge gas supplied into the chamber 210 may be 50% or more and less than 100%, preferably 50 To 90%, more preferably greater than 50% and less than 80%. Here, the carrier gas may include an inert gas, and may be, for example, argon (Ar), helium (He), or nitrogen (N ₂ ). _{Helium (He) and nitrogen (N 2} ) may be included in the entire of the carrier gas and the discharge gas supplied into the chamber 210, and the vapor phase source between the surface of the lower layer (110 or 121) and particles It can be used to help the material to be filled, and can improve particle coating properties of the hydrocarbon compound layer.

Since the carrier gas supplied into the chamber 210 and the inert gas of two or more cycles included in the entire discharge gas have a large particle size and a large atomic weight (or mass), the surface of the lower layer 110 or 121 It cannot be diffused into a small space between the particles and the lower layer 110 or 121, and damage may be caused to the lower layer 110 or 121 when contacting (or colliding) with the surface of the lower layer 110 or 121. That is, when the ratio of the inert gas (eg, argon) of two or more cycles is higher than the volume ratio of helium (He) and nitrogen (N _{2 ), as shown in FIG. 6(a), the covering property is deteriorated.} And hydrogen (H) contained in the entire carrier gas and the discharge gas supplied to the inside of the chamber 210 is so reactive that if excessively supplied, the thin film characteristics of the lower layer (110 or 121) may be affected. I can.

However, helium (He) is not only an inert gas, but also has a very small particle size and a small atomic weight, so it does not affect (or damage) the lower layer (110 or 121) and between the surface of the lower layer (110 or 121) and the particles. It can seep (or diffuse) into small spaces. Accordingly, helium (He) may induce the vapor phase source material to be filled between the surface of the lower layer 110 or 121 and the particles by pushing the vapor phase source material between the particles and the surface of the lower layer 110 or 121 . Through this, the organic light emitting laminate 110 or the inorganic layer 121 can be completely covered with the particles with the hydrocarbon compound layer without forming a space between the surface of the lower layer (110 or 121) and the particles, and the organic light emitting laminate Particles existing on the surface of the sieve 110 or the inorganic layer 121 may be prevented from falling off. This can prevent peeling of the inorganic layer 121 (or peeling of the thin film encapsulation layer) due to the particles falling off, and deterioration and durability of the organic light-emitting laminate 110 caused by the peeling of the inorganic layer 121 can be prevented. Can be prevented. In addition, nitrogen (N ₂ ) may have these characteristics in the same way as helium (He).

In the case of FIG. 6(a) _{, the volume ratio of helium (He) and nitrogen (N 2} ) is less than 50% compared to other gases such as an inert gas (eg, argon) of two or more cycles, reducing particle coating properties. Although a gap occurs at the boundary between the hydrocarbon compound layer on the organic light-emitting laminate 110 or the inorganic layer 121 and the hydrocarbon compound layer on the particles, in the case of Figs. 6(b) and (c), the volume ratio of helium is different from the gas. Compared to 50% or more, the hydrocarbon compound layer is continuously formed (or deposited) on the particles, so that a space (or gap) between the surface of the lower layer (110 or 121) and the particles is not formed, and the organic light-emitting laminate (110) with particles Alternatively, the surface of the inorganic layer 121 is completely covered.

_{That is, when the ratio of the volume occupied by helium (He) and nitrogen (N 2} ) in the total of the carrier gas and the discharge gas supplied into the chamber 210 is less than 50%, helium (He) and nitrogen ( Since _{the volume ratio of N 2} ) is relatively smaller than that of the other gases, helium (He) and/or nitrogen (N ₂ ) do not diffuse freely due to the directionality (eg, the direction of gravity) of the other gas(s). The vapor source material cannot be pushed between the surface of the lower layer 110 or 121 and the particles, so that the vapor source material cannot be induced to be filled between the surface of the lower layer 110 or 121 and the particles. Accordingly, the coating properties deteriorate. In addition, since the other gas(s) has a large mass, it may damage the lower layer 110 or 121 when it comes into contact with the surface of the lower layer 110 or 121. On the other hand, when the ratio of the volume occupied by the helium (He) and nitrogen (N ₂ ) is greater than 90%, only the small helium (He) and nitrogen (N ₂ ) having a small particle size and a small mass increases, and the particle size and The volume ratio of the other gas(s) having a large mass becomes relatively small, so that the vaporous source material supplied into the chamber 210 cannot be sufficiently activated (or excited), and the plasma 40 is effectively generated. (Or discharge), and the plasma 40 cannot be stably formed.

_{Therefore, the ratio of the volume occupied by helium (He) and nitrogen (N 2} ) in the total of the carrier gas and the discharge gas supplied into the chamber 210 may be 50% or more and less than 100%, and thus the hydrocarbon The compound layer may completely cover the surface of the organic light emitting laminate 110 or the inorganic layer 121 together with the particles without forming a space between the surface of the lower layer and the particles.

As described above, in the present invention, by forming a thin film encapsulation layer by alternately stacking an inorganic layer having moisture permeation prevention properties and a hydrocarbon compound layer having flexible properties on the organic light-emitting laminate, the thin film encapsulation layer is flexible and can have very excellent moisture permeation prevention efficiency. have. In addition, when particles are present on the surface of the organic light-emitting laminate or the inorganic layer, the hydrocarbon compound layer does not form a space between the surface of the organic light-emitting laminate and the particles or between the surface of the inorganic layer and the particles, and the surface of the organic light-emitting laminate or the inorganic layer It can cover completely on the surface. Accordingly, it is possible to prevent the inorganic layer (or thin film encapsulation layer) from being peeled off as particles fall off the surface of the organic light-emitting laminate or the surface of the inorganic layer, and deterioration and durability of the organic light-emitting laminate due to the peeling of the inorganic layer are prevented. Can be prevented. In addition, since the hydrocarbon compound layer can be vapor-deposited in the same way as the inorganic layer, the overall thickness of the hydrocarbon compound layer can be made uniform and the thickness of the hydrocarbon compound layer can be reduced, as well as preventing the occurrence of damage to the organic light-emitting laminate due to the use of solvents. May be. In addition, since the deposition process of the hydrocarbon compound layer can be carried out in a vacuum atmosphere, it is possible to suppress or prevent the inflow of particles to the deposition surface on the organic light-emitting laminate at atmospheric pressure (or atmospheric pressure), and a vacuum and atmospheric pressure replacement chamber is not required. Alternatively, the inorganic layer and the hydrocarbon compound layer may be stacked in situ in a single chamber. Through this, the footprint of the entire equipment can be reduced, equipment manufacturing cost can be reduced, and space in a clean room can be easily secured. On the other hand, by controlling the ratio of helium in the total of the carrier gas and the discharge gas supplied into the chamber, the particle coating characteristics of the hydrocarbon compound layer can be controlled, and the particles can be completely covered even with a thin thickness.

The meaning of “on” used in the above description includes a case where it is in direct contact and a case where it is not in direct contact but is located opposite to the upper or lower surface, and is not only located opposite to the entire upper or lower surface, but also partially It is also possible to be positioned opposite to each other, and was used to mean that it faces apart from the position or directly contacts the upper or lower surface.

Although preferred embodiments of the present invention have been illustrated and described above, the present invention is not limited to the above-described embodiments, and common knowledge in the field to which the present invention pertains without departing from the gist of the present invention claimed in the claims. Those who have a will understand that various modifications and equivalent other embodiments are possible from this. Therefore, the technical protection scope of the present invention should be determined by the following claims.

10: substrate 20: particle
30: source material solution 40: plasma
100: organic light emitting device 110: organic light emitting laminate
115: hydrocarbon planarization layer 120: thin film encapsulation layer
121: inorganic layer 122: hydrocarbon compound layer
210: chamber 220: substrate support
230: source container 241: spray unit
242: supply pipe

Claims (11)

An organic light emitting laminate formed on the substrate; And
Including; provided on the organic light-emitting laminate, a thin film encapsulation layer in which inorganic layers and hydrocarbon compound layers are alternately stacked, and
An organic light-emitting device further comprising a hydrocarbon planarization layer interposed between the organic light-emitting laminate and the thin film encapsulation layer. The method according to claim 1,
The hydrocarbon compound layer is an organic light-emitting device comprising an oligomer containing carbon and hydrogen. The method according to claim 1,
The hydrocarbon compound layer is an organic light emitting device having a thicker thickness than the inorganic layer. delete Carrying the substrate on which the organic light-emitting laminate is formed into the chamber;
Depositing an inorganic layer on the organic light emitting laminate; And
Including; depositing a hydrocarbon compound layer on the inorganic layer,
The process of depositing the inorganic layer and the process of depositing the hydrocarbon compound layer are performed by vapor deposition in a vacuum atmosphere,
The process of depositing the hydrocarbon compound layer,
Providing a vapor phase source material containing carbon and hydrogen;
Supplying a process gas including the source material and a carrier gas for transporting the source material into the chamber; And
A method of manufacturing a thin film encapsulation layer comprising the step of polymerizing an oligomer containing carbon and hydrogen by forming a plasma in the chamber. The method of claim 5,
The method of manufacturing a thin film encapsulation layer further comprising a; process of further depositing an inorganic layer on the hydrocarbon compound layer. delete The method of claim 5,
The source material is a method of manufacturing a thin film encapsulation layer containing an aliphatic hydrocarbon. The method of claim 5,
The source material is methane, ethane, propane, butane, pentane, hexane, heptane, octane , Cetane, ethylene, propylene, butylene, amylene, hexene, isoprene, acetylene, cyclopropane , Cyclobutane, cyclopentane, cyclohexane, butylcyclohexane, isopropylcyclohexane, cycloheptane, cyclooctane cyclooctane), 1-hexene, 2-methyl-1-hexene, 5-methyl-1-hexene, butadiene Thin film encapsulation layer manufacturing method comprising at least any one of. The method of claim 5,
The process of depositing the hydrocarbon compound layer further comprises supplying a discharge gas including hydrogen, helium, nitrogen, and an inert gas of two or more cycles into the chamber. The method of claim 10,
The method of manufacturing a thin film encapsulation layer in which the ratio of the volume occupied by helium and nitrogen in the total of the carrier gas and the discharge gas supplied into the chamber is 50% or more and less than 100%.

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