JP2003282237A - Organic electroluminescent element, apparatus for manufacturing the same, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protective film with a high shielding property of moisture and oxygen in the air and a high resistance to high temperature and to high humidity. <P>SOLUTION: An organic EL element has at least one organic compound layer 30 interposed between a first electrode 12 and a second electrode 18, thus forming an element region, the element region being covered with the protective film 20 composed of at least amorphous carbon nitrite. Since the amorphous carbon nitrite film has a dense film structure similar to an inorganic film while being flexible and having an stress relieving ability as an organic protective film, the amorphous carbon nitrite film can protect the organic EL element from moisture and oxygen without degrading even at a high temperature and a high humidity. A laminated structure with the amorphous carbon nitrite film and an inorganic film such as SiN film may be provided. Such a protective film can be disposed between a substrate and the organic EL element. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device (hereinafter referred to as an organic EL device), and more particularly to a protective film for protecting this device.

[0002]

2. Description of the Related Art An organic EL device comprises an organic layer having electrodes and at least a light emitting layer between the electrodes on a substrate, and electrons and holes are injected from the electrodes on both sides to the light emitting layer in the organic layer to form an organic layer. It is an element that emits light in the light emitting layer and is capable of high brightness light emission. Further, since it uses the light emission of an organic compound, it has a feature that the selection range of the emission color is wide, and it is expected as a light source, a display, etc., and its practical application is now beginning.

Such an organic EL element is apt to be corroded by moisture and oxygen in the air, and when they are present, a dark spot is generated or the element is short-circuited or deteriorated. In order to prevent such deterioration, means for protecting the element is required, and currently, a method of sealing the entire element with a cover glass or a can package in an atmosphere of dry nitrogen, argon gas, etc. is used. There is.

Further, as a method of lowering the cost and easily increasing the area of the element panel, a method of covering the entire organic EL element with a protective film has been proposed. As such a protective film, amorphous carbon (Japanese Patent Laid-Open No. 63-259994) is used.
JP-A-7-161474), silicon nitride film and silicon oxide film (JP-A-4-73886), DLC (Diamond Like Carbon, JP-A-5-10).
1885), it has been proposed to use polyparaxylene (JP-A-4-137483), polyurea (JP-A-8-222368) and the like as the organic material. Further, a structure in which several protective layers are laminated is also proposed, and for example, a laminated structure of a layer formed by a vapor phase method and a layer made of a photocurable resin (Japanese Patent Laid-Open No. 4-2670).
97) or a laminated structure of an inorganic protective film and a sealing resin (Japanese Patent Laid-Open No. 11-40345).

[0005]

A display device using an organic EL element (organic EL display device) is being considered for mounting in various devices. For example, a display device mounted in an automobile (on-vehicle). In order to apply as, it is required to adapt to high temperature and high humidity conditions. It is considered that shielding the organic EL element from moisture and oxygen by using the protective film is an indispensable technique for making the organic EL display device thin, low in cost, and large in area. However, in the in-vehicle use as described above, it is necessary to reliably prevent the phenomenon that the protective film is cracked or the protective film is peeled off due to thermal stress or hygroscopic stress under high temperature and high humidity. Then, in order to avoid such a phenomenon, the protective film needs to be a thin film having excellent stress durability and excellent adhesion to the organic EL element.

An inorganic protective film such as a silicon nitride film or a silicon oxide film, which is often used as a protective film in the field of semiconductors, has a high shielding property against moisture and oxygen in the air and a high thermal conductivity, but has a large Young's modulus and thus has a high thermal conductivity. Stress increases,
Since it is a relatively fragile material, it has a drawback that cracks easily occur. Especially when it is used as a protective film for an organic EL element, it is necessary to form it with a thickness of 1 μm or more in order to enhance the moisture resistance, and the influence of stress is even greater, causing cracking or peeling under high temperature or high humidity conditions. It becomes easier to do.
Therefore, it is not suitable as a protective film in an organic EL display device for in-vehicle use.

The above organic protective film of polyparaxylene, polyurea or the like is a film having excellent flexibility and therefore has high stress durability, but since the film is low in density, it has a low moisture and oxygen shielding property. Again, it is not suitable as a protective film for an organic EL display device for a vehicle.

Amorphous carbon film (a-C)
The protective film made of is inferior in adhesion to the organic EL element, and it is difficult to control stress applied to the film itself,
There is a problem that problems such as cracking and peeling occur under high temperature and high humidity conditions.

Therefore, in order to solve the above problems, it is an object of the present invention to provide a film having an excellent protective function even under high temperature and high humidity as a protective film for an organic EL element.

[0010]

In order to achieve the above object, the present invention is directed to an organic electroluminescence device, which is formed by forming an element region having at least one organic compound layer between electrodes and covering the element region. And a protective film, the protective film containing amorphous carbon nitride.

According to another aspect of the present invention, in an organic electroluminescence device, a protective film is provided between an organic electroluminescence device having at least one organic compound layer between electrodes and a substrate on which the device is formed. The protective film includes amorphous carbon nitride.

In another aspect of the present invention, in the above organic electroluminescent device, the protective film is a single film of the amorphous carbon nitride or a laminated film with an inorganic film.

According to another aspect of the present invention, in the above organic electroluminescent device, the film containing amorphous carbon nitride is:
A film is formed by a vapor phase growth method using a gas containing at least one kind of alkane, alkene or alkyne and a gas containing nitrogen or ammonia as raw materials.

In another aspect of the present invention, in the above organic electroluminescent device, the inorganic film includes any one of a nitride film, an oxide film, a carbon film and a silicon film.

In another aspect of the present invention, the inorganic film is a silicon nitride film, a boron nitride film, an aluminum nitride film, a silicon oxide film, an aluminum oxide film, a titanium oxide film, an amorphous silicon film, an amorphous carbon film or a diamond shape. It is one of the carbon films.

[0016] In another aspect of the present invention, in the organic electroluminescence device, the protective film has a laminated structure of two or more layers of a film containing the amorphous carbon nitride and the inorganic film. The inorganic film is formed between the film and the organic electroluminescent element.

As described above, by using at least the film containing amorphous carbon nitride as the protective film of the device such as the organic EL element, the resistance thereof can be remarkably improved.
Such amorphous carbon nitride has excellent flexibility as an organic protective film and has stress durability, and functions as a stress relaxation film of an element. On the other hand, since it has a denseness similar to that of an inorganic film, it has a very high ability to shield moisture and oxygen. Furthermore, this amorphous carbon nitride film (a-CNx:
The H film) is easy to control the stress characteristic of the film by controlling the nitrogen amount (x) to be introduced. Therefore, it is possible to easily form the protective film having the characteristics required.

Further, a nitride film, an oxide film, a silicon film, a DL
By forming a laminated structure of an inorganic film using a C film or the like and the above amorphous carbon nitride film, it is possible to further improve the shielding property against water and oxygen.

Here, the protective film for the organic electroluminescent device is provided between the substrate and the device, in addition to the protective film formed on the substrate to cover the device and protect the device from the outside. It is also useful as a protective film for preventing moisture and the like from entering the device from the substrate side.

In another aspect of the present invention, at least an amorphous carbon nitride film is used as a protective film that covers the organic electronic device and has high temperature and high humidity resistance. Organic E
There is a strong demand not only for L elements but also for organic electronic devices such as liquid crystal displays and organic transistors, etc., to have high resistance to high temperature and high humidity. By using an amorphous carbon nitride film as a protective film as described above, The reliability and life of the device can be dramatically improved.

Another aspect of the present invention comprises an element region having at least one organic compound layer between electrodes and a protective film covering at least the element region, the protective film being an amorphous carbon nitride film and an inorganic film. An apparatus for manufacturing an organic electroluminescent device having a laminated structure of, which covers the element region, comprising: an element film forming chamber for forming each layer forming the element region, and a protection for forming the amorphous carbon nitride film. A film forming chamber; and an inorganic film forming chamber for forming the inorganic film,
At least each protective film forming chamber for forming the amorphous carbon nitride film or the inorganic film which is formed first to cover the element region and the element film forming chamber are connected directly or via a transfer vacuum chamber. Has been done.

With such a structure, the organic E
The substrate on which the L element is formed can be conveyed to the protective film forming apparatus without exposing the substrate to the atmosphere. By allowing the organic EL element to be transported to the protective film forming apparatus without exposing it to the atmosphere, it is possible to stack the layers in-situ.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention (hereinafter referred to as embodiments) will be described below with reference to the drawings.

[Embodiment 1] FIG. 1 shows a schematic sectional structure of an organic EL element according to Embodiment 1 of the present invention.
An element region is formed by laminating a first electrode 12, an organic compound layer 30, and a second electrode 18 on a substrate 10, and electrons and holes are formed from the first electrode 12 and the second electrode 18 into a light emitting layer. By injecting, the organic compound in the light emitting layer is excited to emit light. The substrate 10 may be a transparent glass substrate, a plastic substrate, or the like, and the material of each layer of the organic EL element formed on the substrate 10 is not particularly limited. In addition to the materials that have been proposed as materials for the above, materials that are newly developed in the future and combinations thereof can be used. As an example,
The first electrode 12 functions as a hole injecting electrode (anode),
The second electrode 18 is configured by using a transparent electrode such as TO (Indium Tin Oxide), functions as an electron injection electrode (cathode), and can be configured by a metal electrode such as Al. The organic compound layer 30 includes at least an organic light emitting material, and has a single-layer structure of a light emitting layer, a hole transporting layer / light emitting layer, a light emitting layer / electron transporting layer, depending on characteristics of an organic material to be used. And the like, a three-layer structure of a hole transport layer / a light emitting layer / an electron transport layer, and a multilayer structure including a charge (hole, electron) injection layer and the like. Figure 1
In the example shown in, the hole injection layer 32, the hole transport layer 34, and the organic light emitting layer 36 are laminated in this order between the transparent first electrode 12 and the second metal electrode 18. Note that, in FIG. 1, the metal second electrode 18 is actually configured by a laminated structure with the electron injection layer 16 formed of lithium fluoride or the like formed on the surface facing the organic light emitting layer 36. .

In the first embodiment, the protective film 20 is formed so as to cover the organic EL element having the above structure. As shown in FIG. 1, the protective film 20 is formed so as to cover the entire element region on the substrate 10 after the second electrode 18 which is the uppermost layer of the element is formed. Protect from oxygen etc. As a material of the protective film 20,
Amorphous carbon nitride (a-CNx: H) is used. a
Since the -CNx: H film has a density close to that of an inorganic film, it has a high shielding property against moisture and oxygen in the air. Furthermore, since it has excellent coverage and flatness, and also has flexibility as an organic film, it has high stress durability, and thermal stress and moisture absorption stress can be relaxed by this a-CNx: H film. Furthermore, a-C
The Nx: H film can realize a low-stress film because the element N contained in the film enhances the bonding force with the base material, and can be used as a protective film for an organic EL device when placed under high temperature and high humidity. Also, it is possible to prevent peeling and cracks. Also, a-
The CNx: H film can be formed by a plasma vapor phase growth method using methane gas and nitrogen gas as raw materials, methane gas and nitrogen gas as raw materials are inexpensive, and a film forming apparatus (plasma vapor phase growth apparatus) is also used. It is relatively inexpensive and very advantageous in reducing the manufacturing cost of organic EL devices. Also,
The ratio of N in the film can be adjusted by controlling the ratio of methane gas and nitrogen gas that are raw materials, and the characteristics of the a-CNx: H film formed according to the ratio (x) of N, particularly stress and the like, can be accurately measured. You have good control. Therefore, this a-CNx: H film is very excellent as a protective film for an organic EL element.

The protective film 20 is formed of the a-CN as shown in FIG.
The x: H film is not limited to a single layer structure, and may have a laminated structure with another protective material film. By forming a laminated structure with, for example, an inorganic protective film having a high shielding property against moisture and oxygen, the protective film 20
As a result, it is possible to further improve the shielding property against moisture and oxygen and the stress relaxation ability, and to improve the adhesiveness with the organic EL element. The inorganic protective film used in combination with the a-CNx: H film has a high stress when formed thick, and thus is preferably formed thin. As the inorganic protective film, a nitride film, an oxide film, a carbon film, a silicon film, or the like can be adopted, and more specifically, a silicon nitride film (Si
N film), boron nitride film, aluminum nitride film, silicon oxide film (SiO ₂ film), aluminum oxide film (Al ₂ O)
₃ films), a titanium oxide film (TiO ₂ film, TiCO film, etc.), an amorphous silicon film, an amorphous carbon film or a diamond-like carbon (DLC) film.

As shown in FIG. 2, another structure of the protective film 20 is, in order from the organic EL element side, an a-CNx: H film 22.
It is also possible to adopt a structure in which the SiN film 24 and the SiN film 24 are laminated. Since the SiN film is a very dense film, this S
By stacking the iN film on the a-CNx: H film, it is possible to enhance the ability to shield moisture and oxygen from entering from above the device, and improve the reliability of the organic EL device.

The protective film 20 is, as shown in FIG.
The stacking order may be reversed and the inorganic protective film and the a-CNx: H film may be stacked in this order. Specifically, the protective film 20 in which the SiN film 24 and the a-CNx: H film 22 are stacked in this order from the organic EL element side can be adopted. The film structure of the a-CNx: H film is
Since there is an underlayer dependency, by adopting a dense film such as the SiN film 24 as the underlying film, the a-CNx: H film 22 formed thereon is more dense and has a moisture and oxygen shielding function. It can be a high membrane.

Further, the SiN film has a high adsorptivity to the surface of the base material of the film because silane, which is a raw material, is chemically active. On the other hand, an alkane such as methane gas which is a raw material of the a-CNx: H film, Since a gas such as alkene is not as active as silane, for example, when compared with the SiN film, the second electrode (metal electrode) 18 of the organic EL element is a-CN.
The x: H film has lower coverage. Therefore, a-CNx: H
If a SiN film is formed below the film, the SiN film covers the organic EL element with good adhesion, and an a-CNx: H film with good film quality can be formed on this SiN film, further improving resistance to high temperature and high humidity. Can be increased. Although particles such as dust may be attached to the surface of the organic EL element during the formation of the protective film, the SiN film 24 has good adhesion to the surface of the dust as well as the surface of the organic EL element. Since the SiN film 24 can be formed and the a-CNx: H film 22 covers the SiN film 24, it is easy to cover the particle adhesion region with the a-CNx: H film 22 having high flatness and coverage. For this reason, it is possible to prevent the protective film from being poorly covered in the particle region and prevent moisture and oxygen from entering the organic EL element from the discontinuous portion of the protective film.

The protective film 20 is formed of a-CN shown in FIG.
x: a film having a higher ability to shield moisture and oxygen from the upper layer of the H film,
For example, an inorganic protective film such as a SiN film may be formed. Figure 4
Shows the structure of the protective film 20 having such a three-layer structure, and the SiN film 24, a-CNx: H are arranged from the organic EL element side.
The film 22 and the SiN film 24 are formed in this order. Since the SiN film 24 is formed on the uppermost layer of the protective film, the organic E
It is possible to more reliably prevent the entry of moisture or the like from above the L element. Note that, as in the above-described configuration example, the uppermost Si layer
Also for the N film 24, in order not to increase the stress in the film,
It is preferable to form the thin film within a range where the effect of shielding moisture and the like is obtained and the necessary strength is obtained.

The protective film 20 is an a-CNx: H film,
It may have a structure in which SiN films are further laminated.
By doing so, the reliability of the protective film can be further enhanced.

[Embodiment 2] FIG. 5 shows a schematic sectional structure of an organic EL device according to Embodiment 2. Embodiment 1
The difference is that not only is the organic EL element covered with the protective film 20 from the second electrode 18 side, but also the substrate 11 and the organic E element are covered.
The point is that a protective film (buffer layer) 21 is formed between the L element (here, the first electrode 12). When a plastic substrate, which is excellent in flexibility and is cheaper than a glass substrate, is used as the substrate 11 for forming the element, the plastic substrate has a lower moisture and oxygen shielding property than the glass substrate, so It is necessary to prevent the ingress of water and oxygen. Therefore, as shown in FIG. 5, the substrate 11 and the organic EL are
By forming the protective film 21 between the element and the organic E
The protection of the L element becomes more reliable. As the protective film 20 covering the organic EL element, as shown in the first embodiment, a-
A single layer structure of a CNx: H film or a multilayer structure of a SiN film or the like can be adopted.

The protective film 21 also has a-CNx: H.
It is preferable to use a film from both viewpoints of stress relaxation and shielding of moisture and oxygen. Further, it is not limited to the single layer structure of the a-CNx: H film, and it is more preferable to have a laminated structure with an inorganic protective film such as a thinly formed SiN film. As the laminated structure, for example, an a-CNx: H film / SiN film, a SiN film / a-CNx: H film, or the like formed in this order from the substrate 11 side or a multi-layered structure can be employed.

Here, the organic EL element covered with the protective film as in Embodiments 1 and 2 can be formed by using a manufacturing apparatus as shown in FIG. In the manufacturing apparatus shown in FIG. 6, an element film forming chamber (organic compound layer film forming chamber 102, second electrode film forming chamber 103) for forming each layer of an organic EL element including an organic layer between electrodes, The respective film forming chambers including the film forming chambers (201, 202) for the protective film formed on the element forming region are all connected to a common transfer vacuum device 300 via a gate valve (GV). Has a cluster structure. The substrate introducing chamber and the substrate unloading chamber can be configured as a common chamber 100.

By adopting such a cluster structure, the tolerance to changes in the forming process of the manufacturing apparatus, for example,
The protective film 20 can be easily adapted from the above-mentioned stacking order shown in FIG. 2 to the reverse stacking order as shown in FIG. 3 or when the number of stacked protective films 20 is increased as shown in FIG. You can
Further, it is easy to reduce the installation area of the device.
Of course, a so-called in-line structure in which the element film forming chamber and the protective film forming chamber are directly connected may be used. A gate valve is provided between the chambers so that the chambers are independent of each other. In any of these device configurations, the element region is protected by the protective film 2 without being exposed to the outside air at a step after the organic compound layer forming the organic EL element is formed.
It is possible to surely protect the element organic compound layer which can be covered with 0 and is easily deteriorated when exposed to the atmosphere.

As described above, a-CN forming the protective film
The x: H film can be formed by plasma vapor deposition (CVD). In addition, regarding an SiN film, which is an inorganic protective film having a multilayer structure with the a-CNx: H film,
It is suitable to form by plasma CVD method.
Of course, the inorganic protective film such as SiN film and SiO ₂ film is
It can be formed by a sputtering method used in a semiconductor device or the like. However, in the sputtering method, the damage to the organic EL element, which is more susceptible to damage than semiconductor devices and the like, is large, and the important existence of the protective film is to shield the element from the outside air. Since the obtained film density and coverage are inferior to those of CVD, it is more preferable to form the film by the plasma CVD method. In particular, when the SiN film is formed on the organic EL element side as shown in FIGS. 3 and 4, it is desirable to form it by the plasma CVD method in order to prevent damage to the organic EL element.

In the above, the organic EL is to be protected.
Although the element is described as an example, the protective film using the amorphous carbon nitride material according to the embodiment of the present invention,
In organic electronic devices such as so-called organic transistors that use organic materials as active layer materials, even when used as protective films for elements that require high protection from moisture and oxygen, the same high effects are achieved. it can.

[0038]

EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 3 will be described below. The configurations of the organic EL elements used in Examples 1 to 4 and Comparative Examples 1 and 2 are the same.

Referring to FIG. 1, the element portion of the organic EL element is formed on the glass substrate 10 with the first electrode 12, the hole injection layer 32, the hole transport layer 34, the organic light emitting layer 36, and the electron injection layer. The second electrode 18 including 16 was laminated in this order. Further, also in Example 5 and Comparative Example 3, the structure of the organic EL element is the same except that the polyethylene terephthalate (PET) film substrate 11 is used as the substrate.

More specifically, the structure of the organic EL element is as follows.
In Examples 1 to 5 and Comparative Examples 1 to 3, ITO (Indium) was used as the first electrode 12 on the substrate 10 (or substrate 11).
TinOxide) is 150 nm, copper phthalocyanine (CuPc) is 10 nm as the hole injection layer 32, and the hole transport layer 34 is
As triphenylamine tetramer (TPTE) 50n
m, a quinolinol aluminum complex (Alq
₃ ) 60 nm, lithium fluoride (LiF) 0.5 nm was formed as the electron injection layer 16, and aluminum (Al) 100 nm was formed as the second electrode 18. In addition, Example 1
4. In Comparative Examples 1 and 2, as the ITO, a glass substrate on which ITO was previously formed was used. Each layer other than ITO was formed in-situ by vacuum evaporation.

Example 1 In Example 1, a single layer of a-CNx: H film was used as the protective film covering the organic EL element. FIG. 1 described above corresponds to the cross-sectional structure of the organic EL element according to the first embodiment. In Example 1, an a-CNx: H film was formed by plasma vapor deposition using methane gas and nitrogen gas as raw materials so as to cover the organic EL element from the second electrode 18 side. The pressure during film formation is 200 mTorr (1 Torr≈1
33 pa), the flow rate of methane gas was 10 sccm, the flow rate of nitrogen gas was 5 sccm, the plasma input power was 20 W, and the substrate temperature was room temperature. The thickness of the a-CNx: H film is 2μ
m.

[Embodiment 2] In Embodiment 2, as shown in FIG. 2 above, the protective film 20 covering the organic EL element is a
-CNx: A laminated structure of the H film 22 and the SiN film 24 is formed, and the organic EL element is covered with aC to cover the second electrode 18 side.
An Nx: H film 22 is formed, and a SiN film 24 is further formed thereon.
Was formed. The thickness of the a-CNx: H film 22 is 2 μm,
A film was formed under the same conditions as in Example 1 above. SiN film 24
Was produced by a plasma CVD method using silane gas, ammonia gas, and nitriding gas as raw materials. The pressure during the formation of the SiN film is 400 mTorr, and the silane gas flow rate is 30 scc.
m, ammonia gas flow rate 30 sccm, nitrogen gas flow rate 2
50sccm, plasma input power 10W, substrate temperature 1
A film was formed under the condition of 00 ° C. to a thickness of 0.1 μm.

[Embodiment 3] In Embodiment 3, as shown in FIG. 3, Si is used as the protective film 20 for covering the organic EL element.
The N film 24 and the a-CNx: H film 22 were laminated in this order from the organic EL element side. The film forming conditions and film thicknesses of the respective films are the same as in Example 2 except that the stacking order is different.

[Embodiment 4] In Embodiment 4, as shown in FIG. 4, as the protective film 20 for covering the organic EL element, the SiN film 24 / a-CNx: H film 2 is formed from the organic EL element side.
The 2 / SiN film 24 has a three-layer structure. Similarly, the SiN film covering the organic EL element and the uppermost SiN film are both formed with a thickness of 0.1 μm under the same conditions as in Example 2 above, and a-CNx: H
The film 22 was formed with a thickness of 2 μm under the same conditions as in Example 1 above.

[Embodiment 5] In Embodiment 5, as shown in FIG. 5 described above, PET is used as a substrate for forming an organic EL element.
Using the film substrate 11, on the film substrate 11,
As the protective film 21 (buffer layer), covering the substrate with aC
An Nx: H film 23 having a thickness of 2 μm is formed, and the film is covered with SiN.
The film 25 was formed to a thickness of 0.1 μm. The film forming method is the same as that in each of the above-described embodiments, and the formed SiN film 25 is used.
An organic EL element was formed on the above, similarly to each example.
Then, the protective film 20 is formed so as to cover the organic EL element. As the protective film 20, similarly to the third embodiment, a SiN film 24 having a thickness of 0.1 μm from the device side and an a-CNx: H film 2 are formed.
No. 2 was formed under the same conditions as those of the above-described example, with a thickness of 2 μm.

[Comparative Example 1] Comparative Example 1 with respect to the above embodiment
As a protective film covering the organic EL element formed on the glass substrate, a SiN film, which is an inorganic protective film, was formed to a thickness of 2 μm by the plasma CVD method. This SiN
The film forming conditions were the same as above.

[Comparative Example 2] In Comparative Example 2, a polyparaxylene film which is an organic protective film is used as a protective film for covering the organic EL element formed on the glass substrate by the CVD method.
It was formed to a thickness of 2 μm.

[Comparative Example 3] In Comparative Example 3, as a protective film covering the organic EL element formed on the glass substrate, a
A C: H (amorphous carbon) film was formed to a thickness of 2 μm. This aC: H film was formed by a plasma CVD method using methane gas as a raw material.

[Evaluation] The samples prepared in the respective examples and comparative examples were annealed in the atmosphere at 100 ° C. for 1 hour. However, in Example 5 in which the film was used as the substrate, the condition was 1 hour at 60 ° C. After annealing under such conditions, a high temperature test and a high humidity test were performed.

In the high temperature test, each organic EL device was caused to emit light in an environment of 85 ° C. for 1000 hours, and the rate of change in the light emitting area before and after the test was determined. In the high humidity test, 65
Leave the sample for 100 hours under the condition of ℃ and 95% RH.
The rate of change in the light emitting area before and after the test was determined. The results are shown in Table 1.

[0051]

[Table 1] In each of Examples 1 to 5, the emission area after the test achieved 80% or more in both the high temperature test and the high humidity test, but in Comparative Examples 1 to 3, the high temperature test and the high temperature test were performed. Either one of the humidity tests gives a result of less than 50%. Specifically, when only the SiN inorganic protective film is used as in Comparative Example 1, the resistance under high humidity is high,
As a result of the high temperature test, the entire area is non-luminous. On the other hand, when only the aC: H film was adopted as in Comparative Example 3, a high result of 82% was obtained at high temperature, but the result of the high humidity test was that the protective film peeled off. There is. Therefore, it is understood that the SiN film single layer and the aC: H film single layer are unsuitable for in-vehicle use in which at least high resistance to high temperature and high humidity is strongly required. When a polyparaxylene film was used as the protective film as in Comparative Example 2, the high temperature and high humidity test results were neither extremely bad (near 0%), but the high temperature test was 66%. In the high humidity test, 32%, which are both insufficient. Therefore, it can be seen that the protective film of Comparative Example 2 is also unsuitable for in-vehicle use, which requires resistance to high temperature and high humidity.

In contrast to such a comparative example, the a-CNx: H film of the present invention, which is an organic material, has a high temperature test of 89% and a high humidity test of 81% even if it has a single layer structure as in Example 1. And very favorable results have been obtained. Further, as shown in Examples 2 and 3, if a two-layer structure of an a-CNx: H film and a thin SiN film is adopted, the function as a protective film is improved, and the stacking order of the two layers is It can be seen that Example 3 is more effective. In addition, in Example 4 in which the protective film having a three-layer structure of SiN / a-CNxH / SiN was used, a light emitting area of 99% or more was realized after both the high temperature and high humidity tests. It can be seen that it is particularly effective as a protective film for an organic EL display device for use.

Also, in the device according to Example 5 using the film substrate, the light emitting area of 85% after the high temperature test and 80% after the high humidity test was realized, and the moisture and oxygen were higher than those of the glass. Even when a film substrate having inferior shielding ability is used, the protective film 21 and the protective film 2 as in Example 5 are used.
It can be seen that with 0, the resistance of the organic EL element to high temperature and high humidity can be dramatically improved.

[0054]

As described above, according to the present invention, by covering the electronic device such as the organic EL element with the protective film containing at least the amorphous nitrogen carbide material, the electronic device is not deteriorated even at high temperature and high humidity. This organic EL element or the like can be protected from moisture and oxygen, and the reliability and life of the element can be dramatically improved.

[Brief description of drawings]

FIG. 1 is a diagram showing a schematic cross-sectional configuration of an organic EL element according to Embodiment 1 and Example 1 of the present invention.

FIG. 2 is a diagram showing a schematic sectional configuration of an organic EL element according to Embodiment 1 and Example 2 of the present invention.

FIG. 3 is a diagram showing a schematic cross-sectional configuration of an organic EL element according to Embodiment 1 and Example 3 of the present invention.

FIG. 4 is a diagram showing a schematic cross-sectional structure of an organic EL element according to Embodiment 1 and Example 4 of the present invention.

FIG. 5 is a diagram showing a schematic cross-sectional structure of an organic EL element according to Embodiment 2 and Example 5 of the present invention.

FIG. 6 is a diagram showing an example of an organic EL element manufacturing apparatus of the present invention.

[Explanation of symbols]

10 glass substrate, 11 film substrate, 12 first electrode, 16 electron injection layer, 18 second electrode, 20 protective film, 22, 23 amorphous carbon nitride (a-CNx:
H) film, 24 inorganic protective interlayer film (SiN film, SiO2 film or DLC film, etc.), 25 SiN film, 30 organic compound layer, 32 hole injection layer, 34 hole transport layer, 36
Organic light emitting layer, 100 substrate loading / unloading chamber, 101 substrate loading chamber, 102 organic thin film deposition chamber, 103 cathode deposition chamber, 201 protective film (SiN) deposition chamber, 202 protective film (a-CNxH) deposition chamber , 203 Substrate ejection chamber, 300
Vacuum device for transportation.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Atsushi Miura             Aichi Prefecture Nagachite Town Aichi District             Ground 1 Toyota Central Research Institute Co., Ltd. (72) Inventor Kuki Fujikawa             Aichi Prefecture Nagachite Town Aichi District             Ground 1 Toyota Central Research Institute Co., Ltd. (72) Inventor Yasunori Taga             Aichi Prefecture Nagachite Town Aichi District             Ground 1 Toyota Central Research Institute Co., Ltd. F-term (reference) 3K007 AB11 AB12 AB13 AB14 AB18                       BB01 DB03 FA01 FA02

Claims (10)

[Claims] 1. An organic electroluminescent device comprising: an element region having at least one organic compound layer between electrodes; and a protective film formed so as to cover the element region, wherein the protective film is amorphous carbon nitride. An organic electroluminescent device comprising: 2. An organic electroluminescent device comprising: an organic electroluminescent device having at least one organic compound layer between electrodes; and a substrate on which the device is formed, the protective film being amorphous. An organic electroluminescent device comprising carbon nitride. 3. The organic electroluminescent element according to claim 1 or 2, wherein the protective film is a single film of the amorphous carbon nitride or a laminated film with an inorganic film. 4. The organic electroluminescent device according to claim 1, wherein the film containing amorphous carbon nitride contains a gas containing at least one kind of alkane, alkene or alkyne, and nitrogen or ammonia. An organic electroluminescence device, characterized in that a film containing a gas containing the same is formed by a vapor phase growth method. 5. The organic electroluminescent device according to claim 3, wherein the inorganic film includes any one of a nitride film, an oxide film, a carbon film, and a silicon film. 6. The organic electroluminescent device according to claim 5, wherein the inorganic film is a silicon nitride film, a boron nitride film, an aluminum nitride film, a silicon oxide film, an aluminum oxide film, a titanium oxide film, an amorphous silicon film, An organic electroluminescent device comprising an amorphous carbon film or a diamond-like carbon film. 7. The organic electroluminescent element according to claim 3, 5 or 6, wherein the protective film is formed of two or more layers including a film containing the amorphous carbon nitride and the inorganic film. An organic electroluminescent device having a laminated structure, wherein the amorphous carbon nitride film and the inorganic film are formed in this order from the organic electroluminescent device side. 8. The organic electroluminescent element according to claim 3, 5 or 6, wherein the protective film is formed of two or more layers including a film containing the amorphous carbon nitride and the inorganic film. An organic electroluminescence device comprising a laminated structure, wherein the inorganic film and a film containing amorphous carbon nitride are formed in this order from the organic electroluminescence device side. 9. An organic electronic device characterized in that a film containing at least amorphous carbon nitride is used as a protective film covering the organic electronic device and having high temperature and high humidity resistance. 10. An element region having at least one organic compound layer between electrodes, and a protective film covering at least the element region, the protective film having a laminated structure of an amorphous carbon nitride film and an inorganic film. A device for manufacturing an organic electroluminescent element capable of covering an element region, wherein an element film forming chamber for forming each layer constituting the element region, and a protective film forming chamber for forming the amorphous carbon nitride film, An inorganic film forming chamber for forming the inorganic film, and at least respective protective film forming chambers for forming the amorphous carbon nitride film or the inorganic film formed first to cover the element region, An apparatus for manufacturing an organic electroluminescence device, which is connected to the device film forming chamber directly or via a vacuum chamber for transportation.