JP2010244696A - Organic el device, method for manufacturing organic el device and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic EL device for realizing long light emission life, a method for manufacturing an organic EL device, and an electronic equipment. <P>SOLUTION: The organic EL device 10 includes a plurality of organic EL elements 12 fitted on an element substrate 1, a first gas barrier layer 41 made of an inorganic material at least two-dimensionally covering an emission area 6 including the plurality of organic EL elements 12, and a second gas barrier layer 42 made of inorganic material fitted so as to two-dimensionally superpose the first gas barrier layer 41. The second gas barrier layer 42 has a higher film density than the first gas barrier layer 41, and is arranged on the element substrate 1 so as to cover an outer edge part 41a of the first gas barrier layer 41 at a surrounding area 6a of the emission area 6. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organic EL device provided with an organic EL (electroluminescence) element, a method for manufacturing the organic EL device, and an electronic apparatus.

The organic EL device has a light emitting element provided on a substrate and a protective film covering the light emitting element, and the protective film is formed by a chemical vapor deposition method using ammonia gas. There is known a display device that is composed of different silicon nitride films, and the surface silicon nitride film of the protective film has a higher density than the underlying silicon nitride film (Patent Document 1).
In addition, a step of forming a protective film on the side of the driving substrate on which the display region having the organic light emitting element is provided, a step of disposing a sealing substrate in a region facing the display region, and using the sealing substrate as a mask There is known a method for manufacturing a display device including a step of anisotropically etching a protective film to expose an external connection region in the driving substrate (Patent Document 2).

Each of the protective films in Patent Document 1 and Patent Document 2 has a function of a barrier film that prevents the light emitting element from being deactivated due to intrusion of moisture or the like and a portion where light emission does not occur.
As a method for manufacturing such a barrier film, a wet coating method is used to form an organic film on the workpiece, and an ion plating method is used to form a SiON film or SiOx film on the workpiece. A manufacturing method of a barrier multilayer film having a film forming process is known (Patent Document 3).

JP 2007-184251 A JP 2007-234610 A JP 2005-34831 A

In the display device of Patent Document 1, the substrate and the sealing substrate are bonded together after the peripheral edge of the substrate is completely covered with resin without exposing the peripheral edge of the protective film. However, it is not clear what specific film thickness in each of the first to third embodiments is formed by stacking the low-density and high-density silicon nitride films. Further, in the configuration of the protective film of Example 1, in the high temperature (80 ° C.) and high humidity (75%) test for evaluating the reliability, moisture permeation was recognized from the end face of the substrate to the silicon nitride film 2 mm or more inside. Yes.
In the manufacturing method of the display device disclosed in Patent Document 2, SiN _x (silicon nitride film) having a set film thickness of 2 μm is anisotropically etched to form a protective film whose cross section is perpendicular to the driving substrate. ing. In other words, the protective film is exposed at the end of the sealing substrate.
Therefore, the configurations of the protective films of Patent Document 1 and Patent Document 2 have a problem that they do not have sufficient barrier properties against moisture and the like entering from the end face side of the substrate.

  In addition, the method for manufacturing a barrier multilayer film in Patent Document 3 proposes a configuration of a barrier multilayer film that covers an organic film having a high coverage with respect to a step or a foreign matter on a substrate with a SiON film or a SiOx film that is an inorganic material. Yes. However, since the water vapor permeability of the organic film itself is larger than that of the inorganic material, there is a risk that moisture may permeate from the interface between the organic film and the inorganic film of the barrier multilayer film or the interface between the substrate and the barrier multilayer film. There is a problem that it does not have sufficient barrier properties.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

  Application Example 1 An organic EL device according to this application example includes a plurality of organic EL elements provided on a substrate and a first gas barrier made of an inorganic material that at least planarly covers a light emitting region including the plurality of organic EL elements. And a second gas barrier layer made of an inorganic material provided so as to overlap the first gas barrier layer in a plane, the second gas barrier layer having a higher film density than the first gas barrier layer The substrate is disposed on the substrate so as to cover an outer edge portion of the first gas barrier layer in a peripheral region of the light emitting region.

  According to this configuration, since the outer edge of the first gas barrier layer is covered with the second gas barrier layer having a higher film density than the first gas barrier layer in the peripheral region of the light emitting region, not only from the light emitting region but also from the peripheral region. It is possible to prevent the organic EL element from being deactivated by the intrusion of moisture or the like. That is, it is possible to provide an organic EL device that can obtain a long light emission lifetime.

Application Example 2 In the organic EL device according to the application example described above, it is preferable that film stresses of the first gas barrier layer and the second gas barrier layer are 100 MPa or less.
According to this structure, even if it is a multilayer gas barrier structure, since each film | membrane stress is restrained to 100 Mpa or less, it can reduce that malfunctions, such as a crack, arise in each gas barrier layer by the distortion by film | membrane stress. That is, high reliability can be obtained in the light emission lifetime.

Application Example 3 In the organic EL device according to the application example described above, the second gas barrier layer may be stacked on the first gas barrier layer.
According to this configuration, since the organic EL element is protected by the laminated structure of the first and second gas barrier layers having different film densities, a longer emission lifetime can be obtained as compared with the case where a gas barrier layer made of an organic material is employed. .

Application Example 4 In the organic EL device according to the application example described above, an organic resin layer may be provided between the first gas barrier layer and the second gas barrier layer at least in the light emitting region.
According to this configuration, even if foreign matter or the like adheres during the formation of the organic EL element or the first gas barrier layer, the foreign matter is covered with the organic resin layer. Furthermore, since the organic resin layer is covered with the second gas barrier layer having a high film density, it is possible to prevent a decrease in the light emission lifetime due to foreign substances and the like and realize a long light emission lifetime.

Application Example 5 In the organic EL device according to the application example, the light-emitting region includes a third gas barrier layer including the first gas barrier layer and the second gas barrier layer that are sequentially stacked on the plurality of organic EL elements. An organic resin layer provided so as to cover the third gas barrier layer, and an outer edge portion of the organic resin layer in the peripheral region, and the second gas barrier layer stacked on the organic resin layer. , May be provided.
According to this configuration, an organic EL device having a longer emission lifetime can be provided.

Application Example 6 In the organic EL device according to the application example, the light emitting region includes a third gas barrier layer including the first gas barrier layer and the second gas barrier layer that are sequentially stacked on the plurality of organic EL elements. And an organic resin layer provided so as to cover the third gas barrier layer, and the first gas barrier layer which covers an outer edge portion of the organic resin layer in the peripheral region and is sequentially laminated on the organic resin layer And a fourth gas barrier layer comprising the second gas barrier layer.
According to this configuration, an organic EL device having a long emission life and high reliability can be provided.

Application Example 7 In the organic EL device according to the application example, it is preferable that the first gas barrier layer is made of silicon nitride and the second gas barrier layer is made of silicon oxynitride.
According to this configuration, it is possible to provide an organic EL device that achieves both high gas barrier properties and high transparency that prevent moisture and the like from entering the light emitting region even with a multilayer gas barrier structure.

Application Example 8 In the organic EL device according to the application example described above, it is preferable that the first gas barrier layer and the second gas barrier layer have a thickness of 200 nm to 1200 nm.
According to this configuration, it is possible to provide an organic EL device having high reliability that does not cause defects such as cracks even when the film thickness is increased while ensuring a minimum gas barrier property.
The film thickness of the first gas barrier layer and the second gas barrier layer is more preferably 200 nm to 600 nm, and the film stress can be lowered.

  Application Example 9 An organic EL device manufacturing method according to this application example is a method for manufacturing an organic EL device having a light-emitting region including a plurality of organic EL elements on a substrate, and the plurality of organic EL devices on the substrate. A light emitting element forming step of forming an element, a first gas barrier layer forming step of forming a first gas barrier layer made of an inorganic material using a plasma CVD method so as to cover at least the light emitting region in a plane, and the light emitting region A second gas barrier layer made of an inorganic material is formed using an ion plating method so as to cover the outer edge of the first gas barrier layer in the peripheral region of the first gas barrier layer and to overlap the first gas barrier layer in a plane. And a gas barrier layer forming step.

  According to this method, since the first gas barrier layer is formed by the plasma CVD method in the first gas barrier layer forming step, it is possible to form the first gas barrier layer having good coverage even if the film formation surface has irregularities. Since the ion plating method is used in the second gas barrier layer forming step, the second gas barrier layer having a higher film density than the first gas barrier layer formed by the plasma CVD method can be formed. That is, by combining the first gas barrier layer with good coverage and the second gas barrier layer with higher gas barrier property, it is possible to prevent intrusion of moisture or the like from not only the light emitting region but also its peripheral region, and light emission. An organic EL device having a long lifetime can be manufactured.

Application Example 10 In the method for manufacturing an organic EL device according to the application example, the first gas barrier layer forming step and the second gas barrier layer forming step include forming the first gas barrier layer and the second gas barrier layer at a film forming temperature of 100 ° C. or less. It is preferable to form a two-gas barrier layer.
According to this method, it is possible to manufacture an organic EL device including multiple gas barrier layers while suppressing the film stress of the formed first gas barrier layer and second gas barrier layer to be low.

Application Example 11 In the method for manufacturing an organic EL device according to the application example, the second gas barrier layer forming step may be formed by laminating the first gas barrier layer to form the second gas barrier layer.
According to this method, it is possible to obtain a multi-layered gas barrier layer having a high gas barrier property while ensuring mutual adhesion as compared with a case where a gas barrier layer made of an organic material and a gas barrier layer made of an inorganic material are laminated.

Application Example 12 In the method for manufacturing an organic EL device according to the application example described above, the method further includes an organic resin layer forming step of forming an organic resin layer on the first gas barrier layer at least in the light emitting region, and forming the second gas barrier layer Preferably, in the step, the second gas barrier layer is formed so as to cover outer edges of the first gas barrier layer and the organic resin layer in the peripheral region.
According to this method, even if foreign matter or the like adheres in the light emitting element forming step or the first gas barrier layer forming step, the film forming surface is covered in the organic resin layer forming step, and the second gas barrier layer forming step is formed later. It is possible to reduce the influence of foreign matter or the like in That is, defects such as film defects due to foreign matters in the second gas barrier layer can be reduced, and an organic EL device having a long light emission lifetime can be manufactured with a high yield.

Application Example 13 In the method of manufacturing an organic EL device according to the application example, the first gas barrier layer forming step includes a step of stacking the second gas barrier layer on the first gas barrier layer, and forming the organic resin layer In the step, the organic resin layer may be formed so as to cover the second gas barrier layer laminated on the first gas barrier layer.
According to this method, the second gas barrier layer is laminated on the first gas barrier layer, and an organic EL device having a longer emission lifetime can be manufactured.

Application Example 14 In the method for manufacturing an organic EL device according to the application example, the second gas barrier layer forming step includes a step of stacking the first gas barrier layer on the organic resin layer, The second gas barrier layer may be formed so as to cover outer edges of the first gas barrier layer and the organic resin layer.
According to this method, an organic EL device having a longer emission lifetime and high reliability can be manufactured.

Application Example 15 In the method of manufacturing an organic EL device according to the application example, the first gas barrier layer forming step includes forming the first gas barrier layer made of silicon nitride, and the second gas barrier layer forming step includes oxynitriding. It is preferable to form the second gas barrier layer made of silicon.
According to this method, a multi-layer gas barrier structure having both high light transmittance and gas barrier properties is formed, and an organic EL device having a longer emission lifetime and high reliability can be manufactured.

Application Example 16 In the method for manufacturing the organic EL device according to the application example, it is preferable that the first gas barrier layer and the second gas barrier layer have a thickness of 200 nm to 1200 nm.
According to this method, it is possible to manufacture a highly reliable organic EL device that does not cause defects such as cracks even when the film thickness is increased while ensuring a minimum gas barrier property.
In addition, as for the film thickness of a 1st gas barrier layer and a 2nd gas barrier layer, 200 nm-600 nm are more preferable, and a film | membrane stress can be made into a lower state.

Application Example 17 An electronic apparatus according to this application example includes the organic EL device manufactured using the organic EL device according to the application example or the method for manufacturing the organic EL device according to the application example.
According to this configuration, it is possible to provide an electronic device that has both a long light emission lifetime and high reliability in light emission characteristics.

1 is a schematic front view illustrating a configuration of an organic EL device according to Embodiment 1. FIG. FIG. 3 is a cross-sectional view of a main part showing the structure of the organic EL device of the first embodiment. FIG. 2 is a schematic diagram illustrating a configuration of an organic EL element according to Embodiment 1. 5 is a flowchart showing a method for manufacturing the organic EL device according to the first embodiment. The schematic plan view which shows a mother board | substrate. (A)-(c) is a schematic plan view which shows the mask for film-forming of a functional layer. The schematic plan view which shows the mask for film-forming of a gas barrier layer. (A)-(g) is a schematic sectional drawing which shows the manufacturing method of the organic electroluminescent apparatus of Embodiment 1. FIG. (H)-(l) is schematic which shows the manufacturing method of the organic electroluminescent apparatus of Embodiment 1. FIG. FIG. 3 is a schematic cross-sectional view illustrating a method for manufacturing the organic EL device according to the first embodiment. Schematic which shows the structure of a vapor deposition apparatus. Schematic which shows the structure of a plasma CVD apparatus. Schematic which shows the structure of an ion plating apparatus. FIG. 3 is a schematic cross-sectional view of a main part showing the structure of an organic EL device according to Embodiment 2. The graph which shows the relationship between a film | membrane stress and a film thickness. FIG. 6 is a schematic perspective view illustrating a mobile phone as an electronic apparatus according to a third embodiment. (A)-(c) is a schematic sectional drawing which shows the gas barrier structure of a modification.

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, embodiments of the invention will be described with reference to the drawings. Note that the drawings to be used are appropriately enlarged or reduced so that the part to be described can be recognized.

(Embodiment 1)
<Organic EL device>
First, the organic EL device of the present embodiment will be described with reference to FIGS. FIG. 1 is a schematic front view showing the configuration of the organic EL device, FIG. 2 is a main cross-sectional view showing the structure of the organic EL device, and FIG. 3 is a schematic diagram showing the configuration of the organic EL element.

  As shown in FIGS. 1 and 2, the organic EL device 10 includes an element substrate 1 provided with an organic EL element 12 (see FIG. 2) that is a light emitting element corresponding to each pixel 7, and an element substrate 1. A sealing substrate 2 that is bonded and seals at least the plurality of organic EL elements 12 is provided.

  The element substrate 1 includes a circuit unit 11 (see FIG. 2) including a driving element that drives the organic EL element 12. In the light emitting region 6, pixels 7 that can obtain the same light emission color among red (R), green (G), and blue (B) have a so-called stripe configuration in which they are arranged in the same direction. The pixel 7 is actually very fine and is enlarged for the sake of illustration.

  The element substrate 1 is slightly larger than the sealing substrate 2, and two scanning line drive circuits for driving a TFT (Thin Film Transistor) element 8 (see FIG. 2) as a drive element are provided in a frame-like protruding portion. A unit 3 and one data line driving circuit unit 4 are provided. A flexible relay substrate 5 for connecting the drive circuit units 3 and 4 and an external drive circuit is mounted on the terminal portion 1 a of the element substrate 1.

  As shown in FIG. 2, in the organic EL device 10, the organic EL element 12 is laminated on the anode 31 as a first electrode (or pixel electrode), a partition wall 33 that partitions the anode 31, and the anode 31. And a functional layer 32 including a light emitting layer made of an organic film. Further, a cathode 34 as a second electrode (or a common electrode) formed so as to face the anode 31 with the functional layer 32 interposed therebetween.

  The partition wall 33 is made of a photosensitive resin having insulation properties such as phenol or polyimide, and is provided so as to partially cover the periphery of the anode 31 constituting the pixel 7 and to partition the plurality of anodes 31.

  The anode 31 is connected to one of the three terminals of the TFT element 8 formed on the element substrate 1. For example, ITO (Indium Tin Oxide), which is a transparent electrode material, is formed to a thickness of about 100 nm. Electrode. Although not shown, a reflective layer made of Al is provided below the anode 31 (on the planarization layer 28 side) via an insulating layer. The reflective layer reflects light emitted from the functional layer 32 toward the sealing substrate 2. Moreover, the said reflective layer is not limited to Al, What is necessary is just to have the function (reflection surface) which reflects light emission. For example, a method of forming a reflective surface having projections and depressions using an insulating organic material or an inorganic material, a method of forming the anode 31 itself with a conductive material having a reflection function, and forming an ITO film on the surface layer are included. .

  Similarly, the cathode 34 is formed of a transparent electrode material such as ITO.

  The first gas barrier layer 41 is provided so as to cover at least the light emitting region 6 provided with such a plurality of organic EL elements 12. In addition, an organic resin layer 45 and a second gas barrier layer 42 are sequentially stacked on the first gas barrier layer 41.

The first gas barrier layer 41 is, for example, a Si _x N _y (silicon nitride) film made of an inorganic material, and is formed to have transparency using a plasma CVD apparatus described later.

  The second gas barrier layer 42 is, for example, a SiON (silicon oxynitride) film made of an inorganic material, and is formed to have transparency using an ion plating apparatus described later.

  The organic resin layer 45 disposed between the first gas barrier layer 41 and the second gas barrier layer 42 is made of, for example, an epoxy resin material having transparency. The organic resin layer 45 is provided for the purpose of covering foreign matter or the like attached when the first gas barrier layer 41 is formed, and ensuring the flatness of the film formation surface when the second gas barrier layer 42 is formed.

  The second gas barrier layer 42 is formed so that the film density is higher than that of the first gas barrier layer 41. Both the first gas barrier layer 41 and the second gas barrier layer 42 are formed so that the film stress becomes smaller than a predetermined value. Details will be described later in the method for manufacturing an organic EL device.

  As the sealing substrate 2, a substrate made of transparent glass or the like is used. On the side facing the organic EL element 12, red (R), green (G), blue (B), three-color filter elements 36R, 36G, and 36B corresponding to the arrangement of the pixels 7 and a light shielding portion that partitions the filter elements 37 is provided.

  The organic EL device 10 has a so-called top emission type structure, in which a driving current is passed between the anode 31 and the cathode 34 to reflect the white light emitted from the functional layer 32 by the above-described reflection layer, and thereby the filter element. It is configured to be taken out from the sealing substrate 2 side through 36R, 36G, and 36B. Since the element substrate 1 has a top emission type structure, either a transparent substrate or an opaque substrate can be used. Examples of the opaque substrate include a thermosetting resin and a thermoplastic resin in addition to a ceramic sheet such as alumina and a metal sheet such as stainless steel that has been subjected to an insulation treatment such as surface oxidation.

The element substrate 1 is provided with a circuit unit 11 for driving the organic EL element 12. That is, a base protective layer 21 mainly composed of SiO ₂ (silicon dioxide) is formed on the surface of the element substrate 1 as a base, and a silicon layer 22 is formed thereon. On the surface of the silicon layer 22, a gate insulating layer 23 mainly composed of SiO ₂ (silicon dioxide) and / or Si _x N _y (silicon nitride) is formed.

Further, in the silicon layer 22, a region overlapping with the gate electrode 26 with the gate insulating layer 23 interposed therebetween is a channel region 22a. The gate electrode 26 is a part of a scanning line (not shown). On the other hand, a first interlayer insulating layer 27 mainly composed of SiO ₂ (silicon dioxide) is formed on the surface of the gate insulating layer 23 covering the silicon layer 22 and forming the gate electrode 26.

  Further, in the silicon layer 22, a low concentration source region and a high concentration source region 22c are provided on the source side of the channel region 22a, while a low concentration drain region and a high concentration drain region 22b are provided on the drain side of the channel region 22a. Is provided to form a so-called LDD (Light Doped Drain) structure. Among these, the high-concentration source region 22 c is connected to the source electrode 25 through a contact hole 25 a that opens through the gate insulating layer 23 and the first interlayer insulating layer 27. The source electrode 25 is configured as a part of a power supply line (not shown). On the other hand, the high-concentration drain region 22 b is connected to the drain electrode 24 made of the same layer as the source electrode 25 through a contact hole 24 a opened through the gate insulating layer 23 and the first interlayer insulating layer 27.

  Over the first interlayer insulating layer 27 on which the source electrode 25 and the drain electrode 24 are formed, a planarizing layer 28 mainly composed of, for example, an acrylic resin component is formed. The planarization layer 28 is formed of a heat-resistant insulating resin such as acrylic or polyimide, and is formed to eliminate surface irregularities due to the TFT element 8, the source electrode 25, the drain electrode 24, and the like. Are known.

  An anode 31 is formed on the surface of the planarizing layer 28 and is connected to the drain electrode 24 through a contact hole 28 a provided in the planarizing layer 28. That is, the anode 31 is connected to the high concentration drain region 22 b of the silicon layer 22 through the drain electrode 24. The cathode 34 is connected to GND. Accordingly, the driving current supplied to the anode 31 from the power supply line and flowing between the cathode 34 is controlled by the TFT element 8 as a switching element. Thereby, the circuit unit 11 emits light from the desired organic EL element 12 to enable color display.

  The configuration of the circuit unit 11 that drives the organic EL element 12 is not limited to this.

  As shown in FIG. 3, the organic EL element 12 has a functional layer 32 sandwiched between an anode 31 and a cathode 34. The functional layer 32 includes, for example, a plurality of thin film layers called a hole transport layer (HTL) 32h, light-emitting layers 32LR, 32LB, and 32LG for each color, and an electron transport layer (ETL) 32e. Are stacked in this order.

  Examples of the hole transport layer (HTL) 32h include triphenylamine derivatives (TPD), pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives.

As a material for forming the light emitting layers 32LR, 32LB, and 32LG, a known light emitting material capable of emitting fluorescence or phosphorescence is used. For example, as a material for forming the light emitting layer 32LR, a light emitting material containing Alq ₃ (tris (8-hydroxyquinolinol) aluminum) as a host and rubrene as an assist dopant and DCM2 (a dianomethylenepyran derivative) as a red dopant. Is mentioned. As a material for forming the light emitting layer 32LB, a light emitting material containing BD102 which is a blue dopant using BH215 as a host can be given. As a material for forming the light emitting layer 32LG, a light emitting material containing GD206 as a green dopant with BH215 as a host can be given. This configuration includes a light emitting layer of three colors based on the so-called “dopant method” and enables white light emission. BH215 as a host and BD102 and GD206 as dopants are all known materials manufactured by Idemitsu Kosan.

  Examples of the material for forming the electron transport layer (ETL) 32e include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and Examples thereof include a derivative thereof, a fluorene derivative, 8-hydroxyquinoline and a metal complex of the derivative.

  These hole transport layers (HTL) 32h, light-emitting layers 32LR, 32LB, 32LG, and electron transport layer (ETL) 32e are formed of so-called low-molecular materials and can be formed by vacuum deposition.

  The element substrate 1 having such an organic EL element 12 is disposed so as to face the transparent sealing substrate 2 through the space 35, and is bonded and sealed by a sealing material in the peripheral region of the light emitting region 6.

  The organic EL device 10 includes a first gas barrier layer 41 that covers the light emitting region 6 in which the plurality of organic EL elements 12 are provided, and a second gas barrier layer 42 that has a high film density superimposed on the first gas barrier layer 42 in a planar manner. Yes. The second gas barrier layer 42 is formed so as to cover the outer edge of the first gas barrier layer 41 in the peripheral region of the light emitting region 6. Since it has such a gas barrier structure, it is possible to prevent a gas such as moisture from entering the light emitting region 6 from the outside. Therefore, the occurrence of pixel defects called dark spots in which the light emission of the organic EL element 12 is deactivated by the permeation of the gas is prevented, and a long light emission life is realized.

  The organic EL device 10 is not limited to the top emission type, and the cathode 34 is formed using an opaque conductive material such as Al having a reflection function, and the light emitted from the organic EL element 12 is reflected by the cathode 34. A bottom emission type structure that is taken out from the element substrate 1 side may be used.

<Method for manufacturing organic EL device>
4 is a flowchart showing a method for manufacturing an organic EL device, FIG. 5 is a schematic plan view showing a mother substrate, FIGS. 6A to 6C are schematic plan views showing masks for forming functional layers, and FIG. FIG. 8A to FIG. 8G, FIG. 9H to FIG. 9L, and FIG. 10 are schematic views showing a method for manufacturing an organic EL device. FIG. 11 is a schematic view showing the structure of the vapor deposition apparatus, FIG. 12 is a schematic view showing the structure of the plasma CVD apparatus, and FIG. 13 is a schematic view showing the structure of the ion plating apparatus.

  As shown in FIG. 4, the manufacturing method of the organic EL device 10 of the present embodiment includes a plasma processing step (step S1) for performing a surface treatment on the element substrate 1, a hole transport layer forming step (step S2), an R , B, G light emitting layers 32LR, 32LB, 32LG for forming respective light emitting layers (step S3 to step S5), electron transport layer forming step (step S6), cathode forming step ( Step S7), a first gas barrier layer forming step (Step S8) for forming the first gas barrier layer 41 using a plasma CVD method, an organic resin layer forming step (Step S9), and an ion plating method. A second gas barrier layer forming step (step S10) for forming the second gas barrier layer 42.

Hereinafter, a method for forming the organic EL element 12 on the element substrate 1 will be described. Actually, as shown in FIG. 5, the substrate W, which is a mother substrate in which regions corresponding to the element substrate 1 are imposed in a matrix form. On the other hand, each structure of the organic EL element 12 is formed in each light emitting region 6. The substrate W is provided with alignment marks AL _{1 to} AL _{4 at} four corners for alignment with a film-forming mask described later. In addition, the circuit part 11, the anode 31, and the partition part 33 for driving the organic EL element 12 can be formed using a well-known manufacturing method. Therefore, in the schematic diagram illustrating the method for manufacturing the organic EL device 10, the display of the circuit unit 11 is omitted.

  Step S1 in FIG. 4 is a plasma processing step. In step S1, the element substrate 1 on which the anode 31 and the partition wall 33 are formed is put into a plasma processing apparatus. Then, as shown in FIG. 8A, the surface of the anode 31 is plasma-treated using oxygen as a processing gas. This is because the HOMO level of the anode 31 is brought close to the HOMO level of the organic film (hole transport layer) by oxygen plasma, so that the barrier of the organic film (hole transport layer) against holes injected from the anode 31 is relatively set. This is because the light emission performance of the organic EL element 12 is enhanced by lowering. Then, the process proceeds to step S2.

  In the subsequent steps S2 to S6, an organic film is formed for each film formation region E by using a film formation mask by vacuum deposition.

<Deposition mask>
More specifically, as illustrated in FIG. 6A, the vapor deposition mask 50 as a film formation mask includes a plurality of mask regions 52 arranged in a matrix with respect to the base material 51, and the base material 51. And four alignment marks 53 arranged at the four corners. One mask region 52 corresponds to one organic EL device 10, and an opening 50 a corresponding to a film formation pattern, that is, a film formation region E of the substrate W is formed in the mask region 52.

  The opening 50a provided in the vapor deposition mask 50 is an opening corresponding to one pixel 7 (see FIG. 1), for example, as shown in FIG. Considering the overlay accuracy with the substrate W (element substrate 1), the opening area is slightly larger than the film formation region E. In addition, the present invention is not limited to this, and for example, as shown in FIG. 5C, there may be a slit-like opening corresponding to a column composed of a plurality of pixels 7 that can emit light of the same color.

  In the present embodiment, the vapor deposition mask 50 is configured using a metal mask. As a material of the metal mask, for example, a Fe-36 wt% Ni ferromagnetic material called Invar can be used. Its thickness is about 30 μm to 50 μm. The vapor deposition mask 50 is not limited to a metal mask, and may be a silicon mask using a silicon substrate capable of forming the opening 50a with high accuracy.

  Such a vapor deposition mask 50 is attached to a frame-like frame (not shown) so as not to be distorted, and is used by being superimposed on the substrate W as described above.

<Vapor deposition equipment>
Next, a vapor deposition apparatus for forming an organic film will be described with reference to FIG. As shown in FIG. 11A, the vapor deposition apparatus 100 is provided at a chamber 111, a vapor deposition source 110 that is provided at the bottom of the chamber 111 and stores and evaporates a film-forming material, and is opposed to the vapor deposition source 110. And a substrate holder 113 that holds the substrate W in a substantially horizontal state. In addition, a crystal resonator 112 as a film thickness measuring unit for measuring the deposition rate of the film forming material evaporated from the deposition source 110 is disposed above the deposition source 110. In addition, for example, a pressure reducing device for reducing the pressure in the chamber 111 to a predetermined degree of vacuum, a thermometer for detecting the temperature of the substrate W during film formation, and the like are provided, but they are not shown in FIG. ing.

  The substrate holding part 113 includes a support body 115 having a holding part 114 on the outer edge side, and a rotating shaft 116 provided on the support body 115 and suspending the support body 115 in the chamber 111.

  The holding part 114 has a clamp-like form, and holds the peripheral part of the laminated body composed of the vapor deposition mask 50, the substrate W as a work, and the magnet 117, which are sequentially stacked.

As shown in FIG. 11B, the element substrate 1 and the vapor deposition mask 50 are positioned and overlapped so that the film formation region E is opened, and the element substrate 1 is bonded to the magnet 117 and the vapor deposition mask 50 by the holding unit 114. Sandwiched between.
As described above, the vapor deposition mask 50 is a metal mask and is configured to be attracted by the magnet 117, and is in close contact with the partition wall 33 of the element substrate 1.

  The magnet 117 is a permanent magnet that spontaneously generates magnetism (magnetic flux) rather than an electromagnet from the viewpoint that a stable magnetic field can be obtained without using wasted energy, and the structure of the substrate holder 113 is not complicated. Yes. Examples of the magnet 117 include an alnico magnet, a ferrite magnet, and a neodymium magnet. Further, a rubber magnet obtained by mixing these magnet powders with resin or the like may be used.

  The vapor deposition source 110 stores one of the film forming materials of the hole transport layer (HTL) 32h, the light emitting layers 32LR, 32LB, and 32LG and the electron transport layer (ETL) 32e constituting the functional layer 32 described above. Evaporates. While the film forming material evaporates, the rotating shaft 116 rotates to rotate the substrate W held on the substrate holding portion 113. Thereby, it is possible to form the functional layer 32 in the film formation region E of the element substrate 1 in a state where the film thickness variation of each layer is reduced.

  Step S2 in FIG. 4 is a hole transport layer forming step. In step S2, as shown in FIG. 8B, the opening 50a of the vapor deposition mask 50 as a film formation mask and the film formation region E having the anode 31 defined by the partition wall 33 are matched. The element substrate 1 and the vapor deposition mask 50 are positioned and brought into close contact with each other. Then, the hole transport layer forming material is set in the vapor deposition apparatus 100 and evaporated from the vapor deposition source 110 provided in the chamber 111, and a hole transport layer 32 h is formed for each film formation region E. And it progresses to step S3-step S5 sequentially.

  Steps S3 to S5 in FIG. 4 are light emitting layer forming steps. In steps S3 to S5, as shown in FIGS. 8C to 8E, the element substrate 1 is formed with a light emitting layer from the vapor deposition source 110 provided in the chamber 111 in a state of being superimposed on the vapor deposition mask 50. The material evaporates, and the light emitting layers 32LR, 32LB, and 32LG are sequentially formed for each film formation region E. Then, the process proceeds to step S6.

Step S6 in FIG. 4 is an electron transport layer forming step. In step S6, as shown in FIG. 8F, the element substrate 1 is superposed on the vapor deposition mask 50, and the electron transport layer forming material is evaporated from the vapor deposition source 110 provided in the chamber 111. An electron transport layer 32e is formed for each film formation region E.
The above steps S2 to S6 correspond to the functional layer forming step. In the functional layer forming step, the element substrate 1 and the vapor deposition mask 50 are in close contact with each other through the partition wall 33, so that the vapor deposition mask 50 is directly applied to the surface of the plasma-treated anode 31 and various organic films after film formation. can not touch. Therefore, problems such as film defects caused by direct contact of the vapor deposition mask 50 with the anode 31 and various organic films are avoided. Further, since the film is not formed except in the film formation region E, the functional layer 32 having a desired film thickness is formed. Then, the process proceeds to step S7.

  Step S7 in FIG. 4 is a cathode forming step. In step S7, as shown in FIG. 8G, the functional layer 32 and the partition wall 33 are covered by, for example, a vacuum deposition method on the element substrate 1 on which the vapor deposition mask 50 is removed and the functional layer 32 is formed. A cathode 34 is formed on the substrate. The cathode 34 is ITO, and the film thickness is 100 nm to 200 nm. Thereby, the organic EL element 12 having the functional layer 32 between the anode 31 and the cathode 34 is formed. Then, the process proceeds to step S8.

  Step S8 in FIG. 4 is a first gas barrier layer forming step. In step S8, as shown in FIGS. 9H and 9I, the plurality of organic EL elements 12 provided in the light emitting region 6 are covered, and the outer edge portion 41a is positioned in the peripheral region of the light emitting region 6. 1 gas barrier layer 41 is formed.

Specifically, as shown in FIG. 12, a substrate W on which a plurality of organic EL elements 12 are formed and a deposition mask 70 are overlapped at a predetermined position, and Si _x N _y is used by using a plasma CVD apparatus 200. A first gas barrier layer 41 made of (silicon nitride) is formed for each corresponding element substrate 1.

<Plasma CVD equipment>
The plasma CVD apparatus 200 includes a sealable chamber 201 and a pair of high-frequency electrodes 202 and 204 provided to face each other at a predetermined interval in the chamber 201.

  On one high-frequency electrode 202, the substrate W on which the film formation mask 70 is superimposed is placed and fixed by the holding unit 203.

  The other high-frequency electrode 204 has a grid-like opening provided on the side facing the one high-frequency electrode 202 and a gas flow path communicating with the opening. The film-forming material is carried by the carrier gas from the gas flow path through the opening between the high-frequency electrodes 202 and 204 facing each other.

  The inside of the chamber 201 is depressurized by a depressurizing means in advance so as to be a predetermined pressure, and then a carrier gas containing a film forming material is introduced into the chamber 201.

  By causing a discharge between the pair of high-frequency electrodes 202 and 204, the processing gas introduced into the chamber 201 is excited and enters a plasma state. By exposing the substrate W to the plasma processing gas, a film made of a film forming material can be formed in a region corresponding to the opening 72 of the film forming mask 70.

As shown in FIG. 7, the film formation mask 70 includes a base material 71 and a plurality of openings 72 that open to the base material 71. The openings 72 are opened in a matrix corresponding to the light emitting regions 6 in the substrate W. The planar size of the opening 72 is slightly larger than the light emitting region 6. Further, an alignment opening 73 is provided at a position corresponding to the alignment marks AL _{1 to} AL ₄ (see FIG. 5) of the substrate W. As the deposition mask 70, a metal mask made of a ferromagnetic material such as Fe-36 wt% Ni is adopted as the deposition mask 50 described above.

In step S8, plasma was generated by discharging at room temperature using silane (SiH ₄ ) gas as a film forming material and nitrogen (N ₂ ) gas as a carrier gas. The formed first gas barrier layer 41 had a film thickness of about 200 nm, a refractive index of about 1.86, a film stress of about 60 Mpa, and a film density of about 1.7 g / cm ³ .
The film thickness is 200 nm to 1200 nm (preferably 200 nm to 600 nm), and during film formation, the voltage applied between the pair of high-frequency electrodes 202 and 204 is decreased, the film formation pressure is increased, or hydrogen gas is added. By increasing the flow rate, etc., film stress, film density, etc. at a desired film thickness can be obtained.
Since the plasma CVD apparatus 200 is used, the first gas barrier layer 41 coated corresponding to the unevenness on the film forming surface including the light emitting region 6 can be obtained. In addition, since the film is formed around the opening 72 of the film formation mask 70, the film thickness of the first gas barrier layer 41 tends to become thinner toward the outer edge portion 41a in the peripheral region of the light emitting region 6. It becomes. In other words, the outer edge portion 41a is tapered when viewed in cross section.

  Note that the film is also formed on the sample piece simultaneously with the film formation on the substrate W. The film stress is obtained from the warp amount of the sample piece. Similarly, the film density is obtained from the film thickness of silicon nitride in the sample piece and the weight per unit area. The refractive index is obtained by measuring the transmittance of the sample with respect to light of a specific wavelength. Then, the process proceeds to step S9.

Step S9 in FIG. 4 is an organic resin layer forming step. In step S9, as shown in FIG. 9J, an organic resin layer 45 made of, for example, a transparent epoxy resin is formed so as to cover at least the first gas barrier layer 41. The thickness of the organic resin layer 45 is about 5 μm.
As a method for forming the organic resin layer 45, a solvent is added to the organic resin layer forming material to adjust the viscosity to an appropriate level, and printing is performed using a screen or the like. For example, a method of forming a film by applying the film using a quantitative discharge method for drawing and then drying the film may be used.
Thus, by covering the first gas barrier layer 41 with the organic resin layer 45 in the micron order, the foreign matter or the like at the time of forming the functional layer 32, the cathode 34, or the first gas barrier layer 41 is covered, and then the film is formed. The film forming surface of the second gas barrier layer 42 can be flattened and a function as a stress relaxation layer for the second gas barrier layer 42 can be provided. Then, the process proceeds to step S10.

  Step S10 in FIG. 4 is a second gas barrier layer forming step. In step S10, as shown in FIGS. 9 (k) and (l), at least the organic resin layer 45 is planarly covered, and the outer edge portion 41a of the first gas barrier layer 41 and the organic resin layer 45 in the peripheral region of the light emitting region 6 are covered. A second gas barrier layer 42 made of SiON (silicon oxynitride) is formed so as to cover the outer edge 45a.

  Specifically, as shown in FIG. 13, a substrate W on which a plurality of organic EL elements 12 are formed and a film formation mask 80 are overlapped at a predetermined position and made of SiON using an ion plating apparatus 300. The second gas barrier layer 42 is formed for each corresponding element substrate 1.

<Ion plating device>
The ion plating apparatus 300 includes an airtight chamber (vacuum container) 301, a plasma beam generator 310 that generates a plasma beam, and a vacuum pump 350 that decompresses the inside of the chamber 301. For example, a turbo molecular pump or the like is used as the vacuum pump 350.

  The chamber 301 is composed of an upper film forming chamber 302 and a lower plasma chamber 303, and a hearth (anode) 304 as an evaporation source is provided on the inner bottom portion 303 a of the plasma chamber 303. The hearth 304 is a cylindrical container opened upward, and the film forming material M is accommodated therein. Further, an auxiliary anode 340 is provided so as to surround the hearth 304. The auxiliary anode 340 has a coil 340a inside.

  A plasma beam generator 310 and a reactive gas introduction unit 356 for introducing a reactive gas RG into the plasma chamber 303 are attached to the inner wall 303b of the plasma chamber 303.

The plasma beam generator 310 has an introduction tube 305 whose one end opens to the plasma chamber 303. A steering coil SC is provided outside the introduction pipe 305 so as to surround it. The first intermediate electrode 306 and the second intermediate electrode 307 are connected to the introduction pipe 305 so as to be concentric with each other. The first intermediate electrode 306 has a coil 306a inside, and the second intermediate electrode 307 has a permanent magnet 307a and a coil (not shown) inside. An insulating tube 308 made of, for example, a glass tube is connected to the other end of the introduction tube 305 via the first intermediate electrode 306 and the second intermediate electrode 307, and the other end of the insulating tube 308 is The conductor plate 309 is closed. Inside the insulating tube 308, there are a conductive pipe 311 provided with a thermionic emission member 312 on the tip side, and a pipe through which the carrier gas CG is introduced into the pipe 311 through the conductor plate 309. is doing. In this case, the pipe 311 is made of a high melting point material such as molybdenum or tantalum, and the thermionic emission member 312 is made of lanthanum hexaboride (LaB ₆ ). The carrier gas CG is argon (Ar) gas.

The ion plating apparatus 300 includes a first variable power supply V1 whose negative end is connected to the conductor plate 309, and a second variable power supply V2 connected to the coil 306a of the first intermediate electrode 306 and the steering coil SC. And a third variable power source V3 having a positive end connected to a coil (not shown) of the second intermediate electrode 307. The positive end of the first variable power supply V1 is connected to the negative end of the third variable power supply V3, and is connected to the first intermediate electrode 306 via the resistor _R0 . In addition, the auxiliary anode 340 is connected to the hearth 304 via the variable resistor R ₁ . The potential applied to the hearth 304 can be adjusted by adjusting the value of the variable resistor R ₁ .

The first variable power supply V1 applies a potential to the thermoelectron emission member 312 via the conductor plate 309 to emit thermoelectrons. Further, the magnitude of the magnetic field generated by the first intermediate electrode 306 can be controlled by setting the resistance R ₀ to a predetermined magnitude and adjusting the voltage value. The second variable power supply V2 can adjust the magnitude of the magnetic field generated by the steering coil SC by adjusting its voltage level.

  The plasma beam PB generated by receiving the electron emission from the thermionic emission member 312 in the Ar gas which is the carrier gas CG is converged by the first intermediate electrode 306, and is desired depending on the magnitude of the magnetic field generated by the steering coil SC. It is guided in the direction and injected into the plasma chamber 303. Then, by adjusting the voltage level applied to the coil 340 a of the auxiliary anode 340, the magnitude of the magnetic field generated in the auxiliary anode 340 is controlled, and the emitted plasma beam PB is guided to the hearth 304. The third variable power source V3 can not only converge the generated plasma beam PB but also temporarily attract it to the second intermediate electrode 307 by controlling the voltage level. For example, when heating the plasma beam generator 310 by applying a voltage to the conductor plate 309 to ignite the plasma beam PB, control is performed so as to drop the generated plasma beam PB to the nearby second intermediate electrode 307. That is, it is possible to prevent the deposition material M from being wastedly evaporated by irradiating the hearth 304 with the plasma beam PB.

A pipe 355 connected to the vacuum pump 350 is provided on the other inner wall 303 c of the plasma chamber 303. The pipe 355 has a gate valve (GV) 354 on the vacuum pump 350 side and a pressure adjustment valve 353 on the plasma chamber 303 side. The pressure adjustment valve 353 is configured so that a pressure controller (APC) 352 generates a control signal in response to a signal from a vacuum gauge 351 provided in the film formation chamber 302 and operates in response to the control signal. . By installing the vacuum gauge 351 in the film forming chamber 302, it is difficult to be affected by the plasma beam PB, and the reliability and life of the measurement of the vacuum gauge 351 are ensured.
A non-contact type thermometer 360 is provided in the vicinity of the vacuum gauge 351, and the temperature of the substrate W during film formation can be measured.

  In the film forming chamber 302, a substrate mounting portion 321 on which a substrate W as a workpiece is mounted, and the substrate mounting portion 321 are suspended to maintain a predetermined distance from the hearth 304 in a certain direction (X-axis direction). A movable moving mechanism 320 is provided. By moving the substrate W by the moving mechanism 320, a thin film can be uniformly deposited on the surface of the substrate W.

  In such an ion plating apparatus 300, the inside of the chamber 301 is brought into a predetermined reduced pressure state (vacuum state) by the vacuum pump 350. Then, by guiding the plasma beam PB generated from the plasma beam generator 310 to the hearth 304, the stored film forming material M is irradiated with the plasma beam PB. The film forming material M irradiated with the plasma beam PB is heated by Joule heat and evaporated. The evaporated film forming material M reaches the substrate W mounted on the substrate mounting portion 321 and is formed as a thin film. Further, if a reactive gas RG is introduced into the plasma chamber 303, the evaporated film forming material M and the reactive gas RG can be reacted to form a thin film made of a reaction product on the surface of the substrate W.

In step S10, using the ion plating apparatus 300, the deposition mask 80 and the substrate W are overlapped at a predetermined position and held on the substrate mounting portion 321. Silicon monoxide (SiO) is used as the film forming material M. Nitrogen (N ₂ ) is introduced as the reactive gas RG. The inside of the chamber 301 is depressurized to about 1 × 10 ⁻² Pa by the vacuum pump 350. The plasma beam generator 310 is operated to generate a plasma beam PB, and the SiO accommodated in the hearth 304 is heated to approximately 1100 ° C. to 1300 ° C. SiO is a sublimation material and evaporates by heating. On the other hand, N ₂ gas is introduced as the reactive gas RG to create an atmosphere in which the space between the substrate W and the hearth 304 is filled with N ₂ , and oxygen from the outside is blocked, and oxidation of the functional layer 32 is prevented. The evaporated SiO is combined with N ₂ to form SiON (silicon oxynitride) and is formed on the surface of the substrate W.

At this time, the film formation temperature (surface temperature of the substrate W) is 100 ° C. or less, and the film thickness of the formed silicon oxynitride is about 200 nm, the refractive index is 1.79, the film stress is 50 MPa, and the film density is 2 0.7 g / cm ³ .
The film thickness is 200 nm to 1200 nm (preferably 200 nm to 600 nm), and the film stress at a desired film thickness is adjusted by adjusting the film forming pressure during film formation, the power of the plasma beam PB, or the flow rate of the reactive gas RG. The film density can be obtained. These values are obtained by analyzing the sample pieces simultaneously formed by the same method as that for the first gas barrier layer 41.

  The film formation mask 80 used when forming the second gas barrier layer 42 has a plurality of openings 82 corresponding to the light emitting region 6 of the substrate W. The planar size of the opening 82 is slightly larger than the opening 72 of the film formation mask 70 used when forming the first gas barrier layer 41. A metal mask is also used for the film formation mask 80. The film formation of the second gas barrier layer 42 using the ion plating apparatus 300 is less likely to go around the opening 82 of the film formation mask 80 as compared to the film formation of the first gas barrier layer 41 using the plasma CVD apparatus 200. Therefore, in order to form a film so as to cover the outer edge portion 41 a of the first gas barrier layer 41, the size of the opening 82 of the film formation mask 80 takes into account the wraparound during the film formation of the first gas barrier layer 41. Designed.

  In this way, a gas barrier structure covering the light emitting region 6 provided with the plurality of organic EL elements 12 is completed. Then, as shown in FIG. 10, the sealing substrate 2 having the filter elements 36R, 36G, and 36B and the element substrate 1 are joined and sealed through the sealing material 9 disposed in the peripheral region 6a of the light emitting region 6. The The sealing material 9 is, for example, a thermosetting or ultraviolet curable epoxy adhesive. A part of the sealing material 9 is disposed so as to cover the outer edge portion 42 a of the second gas barrier layer 42. In the peripheral region 6 a of the light emitting region 6, the second gas barrier layer 42 is formed so as to cover the outer edge portion 41 a of the first gas barrier layer 41 and the outer edge portion 45 a of the organic resin layer 45.

  According to such a method of manufacturing the organic EL device 10, the first gas barrier is formed by the plasma CVD method in which the plurality of organic EL elements 12 are provided and the light emitting region 6 having unevenness on the film formation surface is formed with high coverage. An organic EL having a high gas barrier property, in which a layer 41, an organic resin layer 45, and a second gas barrier layer 42 formed by an ion plating method having a higher film density than the first gas barrier layer 41 are sequentially laminated. The device 10 can be manufactured.

  In particular, in the peripheral region 6a of the light emitting region 6, the outer edge portion 41a of the first gas barrier layer 41 and the outer edge portion 45a of the organic resin layer 45 are covered with a second gas barrier layer 42 made of SiON (silicon oxynitride) having high gas barrier properties. Therefore, even if a gas such as moisture that interferes with the light emission lifetime passes through the sealing material 9, it can be prevented from entering the light emitting region 6. Therefore, the organic EL device 10 having both a long light emission lifetime and stable light emission characteristics can be manufactured with a high yield.

Furthermore, even if the first gas barrier layer 41 is formed using the plasma CVD method, it is not necessary to anisotropically etch the formed SiN _x film as in Patent Document 2 described above. It can be simplified.

(Embodiment 2)
Next, an organic EL device according to another embodiment will be described with reference to FIG. FIG. 14 is a schematic cross-sectional view showing a main part of the structure of the organic EL device according to the second embodiment. In addition, about the structure similar to Embodiment 1, the same code | symbol is attached | subjected and demonstrated. Further, the configuration of the circuit unit 11 for driving the organic EL element 12 is not shown.

As shown in FIG. 14, the organic EL device 10 </ b> A of the present embodiment includes an anode 31 partitioned by a partition wall 33 on the element substrate 1, a functional layer 32 including a light emitting layer formed on the anode 31, The light emitting region 6 is provided with a plurality of organic EL elements 12 each including a cathode 34 formed on the functional layer 32.
Further, the second gas barrier layer 42 covering at least the light emitting region 6, the first gas barrier layer 41 laminated on the second gas barrier layer 42, and the outer edge portion 41 a of the first gas barrier layer 41 in the peripheral region 6 a of the light emitting region 6. And a second gas barrier layer 42 laminated on the first gas barrier layer 41 so as to cover it.

The first gas barrier layer 41 is formed using the plasma CVD apparatus 200. As film formation conditions, the flow rates of the silane gas and the nitrogen gas are adjusted so that the film formation rate is 100 nm / min or more at room temperature. Thereby, Si _x N _y (film thickness is 0.5 μm to 10 μm (preferably 0.5 μm to 3 μm), refractive index is approximately 1.86, film density is approximately 1.7 g / cm ³ , and film stress is 50 MPa or less. A first gas barrier layer 41 made of silicon nitride was formed.

The second gas barrier layer 42 is formed using the ion plating apparatus 300. As film formation conditions, the film formation temperature is set to 100 ° C. or less, SiO (silicon oxide) as the film formation material M is heated and sublimated by the plasma beam PB, and reacted with nitrogen gas as the reactive gas RG. A second gas barrier layer 42 made of SiON having a thickness of about 400 nm, a refractive index of 1.79, a film density of about 2.7 g / cm ³ , and a film stress of 50 MPa or less was formed.

  Both the first gas barrier layer 41 and the second gas barrier layer 42 are formed as masks as in the first embodiment.

  The element substrate 1 and the sealing substrate 2 having the filter elements 36R, 36G, and 36B are joined and sealed by the sealing material 9 disposed in the peripheral region 6a of the light emitting region 6. The configuration of the sealing material 9 is the same as that of the first embodiment, and a part thereof is arranged so as to cover the outer edge portion 42 a of the second gas barrier layer 42.

  According to the organic EL device 10 </ b> A and the manufacturing method thereof according to the second embodiment, the organic EL device 10 </ b> A has a multilayer gas barrier structure made of an inorganic material, and the outer edge portion 41 a of the first gas barrier layer 41 is formed in the peripheral region 6 a of the light emitting region 6. A second gas barrier layer 42 having a high film density is formed so as to cover it. Therefore, as compared with the organic EL device 10 of the first embodiment, since the first gas barrier layer 41 is sandwiched between the second gas barrier layers 42, a longer light emission lifetime can be realized.

  Further, by forming the first gas barrier layer 41 thicker than in the first embodiment, it is possible to provide both the functions of the planarizing layer and the stress relaxation layer similar to the organic resin layer 45 in the first embodiment. it can.

The basic idea of the gas barrier structure in the organic EL device 10 and the organic EL device 10A of the above embodiment is that the first gas barrier layer 41 covering at least the light emitting region 6 is formed by using a plasma CVD method having excellent covering properties, and the outer edge portion. The gas barrier layer that covers the region including the first gas barrier layer 41 including 41a and is farthest from the light emitting region 6 is a second gas barrier layer 42 formed by an ion plating method that can obtain a high film density.
By configuring both the first gas barrier layer 41 and the second gas barrier layer 42 with an inorganic material, a higher gas barrier property can be obtained than when an organic material is used. In particular, by using the second gas barrier layer 42 made of SiON (silicon oxynitride), both gas barrier properties and light transmittance can be realized at a high level.
Further, by disposing a stress relaxation layer (the organic resin layer 45 in the case of Embodiment 1 above, the first gas barrier layer 41 formed thick in the case of Embodiment 2) below the second gas barrier layer 42, The film density may be further increased so that the film stress of the second gas barrier layer 42 is 100 MPa or more. Thereby, the gas barrier property can be further improved.

FIG. 15 is a graph showing the relationship between film stress and film thickness. In order to obtain gas barrier properties, Si _x N _y and SiON, which are inorganic materials, need a film thickness of at least about 200 nm. Further, in case of forming a film density of about 1.7g / cm ³ ~2.7g / cm ^3, there is a risk that defects such as cracks when the thickness deposition occurs. Therefore, the film thickness is suitably in the range of 200 nm to 1200 nm.

On the other hand, as the first gas barrier layer 41 or the second gas barrier layer 42 covering the light emitting region 6 provided with the plurality of organic EL elements 12, no extra heat or stress is applied to the organic EL element 12 during film formation. Is preferred.
Therefore, as shown in FIG. 15, it is preferable to set the film forming conditions in the hatched region so that the product of the film stress and the film thickness is 120,000 MPa · nm (120 GPa · nm) or less.
For example, the first gas barrier layer 41 or the second gas barrier layer 42 that directly covers the organic EL element 12 has a film stress of 100 MPa or less and an upper limit of the film thickness of 1200 nm.
For example, as the second gas barrier layer 42 covering the organic resin layer 45 having the function of a stress relaxation layer, the film stress is increased to 600 MPa and the film thickness is suppressed to 200 nm.
In this way, it is possible to achieve both a long light emission lifetime and high reliability.

(Embodiment 3)
Next, the electronic apparatus of this embodiment will be described with reference to FIG. FIG. 16 is a schematic perspective view showing a mobile phone as an electronic apparatus.

As shown in FIG. 16, a mobile phone 500 as an electronic apparatus according to the present embodiment includes a main body 502 provided with operation buttons 503, and a display unit 501 that is attached to the main body 502 via a hinge in a folding manner. I have.
The display unit 501 includes the organic EL device 10 according to the first embodiment or the organic EL device 10A according to the second embodiment.
Accordingly, it is possible to provide the mobile phone 500 having a long light emission lifetime and good appearance.

  Various modifications other than the above embodiment are conceivable. Hereinafter, a modification will be described.

(Modification 1) In the organic EL device 10 and the organic EL device 10A of the above embodiment, the gas barrier structure is not limited to this. FIGS. 17A to 17C are schematic sectional views showing a gas barrier structure according to a modification. For example, as shown in FIG. 17A, the first gas barrier layer 41 and the second gas barrier layer 42 may be laminated so as to cover at least the light emitting region and the outer edge portion 41a. In this case, each film thickness is suitably about 400 nm.
Further, as shown in FIG. 17B, the first gas barrier layer 41 and the second gas barrier layer 42 are different from the third gas barrier layer 43 in which the first gas barrier layer 41 and the second gas barrier layer 42 are stacked. It is good also as a structure which laminates | stacks the 4th gas barrier layer 44 laminated | stacked. In this case, the thickness of each layer is suitably about 200 nm.
Furthermore, as shown in FIG. 17C, an organic resin layer 45 may be provided between the third gas barrier layer 43 and the fourth gas barrier layer 44.
According to these configurations, since a configuration in which the first gas barrier layer 41 having a high covering property and the second gas barrier layer 42 having a high film density are stacked is employed, a longer light emission lifetime can be realized.

  (Modification 2) In the manufacturing method of the organic EL device 10 and the organic EL device 10A of the above embodiment, the functional layer forming step is not limited to the method of forming the organic film constituting the functional layer 32 by vapor deposition. For example, the functional layer 32 may be formed using a method of applying and solidifying a liquid containing a functional material. The gas barrier structure of the above embodiment can also be applied using such a liquid coating method.

  (Modification 3) In the organic EL device 10 and the organic EL device 10A of the above-described embodiment, the organic EL element 12 is not limited to one capable of obtaining white light emission. For example, organic EL elements that can obtain red (R), green (G), and blue (B) emission colors may be disposed in the light emitting region 6. In that case, it is not necessary to provide the filter elements 36R, 36G, and 36B on the sealing substrate 2.

  (Modification 4) In the organic EL device 10 and the organic EL device 10A of the above embodiment, the space 35 formed by joining the element substrate 1 and the sealing substrate 2 using the sealing material 9 is made of a transparent resin material. It may be filled. The element substrate 1 and the sealing substrate 2 can be arranged to face each other with a predetermined interval.

  (Modification 5) The electronic device on which the organic EL device 10 of the first embodiment and the organic EL device 10A of the second embodiment are mounted is not limited to the mobile phone 500. For example, an electronic device having a display unit such as a personal computer, a portable information terminal, a navigator, or a viewer can be given. Further, the organic EL device 10 and the organic EL device 10A are not limited to those capable of full color light emission (display), and may be monochromatic light emission. In the case of a single color, it can be applied to an illumination device or an exposure device that exposes photosensitive toner.

  DESCRIPTION OF SYMBOLS 1 ... Element board | substrate as a board | substrate, 6 ... Light emission area | region, 6a ... Peripheral area | region of a light emission area | region 10, 10A ... Organic EL apparatus, 12 ... Organic EL element, 41 ... 1st gas barrier layer, 41a ... Outer edge of 1st gas barrier layer Part 42, second gas barrier layer 43, third gas barrier layer 44, fourth gas barrier layer 45, organic resin layer, 45a, outer edge of organic resin layer, 500, portable telephone as an electronic device.

Claims (17)

A plurality of organic EL elements provided on a substrate;
A first gas barrier layer made of an inorganic material covering at least a planar light emitting region including the plurality of organic EL elements;
A second gas barrier layer made of an inorganic material provided to overlap the first gas barrier layer in a plane,
The second gas barrier layer has a higher film density than the first gas barrier layer, and is disposed on the substrate so as to cover an outer edge of the first gas barrier layer in a peripheral region of the light emitting region. An organic EL device.   The organic EL device according to claim 1, wherein film stresses of the first gas barrier layer and the second gas barrier layer are 100 MPa or less.   The organic EL device according to claim 1, wherein the second gas barrier layer is stacked on the first gas barrier layer.   The organic EL device according to claim 1, wherein an organic resin layer is provided between the first gas barrier layer and the second gas barrier layer at least in the light emitting region. The light emitting region is covered with a third gas barrier layer composed of the first gas barrier layer and the second gas barrier layer sequentially stacked on the plurality of organic EL elements,
An organic resin layer provided to cover the third gas barrier layer;
Covering the outer edge of the organic resin layer in the peripheral region, and the second gas barrier layer laminated on the organic resin layer;
The organic EL device according to claim 1, further comprising: The light emitting region is covered with a third gas barrier layer composed of the first gas barrier layer and the second gas barrier layer sequentially stacked on the plurality of organic EL elements,
An organic resin layer provided to cover the third gas barrier layer;
A fourth gas barrier layer that covers the outer edge of the organic resin layer in the peripheral region and includes the first gas barrier layer and the second gas barrier layer sequentially stacked on the organic resin layer. The organic EL device according to claim 1 or 2.   The organic EL device according to any one of claims 1 to 6, wherein the first gas barrier layer is made of silicon nitride, and the second gas barrier layer is made of silicon oxynitride.   The organic EL device according to claim 7, wherein the first gas barrier layer and the second gas barrier layer have a thickness of 200 nm to 1200 nm. A method of manufacturing an organic EL device having a light emitting region including a plurality of organic EL elements on a substrate,
A light emitting element forming step of forming the plurality of organic EL elements on the substrate;
A first gas barrier layer forming step of forming a first gas barrier layer made of an inorganic material using a plasma CVD method so as to cover at least the light emitting region in a plane;
A second gas barrier layer made of an inorganic material is formed using an ion plating method so as to cover the outer edge of the first gas barrier layer in the peripheral region of the light emitting region and to overlap the first gas barrier layer in a planar manner. A second gas barrier layer forming step,
A method for producing an organic EL device, comprising:   The said 1st gas barrier layer formation process and the said 2nd gas barrier layer formation process form the said 1st gas barrier layer and the said 2nd gas barrier layer at the film-forming temperature of 100 degrees C or less, The Claim 9 characterized by the above-mentioned. Manufacturing method of organic EL device.   11. The method of manufacturing an organic EL device according to claim 9, wherein in the second gas barrier layer forming step, the second gas barrier layer is formed by being stacked on the first gas barrier layer. An organic resin layer forming step of forming an organic resin layer on the first gas barrier layer at least in the light emitting region;
The said 2nd gas barrier layer formation process forms the said 2nd gas barrier layer so that the outer edge part of the said 1st gas barrier layer and the said organic resin layer may be covered in the said peripheral region. Manufacturing method of the organic EL device. The first gas barrier layer forming step includes a step of laminating and forming the second gas barrier layer on the first gas barrier layer,
13. The method of manufacturing an organic EL device according to claim 12, wherein the organic resin layer forming step forms the organic resin layer so as to cover the second gas barrier layer stacked on the first gas barrier layer. .   The second gas barrier layer forming step includes a step of laminating and forming the first gas barrier layer on the organic resin layer, and covers the outer edge of the first gas barrier layer and the organic resin layer that are laminated and formed. The method of manufacturing an organic EL device according to claim 12, wherein the second gas barrier layer is formed.   The first gas barrier layer forming step forms the first gas barrier layer made of silicon nitride, and the second gas barrier layer forming step forms the second gas barrier layer made of silicon oxynitride. Item 15. The method for producing an organic EL device according to any one of Items 9 to 14.   The method of manufacturing an organic EL device according to claim 15, wherein the first gas barrier layer and the second gas barrier layer have a thickness of 200 nm to 1200 nm.   An organic EL device manufactured using the organic EL device according to any one of claims 1 to 8 or the organic EL device manufacturing method according to any one of claims 9 to 16. Features electronic equipment.

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