JP5798886B2 - Manufacturing method of organic EL device - Google Patents

Description

The present invention relates to a method of manufacturing an organic EL (Electro Luminescence) equipment.

  In recent years, organic EL devices have attracted attention as a lighting device that can replace incandescent lamps and fluorescent lamps, and many studies have been made. In addition, an organic EL method is attracting attention as a method for changing to a liquid crystal method or a plasma method in a display member typified by a television.

Here, the organic EL device is obtained by laminating an organic EL element on a base material such as a glass substrate or a transparent resin film.
In addition, the organic EL element has two or more light-transmitting electrodes facing each other, and a light emitting layer made of an organic compound is laminated between the electrodes. The organic EL device emits light by the energy of recombination of electrically excited electrons and holes.
Since the organic EL device is a self-luminous device, a high-contrast image can be obtained when used as a display material. In addition, light of various wavelengths can be emitted by appropriately selecting the material of the light emitting layer. Further, since the thickness is extremely thin compared to incandescent lamps and fluorescent lamps, and the light is emitted in a planar shape, there are few restrictions on the installation location.

  By the way, the organic EL element has a problem that when it is driven for a certain period, the light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are significantly deteriorated as compared with the initial case. The causes of such deterioration of the light emission characteristics include oxidation of the electrode due to oxygen that has entered the organic EL element, oxidative decomposition of the organic material due to heat generated during driving, and the electrode due to moisture in the air that has entered the organic EL element. Examples thereof include oxidation and modification of organic substances. In addition, the interface of the structure is peeled off due to the influence of oxygen and moisture, the heat generated during driving and the environment during driving are high temperature, etc. Mechanical deterioration of the structure such as stress is generated at the interface and the interface is peeled off can also be cited as a cause of deterioration of the light emission characteristics.

  That is, in order to prevent the deterioration of the organic EL device, it is necessary to prevent the liquid such as water or the gas such as oxygen from entering the organic EL element.

  In order to prevent such a problem, a technique has been proposed in which a sealing film is stacked on an organic EL element to prevent a liquid such as water or a gas such as oxygen from entering the organic EL element.

  For example, as a technique for preventing deterioration due to oxygen and moisture, a technique is disclosed in which a two-layer sealing film having waterproof properties is provided on a substrate on which organic EL elements are stacked (Patent Document 1).

  In the method of manufacturing an organic EL device described in Patent Literature 1, a waterproof first sealing film is formed on a substrate on which organic EL elements are stacked using a plasma CVD method, and then opened to the atmosphere. Thereafter, a silicon oxide film is formed by applying a coating solution containing polysilazane using a wet method and heating the coating solution.

JP 2007-059131 A

  By the way, when manufacturing an organic EL device, when organic EL elements are stacked on a substrate and the organic EL elements are processed, impurities such as dust and dust may be mixed on the surface of the organic EL elements. That is, the organic EL element is manufactured in a clean environment such as a clean room. However, even if extreme care is taken, it is inevitable that a small impurity such as a few nm is mixed. Then, when the first sealing film is formed by moving to a sealing process similar to that of Patent Document 1 while impurities are mixed on the organic EL element, the first sealing film may rise from the impurities as a starting point. is there. That is, this bulge causes a portion where the interface bond is locally weak. If an external force acts on the interface where the bonding at the interface is weak during or after the formation of the first sealing film, in some cases, a void may be generated in the first sealing film due to the external force.

  Thereafter, when the second sealing film is formed on the first sealing film using the wet method in a state where the first sealing film has such voids, water is formed in the voids of the first sealing film. May enter and reach the organic EL element. Therefore, in the manufacturing method of Patent Document 1, there is still a concern about deterioration of the organic EL device due to entry of moisture or the like.

  Therefore, the present invention solves the above-described problems, and an object of the present invention is to develop an organic EL device that can prevent moisture and the like from entering the light emitting portion of the organic EL device and a method for manufacturing the same. is there.

The invention described in claim 1 for solving the above-described problem is a method for manufacturing an organic EL device, wherein a laminate including a first electrode layer, an organic light emitting layer, and a second electrode layer is formed on a substrate. And a sealing step for sealing part or all of the laminate formed in the step, the sealing step including a deposited layer film forming step for forming a deposited layer by applying crystal growth In the deposited layer film forming step, deposited layers having different properties or identically deposited layers are laminated with a predetermined time interval , and the sealing step forms a coating layer on the deposited layer. A coating step of forming a coating layer by coating a liquid polysilazane derivative on the deposited layer, and subjecting the polysilazane derivative to steam oxidation by exposure to steam in the presence of a catalyst to convert to silica. A method for producing an organic EL device which is characterized in that.
That is, the present invention is a method for manufacturing an organic EL device, the step of forming a laminate including a first electrode layer, an organic light emitting layer, and a second electrode layer on a substrate, and the laminate formed in the step A sealing step of sealing part or all of the body, the sealing step including a deposition layer film forming step of forming a deposition layer by applying crystal growth, in the deposition layer film formation step, Stacked layers having different properties or the same properties are stacked with a pause.

  The “deposition layers having different properties” referred to here are concepts including those having the same main component, different component ratios, and different crystal structures. For example, a film having different temperatures, pressures, plasma outputs, substrate surface temperatures, source gas supply ratios, and the like at the time of film formation. In addition, the “main component” as used herein represents that a specific component occupies 50% to 100% of the entire component. That is, it includes those to which a small amount of dopant is added.

  In a method of crystallizing and forming a film using crystal growth such as plasma CVD, crystal nuclei are first formed, and the crystal is grown from the crystal nuclei as a starting point. However, when foreign matter is mixed in as described above, a portion having weak interface bonding may be formed when a deposited layer is formed, and a void may be formed. Once a void is generated in the film during film formation, if the film formation is continued thereafter, crystal growth continues from the same crystal nucleus. Therefore, the film is not formed so much on the portion where the void is generated. That is, after the film formation, a region where the bonding of the interface is weak locally occurs while maintaining the void. When an external force such as compressive stress is applied to a portion where the interface is weakly bonded, the interface may be displaced and the gap may be enlarged. In some cases, the gap reaches the laminate.

  Therefore, in the manufacturing method according to the present invention, in the deposition layer film forming step, a method of stacking deposition layers having different properties or deposition layers having the same properties with a pause time is employed. In other words, a pause time is provided, and the deposited layer is laminated in a plurality of times. That is, after the deposition layer is first laminated, the crystal growth of the deposition layer is temporarily stopped and then the deposition layer is laminated again. Therefore, even if foreign matter is mixed in the step of forming the laminated body and voids are generated in the deposited layer film forming step, the deposited layer is laminated again after temporarily stopping the crystal growth. As a result, a deposited layer is also formed in the gap, so that the gap can be filled. As a whole, a large void reaching the laminated body is not formed, and a good deposited layer can be formed. That is, according to the manufacturing method of the present invention, the sealing property is high, and entry of moisture or the like into the organic light emitting layer can be prevented.

In the manufacturing method according to claim 1, it is preferable that the deposition layer film forming step stacks the deposition layers having different compositions with the predetermined time interval (claim 2).
In the invention related to the present invention, in the deposited layer film forming step, deposited layers having different compositions are stacked with a pause time.
According to a third aspect of the present invention, in the deposition layer film forming step, the deposition layer is formed using a plasma CVD method, and the film formation is performed a plurality of times with an interruption time during which plasma generation is interrupted. 2. The method of manufacturing an organic EL device according to claim 1, wherein the process is performed, and a deposited layer having the same property is formed in the film forming process before and after the interruption time.
The invention according to claim 4 is the method for manufacturing an organic EL device according to claim 3, characterized in that the source gas used in the film forming process before the interruption time continues to flow during the interruption time.
A fifth aspect of the present invention is the method of manufacturing an organic EL device according to the third or fourth aspect, wherein the deposition layer film forming step is performed three or more times.

In the above manufacturing method, the deposition layer forming process, metal oxides, metal nitrides, among the metal carbide, but is intended to deposit one at least preferred (claim 6).

Invention relating to the present invention, the sealing step is a this having a coating step of forming a coating layer coating the upper side of the deposited layer.

  According to such a method, the method includes a coating step of forming a coating layer that coats the deposited layer. That is, since the sealing is performed by the two layers of the deposited layer and the coating layer, the sealing performance is high.

Inventions described above, since both can be formed of a deposited layer of voids reaching laminate is not formed, even if a wet method containing water, capable of being deposited.

Therefore, the invention relating to the present invention, the coating layer is a this is formed using a wet process.

  According to such a method, since the coating layer is formed using a wet method, a dense layer can be formed on the deposited layer, and the sealing property is high.

According to a seventh aspect of the present invention, the organic EL device manufacturing method according to any one of the first to sixth aspects includes a first electrode layer, an organic light emitting layer, and a second electrode layer on a substrate. A laminated body and a sealing layer that seals all or a part of the laminated body, and at least one of the sealing layers has a deposited layer containing foreign matter, and the foreign matter is contained in the deposited layer. An organic EL device manufacturing method comprising manufacturing an organic EL device having a discontinuous interface in the vicinity thereof.

  In the organic EL device manufactured by such a method, at least one of the sealing layers has a deposited layer containing foreign substances. That is, in the deposited layer film forming process, there is a possibility that a place where the bonding of the interface is weak in the vicinity of the foreign matter and voids are likely to occur. However, according to such a method, the discontinuity of the interface is formed in the vicinity of the foreign matter, thereby improving the interface bondability. That is, even if foreign matter is mixed in the sealing layer, it is possible to prevent a large gap from reaching the laminated body from being formed.

The invention related to the present invention includes: a laminate including a first electrode layer, an organic light emitting layer, and a second electrode layer on a substrate; and a sealing layer that seals all or part of the laminate. In the organic EL device, at least one of the sealing layers has a deposited layer containing foreign matter, and a discontinuous interface exists in the vicinity of the foreign matter in the deposited layer. It is.

  According to such a configuration, it is possible to prevent moisture and the like from entering the laminate.

  According to the method for manufacturing an organic EL device of the present invention, it is possible to form a good deposited layer and to have high sealing performance. Therefore, it is possible to prevent moisture and the like from entering the light emitting part of the organic EL device.

It is the cross-sectional perspective view which observed the organic EL device of 1st Embodiment of this invention from the back surface side, and has partially peeled off the sealing film. It is sectional drawing of the organic electroluminescent apparatus of FIG. It is a principal part enlarged view of the organic electroluminescent apparatus of FIG. It is explanatory drawing showing the flow of the electric current of the organic electroluminescent apparatus of FIG. For convenience of explanation, hatching is omitted and the insulating portion is painted black. 2 is a flowchart showing a deposited layer film forming process in the manufacturing process of the organic EL device of FIG. 1. It is a figure which shows the TEM image obtained by observing at the low magnification of the organic electroluminescent apparatus in Example 1. FIG. It is the figure which sketched the TEM image of the organic electroluminescent apparatus of FIG. It is a figure which shows the TEM image obtained by observing at the low magnification of the organic electroluminescent apparatus in the comparative example 1. FIG. It is the figure which sketched the TEM image of the organic electroluminescent apparatus of FIG.

  The present invention relates to an organic EL device and a method for manufacturing the organic EL device. FIG. 1 shows an organic EL device 1 according to the first embodiment of the present invention.

As shown in FIGS. 1 and 2, the organic EL device 1 includes a first electrode layer 3, a functional layer 5 (organic light emitting layer), and a second electrode layer 6 on one surface of a substrate 2 (base material). It has a structure laminated in this order. 1 and 2 schematically show the foreign material 12 scattered on the surface of the second electrode layer 6 for ease of explanation, but in actuality, It is a fine thing such as shavings.
Further, it is sealed by laminating a deposition layer 7 and a coating layer 8 thereon. That is, for convenience of explanation, the drawing assumes that a foreign substance 12 is mixed between the second electrode layer 6 and the deposited layer 7. In the present embodiment, in the organic EL device 1, the three layers of the first electrode layer 3, the functional layer 5, and the second electrode layer 6 are collectively referred to as the organic EL element 10, and the deposition layer 7 and the coating layer 8 are used. These two layers are collectively referred to as a sealing layer 11.

  As shown in FIGS. 1 and 2, the first electrode layer 3 is provided with a first electrode layer separation groove 15 in which the first electrode layer 3 is partially removed. The functional layer 5 is provided with a functional layer separation groove 16 from which the functional layer 5 has been partially removed. Both the second electrode layer 6 and the functional layer 5 are provided with unit light emitting element separation grooves 17 in which both the second electrode layer 6 and the functional layer 5 are partially removed.

Further, in the organic EL device 1, each thin layer is partitioned by the first electrode layer separation groove 15, the functional layer separation groove 16, and the unit light emitting element separation groove 17, so that independent unit EL elements 20a, 20b,. Has been.
That is, as shown in FIG. 2, one of the plurality of first electrode layers 3 partitioned by the first electrode layer separation grooves 15 and the partition of the functional layer 5 stacked on the partitioned first electrode layer 3. A unit EL element 20 is constituted by the section of the second electrode layer 6.

2 and 3, a part of the second electrode layer 6 enters the functional layer separation groove 16, and a part of the second electrode layer 6 is in contact with the first electrode layer 3b. One unit EL element 20a is electrically connected in series with the adjacent unit EL element 20b.
That is, since the first electrode layer separation groove 15 and the functional layer separation groove 16 are at different positions, the functional layer 5a belonging to one unit EL element 20a and the second electrode layer 6 protrude from the first electrode layer 3a. It straddles the adjacent unit EL elements 20b. And the approach part 13a which entered the functional layer separation groove 16 of the second electrode layer 6a is in contact with the first electrode layer 3b of the adjacent unit EL element 20b.

  As a result, the unit EL element 20a on the substrate 2 is connected in series with the adjacent unit EL element 20b through the entry portion 13a of the second electrode layer 6a.

  As shown in FIG. 4, the current supplied from the outside flows from the first electrode layer 3a side to the second electrode layer 6a side through the functional layer 5a, but a part of the second electrode layer 6a is a functional layer separation groove. 16 is in contact with the adjacent first electrode layer 3b through the entry portion 13a, and a current flows through the first unit EL element 20a to the first electrode layer 3b of the adjacent unit EL element 20b. As described above, in the organic EL device 1, all the unit EL elements 20 are electrically connected in series, and all the unit EL elements 20 emit light. At this time, since an insulating layer is formed at the bottom of the first electrode layer separation groove 15, no current flows from the first electrode layer 3b to the first electrode layer 3a.

  Next, components of the organic EL device 1 will be described.

  The material of the substrate 2 is not particularly limited, and is appropriately selected from, for example, a flexible film substrate or a plastic substrate. In particular, a glass substrate or a transparent film substrate is preferable in terms of transparency and good workability.

The material of the first electrode layer 3 is not particularly limited. For example, a metal such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), or zinc oxide (ZnO) is used. An oxide or a metal such as silver (Ag) or chromium (Cr) is employed. In terms of being able to effectively extract light generated from the light emitting layer in the functional layer 5, ITO or IZO having high transparency can be used particularly preferably.
The first electrode layer 3 is formed on the substrate 2 by sputtering, CVD, or vacuum deposition.

  The functional layer 5 is a layer provided between the first electrode layer 3 and the second electrode layer 6 and having at least one light emitting layer. The functional layer 5 is composed of a plurality of layers mainly made of organic compounds. The functional layer 5 can be formed of a known material such as a low molecular dye material or a conjugated polymer material used in a general organic EL device. The functional layer may have a multilayer structure including a plurality of layers such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

In particular, when such a multilayer multilayer structure is adopted, an alkali metal or an alkali such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF ₂ ), etc. is used for the electron injection layer in the functional layer. It is preferable to employ an earth metal compound or the like and laminate the electron injection layer in the functional layer 5 so as to be adjacent to the second electrode layer 6. With this electron injection layer, various conductive materials such as aluminum (Al), silver (Ag), ITO, ITO containing silicon, etc. can be used regardless of the work function between the second electrode layer 6 and the electron injection layer. It can be used as the two-electrode layer 6.

  Moreover, you may add the several dopant which shows different light emission to the light emitting layer of the functional layer 5. FIG. Moreover, you may add a dopant to layers other than a light emitting layer, for example, an electron carrying layer, a hole transport layer, etc.

  The method for forming each layer constituting the functional layer 5 is not particularly limited, and is a vacuum deposition method, a sputtering method, a CVD method, a dipping method, a roll coating method (printing method), a spin coating method, a bar coating method, a spray method. The film can be formed by a known method such as a die coating method or a flow coating method. At this time, each layer may be formed by the same film formation method, or may be formed by different film formation methods.

  When the eyes are moved to the second electrode layer 6, a known substance can be used as the material of the second electrode layer 6. Examples thereof include silver and aluminum. These materials are preferably deposited by sputtering or vacuum evaporation.

The deposited layer 7 is made of metal oxide (MO), metal nitride (MN), and metal carbide (MC). M represents a metal. Silicon nitride and silicon oxide made of Si—N, Si—H, N—H, or the like, and silicon oxynitride that is an intermediate solid solution of both are preferable.
The thickness of the deposited layer 7 is preferably 1.0 to 5.0 μm.
The deposited layer 7 may have a plurality of layers having different compositions.

Specifically, the coating layer 8 is made of dense silica. The coating layer 8 is preferably made of a polysilazane derivative. Silica conversion using a polysilazane derivative causes an increase in weight at the time of silica conversion, has a small volume shrinkage, and is sufficient at a temperature that can be withstood by the resin at the time of silica film conversion, and can make cracking difficult.
The polysilazane derivative here is a polymer having a silicon-nitrogen bond, such as SiO _{2 made of} Si—N, Si—H, N—H, etc., Si ₂ N ₄ , and an intermediate solid solution SiO _x N _{y of} both. It is a ceramic precursor polymer. The polysilazane derivative is represented by the following general formula (1). That is, R _{1 to} R ₃ are basically H, and a part thereof may contain an alkyl group such as a methyl group. n represents an integer of 1 to 99.

The material of the coating layer 8 in this embodiment is preferably a perhydropolysilazane whose side chain is all hydrogen, or a derivative in which a hydrogen part bonded to Si is partially substituted with a methyl group, among polysilazane derivatives.
Further, the polysilazane derivative used in the present invention is used in a solution state dissolved in an organic solvent.
As the organic solvent, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used.

Next, a method for manufacturing the organic EL device 1 according to this embodiment will be described.
The organic EL device 1 is manufactured using a vacuum vapor deposition device (not shown) and a laser scribing device (not shown).

  The manufacturing process of the organic EL device 1 is roughly divided into an organic EL element forming process for forming the organic EL element 10 and a sealing process for sealing the organic EL element 10. Hereinafter, it demonstrates in order of the manufacturing process of the organic electroluminescent apparatus 1. FIG.

First, an organic EL element formation process is performed.
Specifically, first, the first electrode layer 3 is formed on the substrate 2.
The surface of the substrate 2 used at this time has a uniform smoothness over the entire substrate, and even after the first electrode layer 3 is formed, the entire smoothness is uniform.

  Subsequently, a first laser scribing process is performed as necessary to form a first electrode layer separation groove 15 in the first electrode layer 3.

  The laser scribing device used in the laser scribing step has an XY table, a laser generator, and an optical engagement member. The laser scribing step is performed by placing the substrate on an XY table and moving the substrate linearly at a constant speed in the vertical direction while irradiating a laser beam. Then, the X / Y table is moved in the horizontal direction to shift the irradiation position of the laser beam, and the substrate is linearly moved again in the vertical direction while irradiating the laser beam.

  The substrate after the first laser scribing step is cleaned on the surface in order to remove the scattered film as necessary. As a cleaning method, a known cleaning method can be applied.

  Next, the substrate is inserted into a vacuum vapor deposition apparatus, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like are sequentially deposited to form the functional layer 5.

  Then, a second laser scribing step is performed on the substrate taken out from the vacuum deposition apparatus as necessary, and the functional layer separation groove 16 is formed in the functional layer 5.

  Subsequently, the substrate is inserted into a vacuum deposition apparatus, and the second electrode layer 6 is formed on the functional layer 5.

  Subsequently, a third laser scribing process is performed as necessary to form unit light emitting element isolation grooves 17 in both the second electrode layer 6 and the functional layer 5.

Further, the feeding electrode is formed (not shown), the separation groove (not shown) outside thereof, and the second electrode layer 6 and the like on the outer portion of the separation groove are removed.
The above is the organic EL element forming step.

Subsequently, a sealing process is performed. The sealing process is performed in the order of a deposited layer film forming process for forming a deposited layer and a coating process for forming a coating layer.
In the deposited layer film forming step, the description will be made assuming that the foreign matter 12 remains on the substrate on which the organic EL element 10 is laminated in the organic EL element forming step.
A deposited layer 7 is laminated from above by applying crystal growth.
Specifically, the deposition layer 7 is laminated from above the foreign material 12 attached on the second electrode layer 6 by using a plasma CVD method.

In the deposited layer film forming process, the film forming process is performed a plurality of times with an interruption time as shown in the flowchart of FIG.
In the film forming process, the film is formed by the CVD method. As film formation conditions, the distance between the substrate film formation surface and the electrode in the CVD apparatus is 1 to 30 mm, and preferably 5 to 15 mm. The plasma output is 0.1 to 1.0 W / cm ² , preferably 0.3 to 0.7 W / cm ² . The pressure is 50 to 150 Pa, the temperature in the CVD apparatus is 40 to 100 ° C., and the substrate temperature is 60 to 120 ° C. The source gas used for the film formation is not particularly limited, but a silicon-containing gas such as monosilane (SiH ₄ ) or disilane (Si ₂ H ₆ ), or a gas obtained by diluting these silicon-containing gases with hydrogen can be employed. In particular, in the case of silicon nitride (SiN _x ), a mixed gas of monosilane (SiH ₄ ) and ammonia (NH ₃ ) is suitable. When silicon nitride (SiN _x ) is formed using monosilane (SiH ₄ ) and ammonia (NH ₃ ), when the flow rate of monosilane (SiH ₄ ) is 1, the flow rate of ammonia (NH ₃ ) is It is preferably 0 to 1/3. That is, it may be amorphous silicon containing no nitrogen.
In particular, from the viewpoint of preventing peeling of the organic EL element 10 due to plasma CVD film formation, the density of the film is controlled by controlling the mixing ratio of the source gases and the substrate temperature, and the compressive stress of the deposited layer 7 is reduced. It is preferable to be within 0 to ± 80 MPa.
Further, the number of film forming steps is not particularly limited as long as it is a plurality of times, but is preferably 3 times or more.

The deposition layer film forming process will be described with reference to the flowchart of FIG. 5. The deposition layer 7 is formed on the substrate (steps 1 and 2). Thereafter, when the layers are stacked until a predetermined film thickness is obtained (step 3), the film forming operation is stopped (steps 4 and 5), and the timer is turned on (step 6).
Specifically, it is preferable to move to step 4 with the stage where 3% to 60% of the film thickness at the end of the formation of all the deposited layers 7 is laminated as the switching reference value. It is more preferable to set 5% to 50% of the film thickness at the end of the entire deposition layer 7 as the switching reference value. It is particularly preferable that 10% to 30% of the film thickness at the end of the entire film formation of the deposited layer 7 be the switching reference value.
In the case of the first film formation step, it is preferable to form the film to a thickness comparable to the size of the foreign matter.

Thereafter, when a predetermined time (interruption time) has elapsed (step 7), the timer is turned off (step 8).
Specifically, the interruption time is preferably 5 seconds to 30 minutes, and particularly preferably 5 seconds to 10 minutes. Further, at this time, it is preferable to keep the source gas flowing while the plasma power supply is stopped.

After that, when the film forming process is performed only once, the process returns to step 1 and the film forming process is performed again (step 9).
On the other hand, if the film forming process has been performed once or more, the process proceeds to step 10.

  In step 10, if the film formation amount does not reach the target total film formation amount, the process returns to step 1 to perform the film formation process again.

  On the other hand, when the film formation amount reaches the target total film formation amount, the deposition layer film formation step is terminated.

Subsequently, a coating process for forming the coating layer 8 is performed.
In the coating process, a liquid polysilazane derivative is applied on the deposited layer 7. Then, by performing steam oxidation in the presence of a catalyst and / or heat oxidation in an air atmosphere, a dense coating layer 8 is formed, and the organic EL device 1 is completed.
In addition, as a catalyst used at this time, metal catalysts, such as gold | metal | money, silver, palladium, platinum, nickel, and those carboxylic acid complexes are employ | adopted. Instead of adding the catalyst to the polysilazane derivative, it is also possible to employ a method such as contacting the coated molded product directly with a catalyst solution, specifically an aqueous amine solution, or exposing it to the vapor for a certain period of time. preferable.

  According to the manufacturing method of the present invention, since the deposition layer 7 is again laminated after the crystal growth is temporarily stopped, the deposition layer 7 is also formed in the gap, so that the gap can be filled. Become. Further, in the vicinity of the foreign material 12, the interface formed before the stop and the interface formed after the stop are different from each other because the crystal growth is stopped once, so that a discontinuous interface is formed. In addition, a large gap reaching the organic EL element 10 is not formed, and a favorable deposited layer 7 can be formed. That is, according to the manufacturing method of the present invention, the sealing property is high, and entry of moisture or the like into the organic light emitting layer can be prevented.

  In the above-described embodiment, the same property deposition layer 7 is laminated before and after the interruption time. However, the present invention is not limited to this, and the deposition layer 7 having a different property before and after the interruption time may be laminated. Good. As a specific lamination method, a method of forming a film by changing the surface temperature of the substrate during film formation, the temperature of the film formation chamber, the pressure, the plasma output, the substrate temperature, the source gas supply ratio, etc. before and after the interruption time. Etc. can be used.

  In the above-described embodiment, the coating layer 8 is directly laminated on the deposition layer 7, but the present invention is not limited to this, and aluminum is vapor-deposited on the deposition layer 7 or an aluminum foil is adhered. The coating layer 8 may be laminated later. It is possible to more reliably prevent water from entering the functional layer 5 by evaporating aluminum or bonding aluminum foil.

  In the above-described embodiment, the switching reference value used as the reference for the end of film formation in the deposition layer film forming step is based on the film thickness at the end of the entire film formation of the deposited layer 7, but the present invention is not limited to this. Instead of this, the deposition time of the deposition layer 7 relative to the total deposition time of the deposition layer 7 may be used as the switching reference value.

  In the embodiment described above, the end of the interruption time is set as the elapsed time, but the present invention is not limited to this. For example, the change in the surface temperature of the substrate or the change in the temperature in the film forming chamber is used as a reference. Also good. Specifically, when the change in the surface temperature of the substrate is used as a reference, it is preferable that the substrate temperature be reduced from 5% to 50% from the temperature of the substrate at the start of the stop time. More preferably, the temperature of the substrate is reduced by 10% to 30% from the temperature of the substrate at the start of the stop time, and the reference is that the temperature of the substrate is reduced by 15% to 20% from the temperature of the substrate at the start of the stop time. It is particularly preferable that Further, when the change in the temperature in the film formation chamber is used as a reference, it is preferable that the temperature in the film chamber is reduced from 5% to 50% from the temperature of the film formation chamber at the start of the stop time. It is more preferable that the temperature of the film chamber is reduced from 10% to 30% from the temperature of the film forming chamber at the start of the stop time, and it is more preferable that the temperature of the film chamber is 10% to 20% from the temperature of the film forming chamber at the start of the stop time. It is particularly preferable to use the lowering as a reference.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  A specific example of the present invention and a manufacturing procedure of an organic EL device of a comparative example with respect to the example and evaluation results thereof will be described.

[Example 1]
As a substrate for forming the organic EL device, non-alkali glass (thickness 0.7 mm) in which ITO (indium / tin oxide, film thickness 150 nm) is laminated as a first electrode layer on one side was used. Patterning formation of 0.5 mm intervals was performed on this substrate using a laser scribing apparatus, and the first electrode layer separation grooves 15 were formed.
The substrate was washed with a surfactant using a brush, ultrasonically washed with pure water, and then dried in an oven. The substrate was moved to a vacuum deposition apparatus, and the material was deposited in vacuum as follows.

  On the first electrode layer, a mixed layer of 4,4′-bis [N- (2-naphthyl) -N-phenyl-amino] biphenyl (hereinafter abbreviated as NPB) and molybdenum trioxide is used as a hole injection layer. Then, a film having a thickness of 10 nm was formed by a vacuum deposition method. NPB and molybdenum trioxide of the hole injection layer were formed by a co-evaporation method so that the film thickness ratio was 9: 1.

  Subsequently, NPB was formed into a film with a film thickness of 50 nm (deposition rate: 0.08 nm / sec to 0.12 nm / sec) by a vacuum evaporation method as a hole transport layer.

  Next, tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq3) as a light emitting layer / electron transporting layer is formed to a thickness of 70 nm (deposition rate: 0.24 nm / sec to 0.28 nm / sec) by vacuum deposition. A film was formed.

Next, LiF was used as the electron injection layer, and a film having a thickness of 1 nm (deposition rate: 0.03 nm / sec to 0.05 nm / sec) was formed by a vacuum evaporation method.
Finally, as a cathode, Al is deposited with a film thickness of 150 nm (deposition rate: 0.3 nm / sec to 0.5 nm / sec) by a vacuum deposition method, and an organic EL element having a unit shape of 30 mm × 30 mm and a light emitting area of 18 mm × 18 mm Was made.
Thereafter, the organic EL element is moved from a vacuum atmosphere to a glove box filled with a nitrogen atmosphere, and resin particles are dispersed on the organic EL element for easy comparison as an example, and then moved to a plasma CVD apparatus. Then, Si—N (—O) as a deposition layer was stacked. Here, for convenience of explanation, the deposited layer formed by the n-th film formation step is represented as an nth film formation (n is a natural number).
Returning to the description, first, the first film formation is sequentially performed. The gas was adjusted so that the flow ratio of SiH ₄ and NH _{3 as} the supply gas was 600: 95, and silicon nitride was formed (first film formation). When the film thickness of the first film reached 1.1 μm, the generation of plasma was interrupted and stopped for 0.5 minutes. After 0.5 minutes, plasma discharge was started under the same conditions, and silicon nitride was formed again (second film formation). When the film thickness of the second film reached 1.1 μm, the generation of plasma was stopped for 0.5 minutes as an interruption time. After 0.5 minutes, plasma discharge was started under the same conditions, and silicon nitride was formed again (third film formation). When the film thickness of the third film reached 1.0 μm, the generation of plasma was stopped and the film-formed substrate was taken out into the atmosphere. Thereafter, a liquid polysilazane derivative was applied on the silicon nitride film and heated. The organic EL device thus formed was designated as Example 1.

[Example 2]
The organic EL device of Example 2 was prepared according to Example 1, but the film thickness serving as a reference value for switching the film thickness of the first to third film formations was halved of that of Example 1. This is different from the first embodiment. That is, as the switching reference values for the first to third films, the first film thickness is 0.55 μm, the second film thickness is 0.55 μm, and the third film thickness is 0.5 μm. When reached, the film thickness was changed to 1.6 μm.

Example 3
The organic EL device of Example 3 was prepared according to Example 1, but in the second film formation, the supply gas was changed to only SiH ₄ and no NH ₃ gas was supplied. It differs from Example 1 that it formed. That is, in the second film formation, the supply amount of SiH ₄ as the supply gas was adjusted to 600 sccm, and the film was formed so that the flow rate ratio of SiH ₄ and NH ₃ as the supply gas was 600: 0. Then, in the third film formation, the gas was adjusted so that the flow rate ratio of SiH ₄ and NH _{3 as} the supply gas was 600: 95, and the film was formed. The organic EL device thus formed was designated as Example 3.

Example 4
The organic EL device of Example 4 was prepared according to Example 3, but the film thickness serving as a reference value for switching the film thickness of the first to third film formations was halved of that of Example 1. This is different from the third embodiment. That is, as the switching reference values for the first to third films, the first film thickness is 0.55 μm, the second film thickness is 0.55 μm, and the third film thickness is 0.5 μm. When reached, the film thickness was changed to 1.6 μm.

[Comparative Example 1]
In the organic EL device of Comparative Example 1, the film forming process was performed only once in the manufacturing procedure of Example 1. Specifically, the gas was adjusted so that the flow rate ratio of SiH ₄ and NH ₃ as the supply gas was 600: 95, and the film was formed (first film formation). Then, when the film thickness of the first film reached 1.6 μm, the generation of plasma was stopped and the film-formed substrate was taken out into the atmosphere. Thereafter, a liquid polysilazane derivative was applied on the deposited layer and heated.

(Light emission defect measurement)
The organic EL devices of Example 1 and Comparative Example 1 were subjected to a high temperature and high humidity light emission test to evaluate light emission defects. The test conditions were an atmosphere of 60 ° C./85% RH and an applied voltage of 5 V. The evaluation was performed with a stereomicroscope of about 10 times at room temperature. evaluated. The results are shown in Table 1.

  As shown in Table 1, after 1000 hours of test time, in Example 1, the number of light emitting defects was 12, and the number of light emitting defects increased by 1.2 times after 1 hour and 1000 hours. On the other hand, in Comparative Example 1, the number of light emitting defects was 77 after 1000 hours of the test time, and the number of light emitting defects was 5.92 times after 1 hour and 1000 hours. Compared to Comparative Example 1, the amount of increase in light emitting defects in Example 1 decreased.

  Furthermore, in order to investigate the organic EL device of the present invention in detail, a high-temperature and high-humidity light emission test was performed under conditions different from the above-described conditions to evaluate light emission defects. The test conditions were the same as those in Table 1, and the evaluation was performed with a stereomicroscope of about 10 times at room temperature, and the change in the number of increased light emission defects over time was evaluated. The results are shown in Table 2. However, in Table 2, the film was formed in a clean state without spraying resin particles for the purpose of confirming the effect in the normal production state.

As shown in Table 2, when Example 4 that does not use ammonia and Example 2 that uses ammonia are compared in the second film formation, Example 4 that does not use ammonia uses ammonia. Compared with Example 2, the generation time of the light emitting defect was delayed. That is, it is presumed that generation of light emission defects is suppressed by using only the SiH ₄ gas without using ammonia at the time of the second film formation.
Further, comparing Example 2 with a total film thickness of 1.6 μm and Example 1 with a total film thickness of 3.2 μm, Example 2 with a total film thickness of 1.6 μm emits light after 200 hours. While defects occurred, in Example 1 where the total film thickness was 3.2 μm, no light emitting defects occurred even after 300 hours had elapsed. Similarly, when Example 4 with a total film thickness of 1.6 μm is compared with Example 3 with a total film thickness of 3.2 μm, in Example 4 with a total film thickness of 1.6 μm, 300 hours have passed. Whereas light emitting defects occurred, in Example 3 where the total film thickness was 3.2 μm, no light emitting defects occurred even after 300 hours had elapsed. From this result, it was found that by increasing the total film thickness to a predetermined amount (twice in the examples), it is possible to suppress the occurrence of light emission defects and increase the sealing effect.

  The cross sections of the organic EL devices of Example 1 and Comparative Example 1 were observed with a transmission electron microscope. The measurement results are shown in FIGS.

  In Example 1, as shown in FIGS. 6 and 7, the deposited layer 7 is formed in the gap even if foreign matter is mixed. A discontinuous interface is formed in the vicinity of 480 to 520 nm. As a whole, a continuous good deposition layer 7 is formed. On the other hand, in Comparative Example 1, as shown in FIGS. 8 and 9, when foreign matter is mixed in, a void is formed in the deposited layer 7, and the void reaches the organic EL element. Therefore, in Example 1, it is presumed that the entry of water or the like at the time of the test can be prevented, and the increase in light emission defects was reduced.

1 Organic EL device 2 Substrate (base material)
3 First electrode layer 5 Functional layer (organic light emitting layer)
6 Second electrode layer 7 Deposited layer 8 Coating layer 10 Organic EL element (laminated body)
11 Sealing layer 20 Unit EL element

Claims (7)

A method of manufacturing an organic EL device,
A step of forming a laminate including a first electrode layer, an organic light emitting layer, and a second electrode layer on a substrate; and a sealing step of sealing part or all of the laminate formed in the step,
The sealing step includes a deposited layer film forming step of forming a deposited layer by applying crystal growth. In the deposited layer film forming step, a deposited layer having a different property or a deposited layer having the same property is applied for a predetermined time. Are used for stacking,
The sealing step includes a coating step of forming a coating layer on the deposited layer,
In the coating step, a liquid polysilazane derivative is applied on the deposited layer, and the polysilazane derivative is exposed to steam in the presence of a catalyst to be subjected to steam oxidation to form silica, thereby forming the coating layer. Manufacturing method of EL device. 2. The method of manufacturing an organic EL device according to claim 1, wherein in the deposited layer film forming step, deposited layers having different compositions are stacked with the predetermined time interval . The deposited layer film forming step is to form the deposited layer using a plasma CVD method, and a plurality of film forming steps are performed with an interruption time during which plasma generation is interrupted,
2. The method of manufacturing an organic EL device according to claim 1, wherein a deposited layer having the same property is formed in a film forming process before and after the interruption time. 4. The method of manufacturing an organic EL device according to claim 3, wherein the source gas used in the film forming step before the interruption time is continuously supplied during the interruption time. 5. The method of manufacturing an organic EL device according to claim 3, wherein the deposition layer film forming step is performed three or more times. Deposition layer forming process, metal oxides, metal nitrides, among the metal carbide, the organic EL device according to any one of claims 1 to 5, characterized in that the deposition of the at least either Production method. By the manufacturing method of the organic EL device according to any one of claims 1 to 6, a first electrode layer on a substrate, an organic light-emitting layer, a laminate having a second electrode layer, the whole of the laminate Or having a sealing layer that partially seals,
At least one of the sealing layers has a deposited layer containing foreign matter, and an organic EL device is manufactured in which a discontinuous interface exists in the vicinity of the foreign matter in the deposited layer. Manufacturing method.