JP6036279B2 - Organic electroluminescence device manufacturing method - Google Patents

Description

The present invention relates to an organic electroluminescence device manufactured how.

  Organic electroluminescence devices using organic substances (sometimes simply referred to as “organic EL”) are promising for use as solid light-emitting, inexpensive large-area full-color display devices and writing light source arrays. R & D is ongoing. The organic EL element includes a first electrode (anode or cathode) formed on a substrate, an organic compound layer (single layer portion or multilayer portion) containing an organic light emitting material laminated thereon, that is, a light emitting layer, It is a thin film type element having a second electrode (cathode or anode) laminated on the light emitting layer. When a voltage is applied to such an organic EL element, electrons are injected from the cathode and holes are injected from the anode into the organic compound layer. It is known that light is obtained by releasing energy as light when the electrons and holes recombine in the light emitting layer and the energy level returns from the conduction band to the valence band.

  As described above, since the organic EL element is a thin film type element, when an organic EL panel in which one or a plurality of organic EL elements are formed on a substrate is used as a surface light source such as a backlight, a surface light source. It is possible to easily make the device provided with In addition, when a display device is configured using an organic EL panel in which a predetermined number of organic EL elements as pixels are formed on a substrate as a display panel, the liquid crystal display device has high visibility and no viewing angle dependency. There are advantages that cannot be obtained.

  An organic substance such as an organic light emitting material used in such an organic EL element is weak against moisture, oxygen, etc., and its performance is deteriorated. In addition, the characteristics of electrodes are rapidly deteriorated in the atmosphere due to oxidation. In order to prevent these deteriorations, generally, a method has been proposed in which a sealing cap can formed of a metal can, digging glass, or the like is bonded and sealed to an element substrate with an adhesive. This has a hermetically sealed space, is filled with an inert gas, and is further provided with a hygroscopic material. In this case, since the element surface cathode has a space, the element is not deteriorated by external stress. However, although the organic EL element itself is thin, it has a thickness of the sealing member and a space for disposing the hygroscopic material, and the light emitting element is thick as a whole.

  In recent years, there has been a growing demand for flexible and thin organic EL elements, and a close-contact type sealing form in which a sealing material is bonded without providing a space on the element surface has been proposed. This is called solid sealing, and a technique is generally known in which a barrier layer is provided on the surface of an organic EL element, and further, a protective substrate is adhered to the surface of the organic EL element by an adhesive. As such a technique, for example, inventions described in Patent Documents 1 to 3 have been proposed.

  Patent Document 1 includes a substrate, at least a hole injection electrode formed on the substrate, an organic layer involved in a light emitting function, and an electron injection electrode, and the electron injection electrode is sealed on the opposite side of the substrate. The organic EL element which has a stop film and this sealing film contains silicon, oxygen, and nitrogen is described. Moreover, this patent document 1 describes that a sealing film is formed by plasma CVD.

  Patent Document 2 discloses a method of manufacturing an electronic component having a barrier layer that encapsulates a component, the method comprising: preparing a substrate having at least one functional layer; and plasma assisted atomic deposition (plasma ALD). And at least one first barrier layer is deposited on the functional layer using plasma assisted chemical vapor deposition (plasma CVD). A method of making an electronic component having a barrier layer for encapsulating the component.

  Patent Document 3 discloses a thin film encapsulation unit for an optoelectronic component, which includes a first ALD layer deposited using an atomic layer deposition method and a second ALD layer deposited using an atomic layer deposition method. A thin film encapsulating portion characterized by having a laminated structure including an ALD layer is described. This Patent Document 3 describes that the first ALD layer and the second ALD layer are formed of two different materials in order to improve the compatibility of the transmittance with respect to visible light.

JP 2001-60491 A Special table 2011-515789 Special table 2012-521623 gazette

  However, since the invention described in Patent Document 1 forms a sealing film by plasma CVD, a sufficient barrier property cannot be obtained when the film thickness is thin. Therefore, in order to ensure a sufficient barrier property, it is necessary to increase the thickness of the sealing film to the micron order, and there is a problem that productivity is poor.

  In the invention described in Patent Document 2, since the barrier layer is formed by plasma-assisted atomic deposition (plasma ALD), there is a problem that the organic EL element is damaged by the plasma and the active material, and the luminance is deteriorated. It was.

  In the invention described in Patent Document 3, the first ALD layer and the second ALD layer are mainly formed with two different materials because the main purpose is to adjust the transmittance. If the film thickness is the same, it is possible to obtain a higher barrier property by using only a material having a good barrier property and a single film, so the barrier property is inferior in the configuration according to the invention described in Patent Document 3. There was a problem.

The present invention has been made in view of the above situation, and both productivity and barrier properties, and it is an object to provide an organic electroluminescent layer hardly organic electroluminescence device manufacturing how to damage the.

The object of the present invention is achieved by the following means.
1. An organic electroluminescent device manufacturing method for manufacturing an organic electroluminescent device, wherein an atomic layer deposition method using only a thermal reaction is performed on an organic electroluminescent layer formed on a substrate without using plasma support . A first layer forming step of forming a first layer; and a second layer forming step of performing a plasma-assisted atomic layer deposition method on the first layer to form a second layer made of alumina. An organic electroluminescence element manufacturing method.
2. 2. The organic electroluminescence device manufacturing according to 1 above, further comprising a third layer forming step of forming a third layer having a lower elastic modulus than the first layer and the second layer on the second layer. Method.
3. 3. The method of manufacturing an organic electroluminescence element according to 2 above, wherein the third layer is formed by at least one of a plasma CVD method, a sputtering method for reacting in a transition region, and an activated vapor deposition method.
4 . Before Symbol third layer organic electroluminescent device fabrication method according to the 2 or 3, characterized in that an inorganic layer containing Si.
5. The thickness of the first layer and the second layer is 3~25nm respectively, the thickness of the third layer according to any one of the 2 to 4, characterized in that the 100~350nm Organic electroluminescent element manufacturing method.
6). Wherein the on three layers, the organic electroluminescence device manufacturing method according to any one of the 2 to 5, characterized in that it comprises an adhesive layer forming step of forming an adhesive layer.
7). 7. The method for producing an organic electroluminescent element according to 6 above, further comprising a barrier base material forming step of forming a base material imparted with a barrier property on the adhesive layer.
8). The first layer and the second layer are formed in the same chamber of an apparatus for performing an atomic layer deposition method, and trimethylaluminum and H ₂ O or O ₃ are used as raw materials for the first layer. layer, wherein the first layer after forming a predetermined thickness, an organic electroluminescence according raw materials to any one of the items 1 to 7, characterized in that incorporated the plasma switch to trimethylaluminum and O ₂ Luminescence element manufacturing method .

According to the present invention, it is possible to achieve both productivity and barrier properties, and to provide the organic electroluminescent layer provided hardly organic electroluminescence device manufactured how the damage.

(A) is a flowchart which shows the content of the organic EL element manufacturing method which concerns on one Embodiment of this invention, (b) is a conceptual sectional drawing explaining the structure of the organic EL element manufactured by this. (A) is a flowchart which shows the content of the organic EL element manufacturing method which concerns on other embodiment of this invention, (b) is a conceptual sectional drawing explaining the structure of the organic EL element manufactured by this. . (A) is a flowchart which shows the content of the organic EL element manufacturing method which concerns on other embodiment of this invention, (b) is a conceptual sectional drawing explaining the structure of the organic EL element manufactured by this. . (A) is a flowchart which shows the content of the organic EL element manufacturing method which concerns on other embodiment of this invention, (b) is a conceptual sectional drawing explaining the structure of the organic EL element manufactured by this. . It is a composition sectional view showing an example of composition of an organic EL element concerning this embodiment.

  Hereinafter, an organic EL device manufacturing method and an embodiment for carrying out an organic EL device according to the present invention will be described in detail with reference to the drawings as appropriate.

[Organic EL device manufacturing method]
First, with reference to FIG. 1 (a) and (b), the organic EL element manufacturing method concerning this invention is demonstrated.
As shown in FIGS. 1A and 1B, the organic EL device manufacturing method according to the present embodiment includes a first layer forming step S1 and a second layer forming step S2. Perform sequentially in order.

(First layer forming step)
In the first layer formation step S1, the first layer 4 is formed on the organic EL layer 3 formed on the substrate 2 by performing an atomic layer deposition method (thermal ALD) using only a thermal reaction without supporting by plasma. It is a process.
The organic EL layer 3 can be formed on the substrate 2 by a known method. The film formation of the organic EL layer 3 will be described later.

Atomic Layer Deposition (ALD) is a method of forming a film by switching a source gas to alternately adsorb one atomic layer at a time on a substrate and reacting it. Depending on the reaction activation means, it can be divided into thermal ALD and plasma ALD.
As described above, thermal ALD is performed by alternately supplying a gas as a raw material for film formation to a heated substrate without generating plasma.
In plasma ALD, in addition to the thermal ALD method, plasma is generated and the reaction is further promoted to form a film. Plasma ALD can form a denser film with better barrier properties in a lower temperature process region than thermal ALD.

  In the first layer forming step S1, since plasma is not used, it is difficult to damage the organic EL layer 3. In addition, the first layer 4 formed by thermal ALD is inferior in barrier property as a single layer as compared with a layer formed by plasma assisted atomic layer deposition (plasma ALD), but by forming this, organic EL Plasma resistance can be imparted to the layer 3. That is, the first layer 4 functions as a plasma-resistant base film, and damage to the organic EL layer 3 due to plasma ALD in the second layer forming step S2 performed subsequently to this step can be reduced.

When an alumina (Al ₂ O ₃ ) layer is formed as the first layer 4, trimethylaluminum (TMA; (CH ₃ ) ₃ Al) is adsorbed on the substrate as a reaction gas, and then the raw material is switched to water (H ₂ The operation of introducing O) or O ₃ into the reaction chamber and reacting at about 80 to 120 ° C. is repeated any number of times. When the thickness of the first layer 4 becomes 3 to 25 nm, the first layer forming step S1 is finished and the process proceeds to the next step.

  By setting the temperature of the first layer forming step S1 to 80 ° C. or higher, the reactivity when forming the first layer 4 is improved and the film quality is improved, so that the barrier property is improved and the plasma resistant base film is formed. Can function as well. Therefore, when the second layer 5 is formed by plasma ALD in the next step, it is possible to make it difficult to damage the organic EL layer 3 and to prevent the luminance from deteriorating. In addition, by setting the temperature of the first layer forming step S1 to 120 ° C. or less, when the first layer 4 is formed by thermal ALD, the organic EL layer 3 is hardly deteriorated by heat, and an element such as luminance is generated. It is possible to prevent the performance from deteriorating.

  Moreover, the film thickness can be sufficiently increased by setting the thickness of the first layer 4 to 3 nm or more. Therefore, it is possible to make it difficult to damage the organic EL layer 3 when the second layer 5 is formed by plasma ALD in the next step, and it is possible to prevent the luminance from deteriorating. Further, if the thickness of the first layer 4 is 25 nm or less, the film formation time is not excessively required, which is preferable from the viewpoint of cost. The thickness of the first layer 4 is preferably set to 3 to 5 nm in consideration of the function and cost as a plasma-resistant base film.

(Second layer forming step)
The second layer forming step S2 is a step of forming the second layer 5 on the first layer 4 by performing plasma ALD.
In the second layer forming step S2, since the film is formed by applying heat while supporting with plasma, the formed second layer 5 is formed with a denser and defect-free film. Therefore, the organic EL element 1 can be sealed with a high barrier property.

In the case of forming an alumina (Al ₂ O ₃ ) layer as the second layer 5, trimethylaluminum (TMA; (CH ₃ ) ₃ Al) is adsorbed on the substrate as a reaction gas, and then the raw material is switched to oxygen gas (O ₂ ) is introduced into the reaction chamber, and the operation of reacting in a plasma atmosphere at about 80 to 120 ° C. is repeated any number of times. When the thickness of the second layer 5 becomes 3 to 25 nm, the second layer forming step S2 is finished.

  By setting the temperature of the second layer forming step S2 to 80 ° C. or higher, the reactivity when forming the second layer 5 is improved and the film quality is improved, so that it can function sufficiently as a sealing film. Therefore, the organic EL element 1 can be sealed with a high barrier property. Further, by setting the temperature of the second layer forming step S2 to 120 ° C. or lower, it is difficult for the organic EL layer 3 to be thermally deteriorated due to heat, and it is possible to prevent deterioration of element performance such as luminance.

  Moreover, the film thickness can be made sufficiently thick by setting the thickness of the second layer 5 to 3 nm or more. Therefore, the organic EL element 1 can be sealed with a high barrier property. Further, if the thickness of the second layer 5 is 25 nm or less, the film formation time is not excessively required, which is preferable from the viewpoint of cost. The thickness of the second layer 5 is preferably 5 to 15 nm in consideration of barrier properties and cost.

The first layer forming step S1 and the second layer forming step S2 described above are performed in the same chamber (reaction chamber) of an apparatus for performing atomic layer deposition (ALD), and the first layer 4 and the second layer 5 are formed. Is preferred. When these layers are formed, the first layer 4 is formed to a predetermined thickness using TMA and H ₂ O as raw materials, and then the raw materials are switched to TMA and O ₂ , and then supported by plasma. In this way, the number of reaction chambers becomes one and an increase in equipment can be prevented, and since the substrate 2 is not replaced, adhesion of particles and the like can also be prevented. Therefore, the first layer 4 and the second layer 5 with good quality can be formed.

Further, when both the first layer 4 and the second layer 5 are alumina (Al ₂ O ₃ ) layers, no interface is generated between the first layer 4 and the second layer 5. It is possible to cover an uneven film surface having many defects with a minimum necessary thickness without film defects.

  When another layer is formed on the second layer 5, since there are few film defects in the second layer 5, it is possible to form a layer with few defects in the other layer. Therefore, the organic EL element 1 can be sealed with higher barrier properties. In addition, this makes it possible to ensure a high barrier property with a thinner film thickness than in the past.

(Third layer forming step)
In the present embodiment, as shown in FIGS. 2A and 2B, the third layer forming step S3 can be performed following the first layer forming step S1 and the second layer forming step S2. Note that the first layer formation step S1 and the second layer formation step S2 are the same as the steps described above and have already been described, and thus detailed description thereof will be omitted.

  The third layer forming step S3 is a step of forming the third layer 6 having a lower elastic modulus than the first layer 4 and the second layer 5. Even when pressure or impact is applied from the outside by forming the third layer 6 having a lower elastic modulus (that is, higher flexibility) than the first layer 4 and the second layer 5, It is possible to make it difficult to damage the first layer 4 and the second layer 5.

  The elastic modulus of the 3rd layer 6 should just be higher than the 1st layer 4 and the 2nd layer 5, and although it does not specifically limit, For example, it can be set to 60-80 GPa. In addition, as an elasticity modulus in this invention, the nanoindentation elasticity modulus (Er) measured by the following method is said.

  The nanoindentation elastic modulus (Er) can be suitably measured by using, for example, a scanning probe microscope SPI3800N manufactured by SII Nano Technology.

  As the indenter, a triangular pyramid type diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) can be used.

  In the measurement, first, the triangular pyramid-shaped diamond indenter described above is applied at right angles to the sample surface, a load is gradually applied, and the load is gradually returned to 0 after reaching the maximum load. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion can be calculated as nanoindentation hardness (H). The nanoindentation elastic modulus (Er) can be calculated using the following formula, assuming the slope S of the unloading curve.

(Formula) Er = (S × √π) / (2√A)
However, (pi) shows a circumference ratio.
In addition, it is good to calibrate and measure a measuring apparatus beforehand so that the hardness obtained as a result of pushing the attached fused silica as a standard sample may be 9.5 ± 1.5 GPa.

  Details of the principle are described in Handbook of Micro / Nano Tribology (CRC edited by Bharat Bhushan).

  As a measurement sample, one drop of adhesive Aron Alpha (registered trademark) manufactured by Toagosei Co., Ltd. is dropped on a slide glass, and then a sample cut into about 1 cm square is placed and allowed to stand for 24 hours to be cured.

  The maximum load P is preferably set in advance (for example, 50 μN) so that the maximum depth is 15 nm, and both loading and unloading are preferably performed in 5 seconds.

  If the elastic modulus of the third layer 6 thus obtained is 60 GPa or more, the elastic modulus is not too low, and even when pressure or impact is applied from the outside, the first layer 4 or It is possible to prevent the second layer 5 from being damaged. Further, if the elastic modulus of the third layer 6 is set to 80 GPa or less, the elastic modulus does not become too high, so that it does not become weak against pressure and impact. For this reason, even when pressure or impact is applied from the outside, it is possible to prevent the first layer 4 and the second layer 5 from being damaged. The elastic modulus of the third layer 6 is determined by the material of the third layer 6. Therefore, it can be adjusted by variously changing the material of the third layer 6 or mixing a plurality of materials at an arbitrary ratio.

  The third layer 6 is preferably an inorganic layer containing Si. Examples of the inorganic layer containing Si include a silicon nitride film, a silicon oxide film, a silicon oxynitride film, and a carbon-containing silicon oxide film.

  The third layer 6 is preferably formed by at least one of a plasma CVD method, a sputtering method that reacts in a transition region, and an activated vapor deposition method. According to these methods, the third layer 6 can be suitably formed.

  The plasma CVD method is a method of forming a film by decomposing a source gas with plasma to generate chemically active radicals and ions and reacting them on a substrate.

Sputtering that reacts in the transition region is a technique for stably performing sputtering in the case where hysteresis occurs when reactive sputtering is performed, and can be realized by controlling the reaction gas. is there. For example, in the case of forming a silicon oxide film, a sputtering method for reacting in a transition region uses a magnetron sputtering apparatus, using silicon as a target, introducing Ar as a discharge gas, and using a reactive gas, O ₂ (oxygen) gas. These are used to control the flow rate to form a film. The film quality is determined by the amount of O ₂ (oxygen) which is a reactive gas. However, if the amount of oxygen is small, a Si-rich film is formed and a metal region having a high film formation rate is formed. Conversely becomes oxygen is often a film close to the SiO _2, film formation rate is slow oxidation region. The intermediate region is a transition region, and a film close to SiO ₂ can be formed at high speed by maintaining the transition region by controlling O ₂ gas. The transition region state can be controlled by monitoring the plasma emission intensity, but can also be performed by monitoring the discharge voltage.

  The activated vapor deposition method is a kind of ion plating performed using a pressure gradient type plasma gun. In the activated vapor deposition method, an arc discharge is used to evaporate or sublimate a material, and it is possible to promote ionization by exposure to a plasma under the arc discharge, thereby increasing the crystallinity on the substrate at a low temperature. Note that ionized atoms form a dense film and are excellent in orientation. In other words, since a single orientation is obtained, the plane orientation is also set, and a highly smooth film can be formed.

  The thickness of the third layer 6 is preferably 100 to 350 nm. In this way, even when pressure or impact is applied from the outside, it is possible to reliably prevent the first layer 4 and the second layer 5 from being damaged. The thickness of the third layer 6 is more preferably 150 to 300 nm from the viewpoint of the function of protecting the first layer 4 and the second layer 5 and cost. Since the third layer 6 is thick, it is preferable to form the film by a plasma CVD method, a sputtering method that reacts in a transition region, an activated vapor deposition method, or the like, from the viewpoint of performing high-speed film formation.

(Adhesive layer forming process)
In the present embodiment, as shown in FIGS. 3A and 3B, an adhesive layer forming step S4 is performed following the first layer forming step S1, the second layer forming step S2, and the third layer forming step S3. It can be carried out. Note that the first layer formation step S1 to the third layer formation step S3 are the same as those described above, and have already been described, and thus detailed description thereof will be omitted.

  As the adhesive used in the adhesive layer 7, a UV curable adhesive composition made of an acrylic resin, an epoxy resin, a fluorine resin, or the like can be used. For example, UV resin XNR5516 manufactured by Nagase Chemtech Co., Ltd. A UV curable adhesive (resin) such as, for example, can be used. Of course, a heat bonding resin may be used. The adhesive described above is a liquid resin, and can be formed on the third layer 6 with a coating film forming apparatus such as a screen printing apparatus, a flexographic printing apparatus, or a die coat. Moreover, what was formed in the adhesive sheet form can also be used. In this case, it is possible to form the adhesive layer 7 by preparing an adhesive sheet laminated with a double-sided release sheet, peeling the release sheet, and laminating the adhesive sheet on the third layer 6. Of course, an adhesive sheet formed on a barrier base material 8 described later may be prepared, and the barrier base material 8 may be laminated on the third layer 6.

  The thickness of the adhesive layer 7 is not particularly limited, but is preferably set in the range of 10 to 500 μm in view of the balance between the protection performance by the film and the film stress.

(Barrier substrate forming process)
In the present embodiment, as shown in FIGS. 4A and 4B, following the first layer forming step S1, the second layer forming step S2, the third layer forming step S3, and the adhesive layer forming step S4, Barrier base material formation process S5 can be performed. Note that the first layer forming step S1 to the adhesive layer forming step S4 are the same as those described above, and have already been described, and thus detailed description thereof is omitted.

  Barrier base material forming step S <b> 5 is a step of forming a base material provided with barrier properties on the adhesive layer 7. The base material provided with the barrier property refers to the barrier base material 8 provided with the barrier property on the plastic base material. In this way, it is possible to protect the organic EL layer 3 and the first to third layers formed thereon and to prevent excessive moisture intrusion and oxidation.

  Examples of the plastic substrate include ethylene tetrafluoroethyl copolymer (ETFE), high density polyethylene (HDPE), expanded polypropylene (OPP), polystyrene (PS), polymethyl methacrylate (PMMA), and stretched nylon (ONy). A thermoplastic resin film material such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), polyether styrene (PES), or the like can be used. As these thermoplastic resin films, a multilayer film made by coextrusion with a different film, a multilayer film made by laminating at different stretching angles, etc. can be used as needed. Further, it is naturally possible to combine the density and molecular weight distribution of the film used to obtain the required physical properties.

Examples of the film provided to ensure the barrier property of the plastic substrate include inorganic films and metal foils. As inorganic membranes, thin film handbooks p879-p901 (Japan Society for the Promotion of Science), vacuum technology handbooks p502-p509, p612, p810 (Nikkan Kogyo Shimbun), vacuum handbook revised editions p132-p134 (ULVAC Japan Vacuum Technology KK) Inorganic membranes as described in (1). For example, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni, MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O ₃ , TiO ₂ , Cr ₂ O ₃ , Si _x O _y (x = 1, y = 1.5 to 2.0), Ta ₂ O ₃ , ZrN, SiC, TiC, PSG, Si ₃ N ₄ , SiN Single crystal Si, amorphous Si, W, or the like is used. The inorganic film is formed by a dry film forming method such as vapor deposition, sputtering, CVD, or ion plating. Alternatively, an organic / inorganic composite film coated with alkoxysilane by a sol-gel method or an inorganic film coated with polysilazane and baked may be used.
Moreover, as a material of the metal foil, for example, a metal material such as aluminum, copper, or nickel, or an alloy material such as stainless steel or an aluminum alloy can be used, but aluminum is preferable in terms of workability and cost. The film thickness of the metal foil is about 1 to 100 μm, preferably about 10 μm to 50 μm. As this metal foil, a metal foil laminated on a plastic substrate can be used as a barrier substrate.

As a characteristic of the barrier substrate 8, it is preferable that the water vapor permeability is 0.01 g / m ² · day · atm or less. Further, it is preferably a high-barrier substrate (high barrier film) having an oxygen permeability of 10 ⁻³ ml / m ² / day or less and a water vapor permeability of 10 ⁻⁵ g / m ² / day or less.

  The organic EL element manufactured by the organic EL element manufacturing method according to the present embodiment described above provides an organic electroluminescence element that achieves both productivity and barrier properties and hardly damages the organic electroluminescence layer. Is possible.

  In addition, the 3rd layer 6, the contact bonding layer 7, and the barrier property base material 8 formed on the 2nd layer 5 can be provided arbitrarily. For example, the adhesive layer 7 can be formed on the second layer 5 by performing the adhesive layer forming step S4 after the second layer forming step S2. Further, the barrier substrate 8 can be formed on the second layer 5 by performing the barrier substrate forming step S5 after the second layer forming step S2. Further, the third layer forming step S3 is performed after the second layer forming step S2, and the barrier base material forming step S5 is further performed, so that the third layer 6 and the barrier base material 8 are formed on the second layer 5. They can be formed in order. Further, the adhesive layer forming step S4 is performed subsequent to the second layer forming step S2, followed by the barrier base material forming step S5, whereby the adhesive layer 7 and the barrier base material 8 are formed on the second layer 5. Can also be formed in order (both not shown). In any case, the respective effects described with respect to the respective layers (the third layer 6, the adhesive layer 7, and the barrier substrate 8) can be achieved by the respective layers formed on the second layer 5.

  In the organic EL element manufacturing method according to the present embodiment, the organic EL layer is formed by a known material and process until the first layer forming step S1 for sealing the organic EL layer 3, that is, until the organic EL layer 3 is formed. Element 1 can be manufactured. For example, it can be manufactured as follows.

  As shown in FIG. 5, the organic EL element 50 according to this embodiment includes a first electrode (anode) 52, an organic EL layer 53, and a second electrode on a substrate 51 (corresponding to the substrate 2 shown in FIGS. 1 to 4). The electrode (cathode) 54 is laminated, and the first layer 4 and the second layer 5, and the third layer 6, the adhesive layer 7, and the barrier base material 8 as necessary are further formed thereon. Since the first layer 4 and subsequent layers have been described above, the detailed description will be omitted in the following description, and only the substrate 51 to the cathode will be described. In FIGS. 1 to 4, the first electrode 52 and the second electrode 54 are included in the organic EL layer 3.

  In the organic EL element, when a positive voltage is applied to the anode and a negative voltage is applied to the cathode, the injected holes and electrons are recombined in the light emitting layer in the organic EL layer to emit light. The organic EL element is most simply composed of an anode / light emitting layer / cathode. For example, the structure of the anode / hole transport layer / light emitting layer / electron transport layer / cathode, etc. The hole injection layer, electron blocking layer, hole blocking layer, electron injection layer, buffer layer, and other necessary layers are stacked in the specified layer order, so that carriers such as holes and electrons injected from both electrodes are efficiently transferred. Some are configured to do well.

  In FIG. 5, the first electrode (anode) 52, the organic EL layer 53, and the second electrode (cathode) 54 are stacked on the substrate 51 in this order, but conversely, the first electrode on the substrate 1. A cathode may be formed as 52 and an organic EL layer may be formed in the reverse order of the layers, and an anode may be stacked as the second electrode 54 in order.

  As the substrate 51, a transparent plastic substrate represented by polyethylene terephthalate, polycarbonate, or the like can be used in addition to glass.

As the anode 52, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function is preferably used, and an electrode material having a work function of 4 eV or more is particularly preferable. Specific examples of such an electrode material include conductive transparent materials such as metals such as gold, ITO (indium tin oxide), AZO, IZO, SnO ₂ , and ZnO. For example, the anode can be formed as a thin film by depositing these electrode materials on the substrate 1 by a method such as a vacuum deposition method, an ion plating method, or a sputtering method.

  When a transparent glass substrate is used as the substrate 51 and an anode is laminated as the first electrode 52 and light is transmitted through the anode through the substrate 51, the light transmittance of the anode is preferably 80% or more. The sheet resistance of the anode is preferably several hundred Ω / □ or less, particularly preferably 100 Ω / □ or less. Furthermore, the film thickness of the anode varies depending on the material in order to control the characteristics such as light transmittance and sheet resistance of the anode as described above, but is usually preferably 500 nm or less, and more preferably in the range of 10 to 200 nm.

  On the other hand, in the organic EL layer 53, a cathode (for example, the second electrode 54) that is an electrode for injecting electrons into the light emitting layer is an electrode made of a metal, an alloy, an electrically conductive compound, and a mixture thereof having a low work function. It is preferable to use a material, and examples of such an electrode material include sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, and Al / LiF mixture. be able to. The cathode can be produced by forming these electrode materials into a thin film by a method such as vacuum deposition or sputtering. Moreover, when light emission is extracted through the cathode, the cathode preferably has a light transmittance of 80% or more. Although the film thickness of a cathode changes with materials, 500 nm or less is preferable normally, More preferably, it is the range of 100-200 nm.

  Organic light-emitting materials contained in the light-emitting layer include aromatic heterocyclic compounds such as carbazole, carboline, diazacarbazole, triarylamine derivatives, stilbene derivatives, polyarylenes, aromatic condensed polycyclic compounds, aromatic heterocondensed compounds. Examples thereof include, but are not limited to, a ring compound, a metal complex compound and the like, and a single oligo compound or a composite oligo compound thereof.

  The light emitting layer preferably contains about 0.1 to 20% by mass of a dopant in the light emitting material. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and in the case of phosphorescent light emitting layers, for example, tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonate). And complex compounds such as ortho-metalated iridium complexes represented by iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like. The thickness of the light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.

  As the hole injection / transport layer, conductive polymers represented by phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), etc. In addition, for example, carbazole-based light-emitting materials such as 4,4′-dicarbazolylbiphenyl and 1,3-dicarbazolylbenzene, (di) azacarbazoles, , 3,5-tripyrenylbenzene, and the like, and low molecular light emitting materials typified by pyrene-based luminescent materials, polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles, and the like.

  Examples of the electron injection / transport layer material include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, and nitrogen-containing five-membered ring derivatives listed below. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  In the organic EL layer 53, the thickness of each organic layer needs to be about 50 to 300 nm, and preferably about 100 to 200 nm.

  In the embodiment shown in FIG. 5, a first electrode 52, an organic EL layer 53 including a hole transport layer, a light emitting layer, an electron transport layer, and the like, and a second electrode 54 are formed on a substrate 51. A first layer 4 (not shown in FIG. 5) and a second layer 5 (not shown in FIG. 5) are formed on the second electrode 54 of the laminate. Further, as described above, the third layer 6, the adhesive layer 7, and the barrier base material 8 are formed as necessary (none of them are shown in FIG. 5).

  Hereinafter, the content of the present invention will be specifically described with reference to an example that exhibits the effect of the present invention and a comparative example that is not.

(Production of organic EL element)
Using a glass substrate with an ITO (100 nm thickness) having a size of 100 × 100 mm and a thickness of 1.0 mm, the ITO was patterned to form an anode and an anode terminal portion.

Next, the substrate on which the anode was formed was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and each of the constituent materials of each layer of the organic EL layer was filled in each of the deposition crucibles in the vacuum deposition apparatus. Deposition was performed under reduced pressure to a vacuum degree of 4 × 10 ⁻⁴ Pa and rotating around the center of the substrate through a shadow metal mask covering the substrate other than the anode terminal portion and the light emitting region. Thereafter, the following organic layers were sequentially laminated.

Hole injection layer (PEDOT: 40 nm) / hole transport layer (α-NPD: 20 nm) / light emitting layer (CBP, Ir (ppy) ₃ (6%): 30 nm) / hole blocking layer (BAlq: 10 nm) / Electron transport layer (Alq ₃ : 30 nm) / LiF (0.5 nm)
In addition, PEDOT / PSS, the Bayer company make, Baytron PAl4083 was used for PEDOT.
After laminating the organic layer, a cathode made of aluminum (thickness 150 nm) and a cathode terminal portion (cathode feeding portion) were formed by vapor deposition to produce an organic EL device.

(Formation of sealing film)
A sealing film was formed on the organic EL element as follows.

[Example 1]
(Formation of thermal ALD film)
The produced organic EL element was transported in a vacuum and carried into an ALD film forming chamber for forming a thermal ALD film. The temperature in the ALD film forming chamber is heated to 100 ° C., and the organic EL element is heated to the same temperature. Thereafter, a film forming start process is started, and an alumina film (Al ₂ O ₃ ) is formed. The film formation process of thermal ALD is shown below.

1) An inert gas was introduced into the film forming chamber to maintain a pressure of about 50 to 100 Pa.
2) Next, TMA (trimethylaluminum) filled in the bottle was vaporized under reduced pressure and supplied to the film formation chamber for a predetermined time while maintaining the pressure, and adsorbed to the organic EL element.
3) The film forming chamber was replaced with an inert gas.
4) Next, H ₂ O filled in the bottle was vaporized and supplied to the film formation chamber for a predetermined time while maintaining the pressure, and reacted with TMA adsorbed on the organic EL element to form an alumina film.
The steps from 1) to 4) are one cycle, and one atomic layer is formed. This was repeated for a desired film thickness to form a film thickness of 5 nm.

(Formation of plasma ALD film)
After forming the thermal ALD film, in Example 1, the plasma ALD film was continuously formed in the same chamber.
It is more efficient to process in the same room, and the equipment cost can be reduced. The temperature in the plasma ALD film forming chamber was the same as that in thermal ALD. The same alumina film (Al ₂ O ₃ ) as thermal ALD was formed. The film formation process of plasma ALD is shown below.

1) An inert gas was introduced into the film forming chamber to maintain a pressure of about 50 to 100 Pa.
2) Next, TMA (trimethylaluminum) filled in the bottle was vaporized under reduced pressure and supplied to the film formation chamber for a predetermined time while maintaining the pressure, and adsorbed to the organic EL element.
3) The film forming chamber was replaced with an inert gas.
4) Next, the O ₂ gas is supplied to the film forming chamber for a predetermined time, and glow discharge plasma is generated by a high frequency power source to bring the introduced O ₂ gas into an active state and adsorbed on the organic EL element. Reaction was performed to form an alumina film.
The steps from 1) to 4) are one cycle, and one atomic layer is formed. This was repeated for a desired film thickness to form a film thickness of 15 nm.

[Example 2]
(Formation of plasma CVD film)
After the thermal ALD film described in Example 1 was formed on the organic EL element, in Example 2, film formability was continuously performed by plasma CVD.

In the case of plasma CVD, the substrate is put into a film formation chamber for plasma CVD, and SiH ₄ (silane) gas, NH ₃ (ammonia), and N ₂ (nitrogen) gas are introduced so that the pressure becomes 100 Pa. . Then, glow discharge plasma by a high frequency power source was generated and reacted on the organic EL element to form a 200 nm SiN _x film.

Example 3
(Formation of transition region sputtered film)
After the thermal ALD film described in Example 1 was formed on the organic EL element, in Example 3, film formation was continuously performed by transition region sputtering.

When performing transition region sputtering, an organic EL element is placed in a film formation chamber for transition region sputtering, and magnetron sputtering using a DC pulse power source is used. In magnetron sputtering, Ar is introduced, a target is sputtered under a pressure of 0.5 Pa, and a flow rate is controlled while simultaneously supplying O ₂ (oxygen) gas as a reactive gas, and a silicon oxide film (SiO _x ). A film was formed. The transition region was controlled by monitoring the emission intensity and feeding back to the oxygen amount. As a result, a 200 nm thick SiO _x film was formed.

Example 4
(Formation of activated vapor deposition film)
After the thermal ALD film described in Example 1 was formed on the organic EL element, in Example 4, film formability with an activated vapor deposition film was continuously performed.

In the case of an activated vapor deposition film, the substrate is put into the deposition chamber for the activated vapor deposition film, O ₂ gas is introduced while flowing Ar gas into the pressure gradient plasma gun, and the pressure in the vacuum chamber is 0.08 Pa. Ar gas was allowed to flow. Then, electric power is applied to the pressure gradient type plasma gun to generate a plasma beam. This plasma beam is irradiated onto the pellet material made of SiO to sublimate the material and react with O ₂ gas, so that SiO ₂ is formed on the organic EL element. _{An X} film was formed to 200 nm.

[Comparative Example 1]
The thermal ALD film described in Example 1 was formed on the organic EL element.
[Comparative Example 2]
The plasma ALD film described in Example 1 was formed on the organic EL element [Comparative Example 3]
The plasma ALD film described in Example 1 was formed on the organic EL element, and the plasma CVD film described in Example 2 was further formed thereon.

  For Examples 1 to 4 and Comparative Examples 1 to 3, barrier properties and luminance degradation were evaluated as follows.

(Evaluation of barrier properties)
For the barrier property, the water vapor transmission rate was evaluated. According to the method described in Japanese Patent Application Laid-Open No. 2004-333127, the water vapor transmission rate is obtained by depositing various films on a PET substrate and performing 20 × 20 mm square calcium vapor deposition at 60 ° C. and 90%. Under the condition of RH, the water vapor transmission rate M (g / m ² / day) was estimated from the corrosion area of calcium after storage. The barrier property was evaluated based on the water vapor permeability M estimated as described above according to the following evaluation criteria.
X: M ≧ 1E-2
Δ: 1E-2> M ≧ 1E-3
○: 1E-3> M ≧ 1E-4
◎: 1E-4> M

(Evaluation of luminance degradation)
Each produced organic EL element was driven at a constant current value of 25 A / m ² , and the emission luminance of each organic EL element was measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta Sensing). Luminance deterioration was calculated by the ratio of the emission luminance A (cd / m ² ) after the organic EL element was produced to the emission luminance B (cd / m ² ) after the sealing film was produced, that is, B / A * 100.

  Table 1 shows the evaluation results of barrier properties and the evaluation results of luminance deterioration of Examples 1 to 4 and Comparative Examples 1 to 3.

As shown in Table 1, Examples 1-4 were excellent in evaluation of barrier properties and luminance deterioration. Particularly, Examples 2 to 4 in which an appropriate film was further added on the thermal ALD film and the plasma ALD film were extremely excellent in barrier properties. The production of Examples 1 to 4 was not excessively burdensome and the productivity was sufficiently high.
Since the luminance deterioration of Examples 1 to 4 was excellent, it was confirmed that the organic EL layer was hardly damaged.

  On the other hand, Comparative Examples 1 to 3 caused luminance deterioration when there was no thermal ALD film, and resulted in poor barrier properties when only thermal ALD was used.

  Next, an ALD film, a plasma CVD film, a transition region sputtering film, and an activated vapor deposition film were formed as a single film on a substrate, and the elastic modulus was measured as follows. The ALD film is formed by plasma ALD, but when it is formed by thermal ALD, substantially the same elastic modulus is obtained. In addition, the elasticity modulus here is a nanoindentation elasticity modulus (Er), and was measured using the SII nanotechnology company make and scanning probe microscope SPI3800N.

  As the indenter, a triangular pyramid-shaped diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) was used.

  In the measurement, first, the triangular pyramid-shaped diamond indenter was applied to the sample surface at a right angle, a load was gradually applied, and the load was gradually returned to 0 after reaching the maximum load. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as nanoindentation hardness (H). The nanoindentation elastic modulus (Er) was calculated using the following formula, assuming the slope S of the unloading curve.

(Formula) Er = (S × √π) / (2√A)
However, (pi) shows a circumference ratio.
In addition, it calibrated and measured beforehand the measurement apparatus so that the hardness obtained as a result of pushing the attached fused silica as the standard sample would be 9.5 ± 1.5 GPa.

  Details of the principle are described in Handbook of Micro / Nano Tribology (CRC edited by Bharat Bhushan).

  As a measurement sample, a drop of adhesive Aron Alpha (registered trademark) manufactured by Toagosei Co., Ltd. was dropped on a slide glass, and then a sample cut into about 1 cm square was placed and allowed to cure for 24 hours.

  The maximum load P was set in advance so that the maximum depth was 15 nm (50 μN). Both loading and unloading were performed in 5 seconds. The results are shown in Table 2.

  As shown in Table 2, the plasma CVD film forming the third layer, the transition region sputtered film, and the activated vapor deposition film are more elastic than the ALD film forming the first layer and the second layer in the present invention. Was confirmed to be low. Since the ALD film forming the first layer and the second layer has a high elastic modulus, the film is hard and fragile. Therefore, when this layer is in direct contact with the adhesive layer, it is caused by stress or expansion of the adjacent layer due to temperature change or the like. Deformation increases and cracks are likely to occur. However, if the third layer having a low elastic modulus is formed on the ALD film, the ALD film functions as a stress relaxation layer, so that the ALD film is hardly damaged. Therefore, the barrier property is further improved by forming the third layer.

1 Organic electroluminescence device (organic EL device)
2 Substrate 3 Organic electroluminescence layer (organic EL layer)
4 First layer 5 Second layer 6 Third layer 7 Adhesive layer 8 Barrier substrate S1 First layer forming step S2 Second layer forming step S3 Third layer forming step S4 Adhesive layer forming step S5 Barrier substrate forming step

Claims (8)

An organic electroluminescent element manufacturing method for manufacturing an organic electroluminescent element,
A first layer forming step of forming an alumina-made first layer on the organic electroluminescence layer formed on the substrate by performing an atomic layer deposition method only by thermal reaction without supporting by plasma;
A second layer forming step of performing a plasma-assisted atomic layer deposition method on the first layer to form a second layer made of alumina ;
The organic electroluminescent element manufacturing method characterized by including.   The organic electroluminescence device according to claim 1, further comprising a third layer forming step of forming a third layer having a lower elastic modulus than the first layer and the second layer on the second layer. Production method.   3. The method of manufacturing an organic electroluminescence element according to claim 2, wherein the third layer is formed by at least one of a plasma CVD method, a sputtering method of reacting in a transition region, and an activated vapor deposition method. Before Symbol third layer organic electroluminescent device fabrication method according to claim 2 or 3, characterized in that an inorganic layer containing Si. Said first layer and has a thickness of 3~25nm each of the second layer, according to any one of claims 2 4, the thickness of the third layer is characterized in that it is a 100~350nm The organic electroluminescent element manufacturing method of. Wherein the third layer on the method of the organic electroluminescent device produced according to any one of claims 2 to 5, characterized in that it comprises an adhesive layer forming step of forming an adhesive layer   The method for producing an organic electroluminescence device according to claim 6, further comprising a barrier substrate forming step of forming a substrate having a barrier property on the adhesive layer. The first layer and the second layer are formed in the same chamber of an apparatus for performing atomic layer deposition, and
Trimethylaluminum and H ₂ O or O ₃ are used as raw materials for the first layer,
The second layer after the first layer was formed a predetermined thickness, the raw material in any one of claims 1 7, characterized in that to assist in the plasma switch to trimethylaluminum and O ₂ The organic electroluminescent element manufacturing method of description.

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