KR20170045860A - Method of forming a film for preventing humidity from percolation and manufacturing an organic light emitting device using the same - Google Patents

Abstract

The present invention provides a method of forming a waterproof film, which can be applied to an organic light emitting device, and a method of manufacturing an organic light emitting device. The method of forming a waterproof film includes a process of laminating a waterproof layer made of an organic insulating material, and a process of laminating a second waterproof layer made of an inorganic insulating material on the first waterproof layer, wherein the process of laminating the first waterproof layer includes a process of depositing an evaporation material in a fluid state and a process of curing the deposition material deposited.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a moisture permeable barrier film and an organic light emitting device using the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a moisture barrier layer, and more particularly, to a method of forming a moisture barrier layer that can be applied to an organic light emitting diode.

Organic light emitting devices are problematic in that when the moisture penetrates into the organic light emitting devices, the devices are easily deteriorated to deteriorate device characteristics and shorten the lifetime. Therefore, a moisture permeation preventive film for preventing moisture permeation is essentially formed in the organic light emitting element.

Conventionally, as the material of the moisture barrier layer, SiN _x . The SiN _x is deposited by a Plasma Enhanced Chemical Vapor Deposition (PECVD) process.

However, the SiN _x In the case of forming a moisture permeation preventing film, it is possible to prevent the SiN _x There is a possibility that cracks may occur in the substrate. When cracks are generated in the SiNx, the moisture permeation preventing effect is deteriorated, and the organic light emitting device easily deteriorates over time.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method of forming a moisture permeation preventive film capable of improving the effect of preventing moisture permeation due to particles generated during the process, And a method thereof.

In order to achieve the above-mentioned object, the present invention provides a method of manufacturing a semiconductor device, comprising the steps of: laminating a first moisture- And a second moisture barrier layer made of an inorganic insulating material on the first moisture barrier layer, wherein the step of laminating the first moisture barrier layer comprises: a step of depositing an evaporation material in a fluid state; And a step of curing the material.

The process of depositing the deposition material in the fluid state can be performed in a process chamber having a process pressure in the range of 0.8 to 2 Torr.

The step of curing the deposited deposition material may include a step of plasma-treating the deposition material.

The plasma treatment may be performed using N ₂ O or O ₂ as a reaction gas.

The source material of the deposition material may be supplied into the process chamber at a content of 2 times or more as much as the content of O ₂ as the reaction gas during the plasma treatment.

The source material of the deposition material is mixed with the N ₂ O content Can be supplied into the process chamber at a content of 0.5 times or more as compared with that of the process chamber.

The process of depositing the deposition material in the fluid state can be performed within a temperature range of 80 to 110 ° C.

The process of depositing the deposition material in the fluid state and the process of curing the deposited deposition material may be repeated a plurality of times.

The deposition thickness of the deposition material may be in the range of 100 Å to 1000 Å.

The thickness of the first moisture barrier layer obtained after the deposition and curing processes are repeated a plurality of times may be 1000 ANGSTROM to 20000 ANGSTROM.

A foreign matter exists under the first moisture barrier layer, and the first moisture barrier layer may be filled in a recessed space below the foreign matter layer.

The present invention also provides a method of manufacturing a light emitting device, comprising the steps of: forming a light emitting element layer on a substrate; And a step of forming a moisture barrier layer on the light emitting element layer to prevent moisture from penetrating into the light emitting element layer, wherein the step of forming the moisture barrier layer comprises the steps of: And a method of forming a moisture barrier layer according to the present invention.

According to the present invention as described above, the following effects can be obtained.

According to one embodiment of the present invention, a deposition material is deposited in a state of fluidity and then cured to form a first moisture barrier layer made of an organic insulating material, and a second moisture barrier layer made of an inorganic dielectric material is formed on the first moisture barrier layer Thus, even if foreign matter exists under the first moisture barrier layer, the first moisture barrier layer may be filled in the recessed space below the foreign matter layer.

Therefore, no voids are formed below the foreign matter, and cracks can be prevented from being generated in the first moisture barrier and the second moisture barrier, so that the moisture barrier effect can be improved.

1 is a schematic cross-sectional view of an organic light emitting device to which a moisture barrier layer according to an embodiment of the present invention is applied.
FIG. 2 shows a laminated state in the case where the first moisture barrier layer made of SiOC is formed through a printing process.
FIG. 3 shows a laminated structure in the case where the first moisture barrier layer made of SiOC is formed through a deposition process.
4 is a schematic view showing a deposition apparatus for depositing a first moisture barrier layer according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

The shapes, sizes, ratios, angles, numbers, and the like disclosed in the drawings for describing the embodiments of the present invention are illustrative, and thus the present invention is not limited thereto. Like reference numerals refer to like elements throughout the specification. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. In the case where the word 'includes', 'having', 'done', etc. are used in this specification, other parts can be added unless '~ only' is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.

In interpreting the constituent elements, it is construed to include the error range even if there is no separate description.

In the case of a description of the positional relationship, for example, if the positional relationship between two parts is described as 'on', 'on top', 'under', and 'next to' Or " direct " is not used, one or more other portions may be located between the two portions.

In the case of a description of a temporal relationship, for example, if the temporal relationship is described by 'after', 'after', 'after', 'before', etc., May not be continuous unless they are not used.

The first, second, etc. are used to describe various components, but these components are not limited by these terms. These terms are used only to distinguish one component from another. Therefore, the first component mentioned below may be the second component within the technical spirit of the present invention.

It is to be understood that each of the features of the various embodiments of the present invention may be combined or combined with each other, partially or wholly, technically various interlocking and driving, and that the embodiments may be practiced independently of each other, It is possible.

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

1 is a schematic cross-sectional view of an organic light emitting device to which a moisture barrier layer according to an embodiment of the present invention is applied.

1, an organic light emitting diode according to an exemplary embodiment of the present invention includes a substrate 10, a light emitting element layer 20, a capping layer 30, a moisture barrier layer 40, 50, and a protective film 60.

The substrate 10 may be made of glass or plastic. When the organic light emitting diode according to an exemplary embodiment of the present invention is a flexible device, the substrate 10 may be formed of a plastic material such as polyimide.

The light emitting device layer 20 is formed on the substrate 10. The light emitting device layer 20 includes a first electrode 21, an organic light emitting layer 22, and a second electrode 23.

The first electrode 21 may be made of an anode such as ITO.

The organic light emitting layer 22 includes a hole injecting layer, a hole transporting layer, an emitting layer and an electron transporting layer, which are sequentially stacked on the upper surface of the first electrode 21, ), And an electron injection layer (an electron injection layer). However, the present invention is not limited thereto.

The second electrode 23 may be formed of a cathode such as Ag or Al stacked on the upper surface of the organic light emitting layer 22.

The specific structure and manufacturing method of the light emitting element layer 20 may be various structures and methods known in the art

Meanwhile, although not shown, a circuit element layer including a thin film transistor may be additionally formed between the substrate 10 and the light emitting element layer 20. The circuit element layer can control light emission of the light emitting element layer 20 on a pixel-by-pixel basis, and thus the organic light emitting display can be used in an OLED display.

The capping layer 30 is formed on the upper surface of the light emitting device layer 20. The capping layer 30 enhances an extraction effect of light emitted from the light emitting device layer 20. The capping layer 30 may be made of an organic material having a hole transporting capability, but is not limited thereto. However, such a capping layer 30 may be omitted.

The moisture barrier layer 40 is formed on the upper surface of the capping layer 30. When the capping layer 30 is omitted, the moisture barrier layer 40 is formed on the upper surface of the light emitting device layer 20. The moisture barrier layer 40 is also formed on the upper surface of the substrate 10 along the side surfaces of the light emitting device layer 20 and the capping layer 30. The moisture barrier layer 40 prevents moisture from penetrating into the organic light emitting layer 22 in the light emitting element layer 20.

The moisture barrier layer 40 includes a first moisture barrier layer 41 and a second moisture barrier layer 42 formed on the upper surface of the first moisture barrier layer 41.

The first moisture barrier layer 41 is made of an organic insulating material, and the second moisture barrier layer 42 is made of an inorganic insulating material. Specifically, the first moisture barrier layer 41 may be made of SiOC, and the second moisture barrier layer 42 may be made of SiNx.

The first moisture barrier layer 41 is positioned below the second moisture barrier layer 42 to prevent the second moisture barrier layer 42 from cracking due to foreign matter.

The first moisture barrier layer 41 made of SiOC may be generally laminated through a printing process. However, if the SiOC is laminated through the printing process, the effect of preventing cracks from occurring in the second moisture barrier layer 42 due to foreign substances as described above may be reduced. Therefore, according to an embodiment of the present invention, the SiOC is laminated through a deposition process, thereby preventing cracks from being generated in the second moisture barrier layer 42 due to foreign matter.

Hereinafter, a description will be given of a case where a difference in crack prevention effect of the second moisture barrier layer 42 is generated according to the SiOC lamination process.

FIG. 2 shows a laminated structure in the case where the first moisture barrier layer 41 made of SiOC is formed through a printing process.

As shown in FIG. 2, when the first moisture barrier 41 is laminated on the substrate 10 through the printing process, there is a possibility that an empty space is formed below the foreign matter. Particularly, when the size of the foreign matter is large, there is a high possibility that the first moisture barrier layer 41 is not stacked under the foreign matter, and thus the empty space may be enlarged. When a void is formed under the foreign matter, the first moisture barrier layer 41 and the second moisture barrier layer 42 formed on the moisture barrier layer 40 may be removed in the process of attaching the protective film 60 on the moisture barrier layer 40. [ There is a high possibility that cracks are generated in the areas of the first moisture barrier layer 41 and the second moisture barrier layer 42 corresponding to the areas where the voids are formed.

Therefore, it is preferable to laminate the first moisture barrier layer 41 made of SiOC by a deposition process as described later, rather than by a printing process.

FIG. 3 shows a laminated state in the case where the first moisture barrier layer 41 made of SiOC is formed through a deposition process.

3, if the first moisture barrier layer 41 is laminated on the substrate 10 through the deposition process, even if a large-sized foreign substance remains on the substrate 10, an empty space is formed below the foreign substance May not be formed. That is, the first moisture barrier layer 41 is laminated on the upper surface of the substrate 10 and the upper surface of the foreign object, and is also formed in the space between the substrate 10 and the foreign substance. The empty space is not formed under the light emitting diode.

As described above, according to the embodiment of the present invention, the first moisture barrier 41 can be filled in the indented space under the foreign matter even if a space is formed under the foreign matter by the presence of the foreign matter. As a result, no voids are formed below the foreign matter, and cracks can be prevented from occurring in the first moisture barrier 41 and the second moisture barrier 42 deposited thereon.

Meanwhile, in order to allow the first moisture barrier 41 to be laminated on the indented space below the foreign matter, it is necessary to appropriately adjust the deposition process of the first moisture barrier 41.

The deposition of the evaporation material in a flowable state and the curing of the evaporation material in the step of vapor deposition of the first moisture barrier 41 may be performed by using the first moisture barrier 41 in the recessed space below the foreign matter, So that it can be stacked.

In order for the deposition material for the first moisture barrier 41 to be deposited in a flowable state, the process pressure in the process chamber is preferably in the range of 0.8 to 2 Torr. In addition, it is preferable to perform the plasma treatment to cure the evaporated deposited material in a fluid state. That is, when the plasma treatment is performed on the deposited material in a fluid state, O ₂ or H ₂ O is generated in the chemical bond contained in the deposition material, so that the deposition material can be cured. Particularly, it is preferable to perform deposition and curing at 80 to 110 캜 in order to promote curing of the deposition material.

As a result, the deposition pressure is maintained in the range of 0.8 to 2 Torr, the deposition temperature is maintained in the range of 80 to 110 ° C, the deposition material is deposited in a fluid state, and N ₂ O or O ₂ It is preferable to perform the plasma treatment to cure the deposition material.

More preferably, the deposition and curing processes in the state of fluidity as described above are repeated a plurality of times. As a preferred example, a deposition material in a fluid state is deposited in a thickness of 100 to 1000 ANGSTROM while maintaining a process pressure in a chamber within a range of 0.8 to 2 Torr and a deposition temperature in a range of 80 to 110 DEG C, N ₂ O or O ₂ A plasma treatment is performed to cure the deposition material, and the deposition and curing may be repeated to form the first moisture barrier layer 41 having a thickness of 1000 Å to 20000 Å.

It is preferable that the thickness of the deposition at the time of the single deposition is set in the range of 100 ANGSTROM to 1000 ANGSTROM in order to accelerate the deposition and curing process in a fluid state. In addition, if the thickness of the first moisture barrier layer 41 finally obtained is in the range of 1000 ANGSTROM to 20,000 ANGSTROM, it is preferable to prevent a void space below the foreign matter and to prevent cracking of the second moisture barrier layer 42 formed thereon .

On the other hand, in order to deposit the evaporation material in a state of fluidity, it is generally advantageous to set the deposition temperature at a low temperature of 60 캜 or lower. However, as described above, the present invention sets the deposition temperature to a high value in the range of 80 to 110 DEG C in order to promote curing of the deposition material after the deposition process. When the deposition temperature is raised, the deposition material reacts to form a solid state without fluidity and fluidity.

Accordingly, in the present invention, the content (ppm) of the source material was controlled in relation to the reaction gas during the plasma treatment so that the deposition can be performed in a fluid state while being deposited at a relatively high temperature. Specifically, when the content of the source material is maintained at a predetermined ratio or more with respect to the reaction gas during the plasma treatment, the deposition material can be deposited in a fluid state while being deposited at a relatively high temperature.

More specifically, according to one embodiment of the present invention, when the reaction gas during the plasma treatment is O ₂ , The content of the source material is preferably at least two times the content of the O ₂ . When the reaction gas in the plasma treatment is N ₂ O, the content of the source material is preferably 0.5 times or more as large as the content of N ₂ O.

4 is a schematic view showing a deposition apparatus for depositing the first moisture barrier layer 41 according to an embodiment of the present invention. Referring to FIG. 4, a process of forming the first moisture barrier layer 41 made of SiOC will be described It is as follows.

4, the deposition apparatus according to an exemplary embodiment of the present invention includes a process chamber 100, a substrate support 110, a substrate heating unit 115, a jetting unit 120, a supply line 130, A plasma source 140, a plasma power source 150, and a feed cable 151.

The process chamber 100 defines a reaction space.

The substrate support 110 may be provided on the lower side of the process chamber 100. The substrate 10 is mounted on the substrate support 110. The substrate support 110 may be configured to be rotatable.

The substrate heating part 115 is provided inside the substrate supporting part 110 and is capable of heating the substrate 10 during a deposition process. The substrate heating unit 115 is controlled to have a deposition temperature ranging from 80 to 110 ° C. The substrate heating part 115 is not necessarily provided inside the substrate supporting part 110 but may be provided at various positions where the substrate heating part 115 can be heated. For example, the substrate heating part 115 may be formed under the substrate supporting part 110.

The jetting unit 120 may be provided on the upper side of the process chamber 100. The jetting unit 120 communicates with the supply line 130 to jet the raw material supplied from the supply line 130 to the substrate 10. The dispensing part 120 may be provided with a distribution plate so that the raw material can be uniformly supplied to the substrate 10. The configuration of the jetting unit 120 may be changed into various forms known in the art.

The supply line 130 is connected to the upper side of the process chamber 100 and communicates with the jetting unit 120. The supply line 130 may be variously changed depending on the kind of the raw material to be supplied. According to one embodiment of the present invention, since two types of raw materials, such as a source material for depositing SiOC and a reactive gas for plasma treatment, can be supplied into the process chamber 100, a bifurcated supply Line 130 is shown. The supply line 130 may also be modified into various forms known in the art.

The supply unit 140 is connected to the supply line 130. The supply unit 140 includes a first supply unit 141 and a second supply unit 142.

The first supply part 141 receives a source material for depositing SiOC. Specifically, the first supply unit 141 may contain HMDSO (Hexamethyldisiloxane) as a source material, but the present invention is not limited thereto.

The second supply part 142 receives the reaction gas during plasma processing. Specifically, the second supply unit 142 supplies O ₂ Or it accommodates N ₂ O.

When the second supply part 142 receives O ₂ , the content of HMDSO, which is a source material supplied from the first supply part 141 into the process chamber 100, is larger than the content of ODS supplied from the second supply part 142 ₂ . When the second supply part 142 receives N ₂ O, the content of HMDSO, which is a source material supplied from the first supply part 141 into the process chamber 100, It should be 0.5 times or more than the content of N ₂ O supplied.

The plasma power source 150 is connected to the reaction chamber 100 through a feed cable 151. The plasma power source 150 generates a plasma in the reaction chamber 100 to cure the deposited SiOC in a fluid state. The connection structure between the plasma power source 150 and the reaction chamber 100 may be changed into various forms known in the art.

The deposition apparatus according to the present invention is not limited to the structure shown in FIG. 4, and the deposition apparatus according to the present invention can be changed into various forms known in the art.

Referring again to FIG. 2, the second moisture barrier layer 42 made of SiNx may be formed through a plasma enhanced chemical vapor deposition (PECVD) process. More specifically, the SiNx may be deposited through a plasma enhanced chemical vapor deposition (PECVD) process using a Si-based source material and a reactant material. The Si-based source material is silane (Silane; SiH _4), disilane _{(Disilane; Si 2 H 6)} , trisilane _{(Trisilane; Si 3 H 8)} , TEOS (Tetraethylorthosilicate), DCS (Dichlorosilane), HCD (Hexachlorosilane) , A source gas composed of tri-dimethylaminosilane (TriDMAS), a trisilylamine (TSA), a hexamethyldisiloxane (HMDSO), and a hexamethyldisilazane (HMDSN), but the present invention is not limited thereto. The reaction material may include at least one reaction gas selected from nitrogen oxide (N ₂ O), oxygen (O ₂ ), ammonia (NH ₃ ), and nitrogen (N ₂ ), but is not limited thereto.

As described above, the moisture-permeable barrier layer 40 according to the present invention can be applied to various devices in various fields that require moisture-proof prevention in addition to the organic light-emitting device.

The adhesive layer 50 serves to adhere the protective film 60 to the moisture barrier layer 40. Such an adhesive layer 50 may use a variety of adhesive materials known in the art, for example, a silicone adhesive material.

The protective film 60 is bonded to the moisture barrier layer 40 by the adhesive layer 50. The protective film 60 can also prevent moisture penetration. The protective film 60 may be made of various materials known in the art such as glass, plastic, or metal.

Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, it is to be understood that the present invention is not limited to those embodiments and various changes and modifications may be made without departing from the scope of the present invention. . Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of protection of the present invention should be construed according to the claims, and all technical ideas within the scope of equivalents should be interpreted as being included in the scope of the present invention.

10: substrate 20: light emitting element layer
30: capping layer 40: moisture-proofing film
41: first moisture barrier layer 42: second moisture barrier layer
50: adhesive layer 60: protective film

Claims (12)

A step of laminating a first moisture barrier layer made of an organic insulating material; And
A step of laminating a second moisture barrier layer made of an inorganic insulating material on the first moisture barrier layer,
Wherein the step of laminating the first moisture barrier layer comprises a step of depositing an evaporation material in a fluid state and a step of curing the deposited evaporation material. The method according to claim 1,
Wherein the process for depositing the evaporation material in the fluid state is performed in a process chamber having a process pressure in the range of 0.8 to 2 Torr. The method according to claim 1,
Wherein the step of curing the evaporated deposition material comprises a step of plasma-treating the evaporated material. The method of claim 3,
Wherein the plasma treatment is performed using N ₂ O or O ₂ as a reaction gas. The method of claim 3,
Wherein the source material of the deposition material is supplied into the process chamber at a content of at least 2 times the content of O ₂ as the reaction gas during the plasma treatment. The method of claim 3,
The source material of the deposition material is mixed with the N ₂ O content Wherein the moisture content of the moisture permeable film is at least 0.5 times as large as that of the moisture permeable film. The method according to claim 5 or 6,
Wherein the step of depositing the evaporation material in the fluid state is performed within a temperature range of 80 to 110 캜. The method according to claim 1,
Wherein the step of depositing the deposition material in the fluid state and the step of curing the deposited deposition material are repeated a plurality of times. 9. The method of claim 8,
Wherein the vapor deposition material has a thickness of 100 to 1000 angstroms per deposition. 9. The method of claim 8,
Wherein the thickness of the first moisture barrier layer obtained after the deposition and curing processes are repeated a plurality of times is 1000 ANGSTROM to 20000 ANGSTROM. The method according to claim 1,
Wherein a foreign matter exists under the first moisture barrier layer and the first moisture barrier layer is filled in a space recessed below the foreign matter layer. Forming a light emitting element layer on a substrate; And
And forming a moisture barrier layer on the light emitting element layer to prevent moisture from penetrating into the light emitting element layer,
Wherein the step of forming the moisture barrier layer comprises the method of forming the moisture barrier layer according to any one of claims 1 to 10.

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