JP2017063008A - Organic electronic element manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronic element manufacturing method that can form a protection layer having less defect without damaging members constituting an organic electronic element by washing with liquid containing water.SOLUTION: An organic electronic element manufacturing method comprising a step of forming a lower electrode 2, a step of forming an organic compound layer 3 on the lower electrode, a step of forming an upper electrode 4 on the organic compound layer, a step of forming a first protective layer on the upper electrode, and a step of forming an ALD protective layer on the first protective layer by an atomic layer deposition method, further includes a step of washing at least one of the organic compound layer, the upper electrode, and the first protective layer with liquid 6 containing water after the step of forming the organic compound layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing an organic electronic device.

  An organic electronic device is an electronic device using an organic compound, and various organic electronic devices have been researched and developed in recent years.

  An organic light-emitting element, which is an example of an organic electronic element, is an element having an anode, a cathode, and an organic compound layer disposed therebetween. In the organic light-emitting element, excitons are generated by recombination of holes injected from the anode and electrons injected from the cathode in the light-emitting layer, and light is emitted when the excitons return to the ground state.

  An organic photoelectric conversion element, which is an example of an organic electronic element, is an element having two electrodes and an organic photoelectric conversion layer disposed therebetween. When light is applied to the organic photoelectric conversion element, the electron donor in the organic photoelectric conversion layer absorbs the light to generate excitons. The excitons diffuse and move to the interface between the electron donor and the electron acceptor, and electrons flow from the electron donor to the electron acceptor, whereby charge separation occurs. The holes and electrons generated by the charge separation flow to the respective electrodes, whereby a current flows to the external circuit.

  Organic electronic devices are desired to be thin, light and flexible. Therefore, as a method for sealing the organic electronic element, a sealing method in which a protective layer (passivation film) is formed on the element is known instead of the conventional cap sealing using metal or glass. As a sealing method using a protective layer, for example, a technique of coating a silicon nitride (SiN) film on an organic electronic element by a CVD method is known. From the viewpoint of blocking moisture and oxygen and protecting the organic electronic device, the protective layer is required to have a high density and a high covering property.

  By the way, it is known that when water or oxygen enters inside the organic electronic element, the organic electronic element is deteriorated. For example, when the electron injection layer or the cathode constituting the organic light emitting device reacts with moisture, the electron injection property of the reacted region may be lowered. Thus, the region where the electron injecting property is deteriorated becomes a non-light-emitting defect called a dark spot. In other organic electronic devices, it is not preferable that moisture penetrates into the device.

  In a process of manufacturing an organic electronic element, for example, a substrate transport process or an organic layer film forming process, foreign matter may adhere to the substrate or the organic electronic element. If foreign matter is attached to the organic electronic element before the protective layer is formed, a moisture or oxygen intrusion path is formed in the formed protective layer. The protective layer in such a state is not preferable because moisture and oxygen enter with time. In the organic light emitting device, the non-light emitting region is enlarged, and the dark spot is generated in the organic light emitting device.

  On the other hand, even if foreign matter is attached, if the protective layer is formed thick so that the intrusion path of moisture or oxygen is not formed, protection performance from moisture and oxygen can be obtained. However, in the case where the protective layer is formed thick, the film formation time is significantly increased, resulting in an increase in manufacturing cost.

  Therefore, in order to form a protective layer having high protection performance without lengthening the film formation time of the protective layer, it is necessary to remove foreign substances present on the substrate and the organic electronic element before forming the protective layer. preferable.

  Patent Document 1 describes a cleaning method using carbon dioxide particles as a method for removing foreign matter. Since foreign matter removal using carbon dioxide particles does not use moisture, foreign matter can be removed without causing deterioration of the organic compound layer due to reaction with moisture.

JP 2011-81966 A

  The method for removing foreign matter of Patent Document 1 has a problem that physical damage is caused to the organic compound layer at the time of collision of carbon dioxide particles. Further, even if the object from which the foreign matter is removed becomes the upper electrode, physical damage is similarly caused.

  The present invention provides a method for manufacturing an organic electronic element that hardly causes a moisture or oxygen intrusion path in a protective layer by removing foreign substances while suppressing physical damage to an organic compound layer and an upper electrode. With the goal.

  Therefore, the present invention includes a step of forming a lower electrode, a step of forming an organic compound layer on the lower electrode, a step of forming an upper electrode on the organic compound layer, and on the upper electrode. A method of manufacturing an organic electronic device, comprising: forming a first protective layer; and forming an ALD protective layer on the first protective layer by an atomic layer deposition method, wherein the organic compound layer A method for producing an organic electronic device, comprising a step of washing at least one of the organic compound layer, the upper electrode, and the first protective layer with a liquid containing water after the step of forming I will provide a.

  According to the present invention, at least one of the organic compound layer, the upper electrode, or the first protective layer is washed with a liquid containing water to remove foreign matters while suppressing physical damage, Since the protective layer having a high coverage is provided, it is possible to provide a highly reliable manufacturing method of an organic electronic element that is unlikely to generate a moisture or oxygen intrusion route.

It is a schematic diagram which shows an example of the process wash | cleaned with the liquid containing water in the manufacturing method of the organic electronic element of this invention.

  The present invention includes a step of forming a lower electrode, a step of forming an organic compound layer on the lower electrode, a step of forming an upper electrode on the organic compound layer, and a first step on the upper electrode. A method for forming an organic electronic device, comprising: forming a protective layer of the first layer; and forming an ALD protective layer on the first protective layer by an atomic layer deposition method.

  The production method of the present invention includes a step of washing at least one of the organic compound layer, the upper electrode, and the first protective layer with a liquid containing water after the step of forming the organic compound layer. This is a method for producing an organic electronic device.

  The step of cleaning with a liquid containing water in the present embodiment is a step of removing foreign matter on or in the formed layer.

  FIG. 1 is a schematic diagram showing a process of cleaning the upper electrode with a liquid containing water after forming the upper electrode. A lower electrode 2, an organic compound layer 3, and an upper electrode 4 are formed on the substrate 1. The foreign matter 5 on the upper electrode 4 is removed by the liquid 6 containing water supplied from the nozzle 7.

  In FIG. 1, an example in which the upper electrode is cleaned is given as an example of the present invention. However, even when the organic compound layer and the first protective layer are cleaned, foreign matters can be similarly removed.

  In the present embodiment, the liquid containing water is a liquid containing water as a main component, and the weight ratio of water is 50% by weight or more when the weight of the whole liquid is 100% by weight. Preferably, when the weight of the whole liquid is 100%, the weight ratio of water is 80% or more, more preferably 90% or more. Cleaning using a liquid containing water is preferable because it has a smaller influence on the organic compound than cleaning using an organic solvent.

  The liquid containing water may have an additive. Specifically, it is at least one of a surfactant, carbon dioxide, an antistatic agent, and a lubricant. In the case of having carbon dioxide, it is preferable because foreign matters can be prevented from reattaching due to electrostatic force.

  The liquid containing water preferably has a boiling point of 100 ° C. or higher and 200 ° C. or lower. This is because the liquid is easily vaporized when the liquid is removed from the organic electronic element after cleaning.

  In the step of washing with a liquid containing water according to the present invention, any of the organic compound layer, the upper electrode, and the ALD protective layer may be washed, or each of them may be washed.

  When cleaning each layer, the upper electrode is formed after cleaning the organic compound layer, the first protective layer is formed after cleaning the upper electrode, and the ALD protection is performed after cleaning the first protective layer. A layer may be formed.

  When performing the process of cleaning with a liquid containing water, the target to be cleaned and the nozzle to which the cleaning liquid is applied may be cleaned while moving relatively.

  The cleaning process using a liquid containing water includes methods such as two-fluid cleaning, ultrasonic cleaning, microbubble cleaning, and high-pressure spray cleaning. However, the cleaning process using a liquid containing water is not limited to these methods. Absent.

  The cleaning step using a liquid containing water preferably uses two-fluid cleaning with a high foreign matter removal rate. In the two-fluid cleaning, a two-fluid liquid is mixed with a gas, water particles having a fine particle diameter are formed, and this is sprayed onto the substrate from a nozzle, thereby removing foreign matters and dust on the substrate. As the gas to be used, an inert gas such as nitrogen or argon can be used.

  Parameters that determine the cleaning effect of the two-fluid cleaning include a gas flow rate, a liquid flow rate, a cleaning time, and the like. As a result, the foreign matter removal rate changes. Nitrogen gas is used as the gas, and pure water is preferably used as the liquid.

  In the case of two-fluid cleaning, it is desirable that the nitrogen flow rate is 10 L / min to 180 L / min and the pure water flow rate is 0.05 L / min to 2.0 L / min.

  For the two-fluid cleaning, a method in which the two-fluid nozzle is swung on the substrate while rotating the substrate at a certain speed is preferably used, and the substrate rotation speed during the cleaning is preferably 100 rpm or more and 2000 rpm or less.

  Instead of cleaning while rotating the substrate, a method may be used in which the substrate is transported and cleaned under a nozzle array in which two fluid nozzles are arranged at a certain interval.

  By cleaning the substrate under the above conditions, it is possible to remove foreign matters, dust, etc. existing in or on the film while suppressing damage to the members constituting the organic electronic element and film peeling. Become. If this cleaning step is not performed, foreign matter is present in the substrate or the organic electronic element, and therefore, there is a possibility that a moisture or oxygen intrusion path is formed in the protective layer.

  In addition, in the removal trace after the foreign matter removal by the cleaning process, a defect of sub μm to several tens of μm may occur from the boundary portion of the removal trace depending on the water resistance of the member constituting the organic electronic element. However, this defect does not increase over time due to storage or driving after the organic electronic device is manufactured, and thus does not affect the reliability of the product. Therefore, if the defect has a size that does not cause a functional problem, it can be applied to a product.

  The step of cleaning with a liquid containing water according to the present invention is preferably performed in an inert gas atmosphere such as nitrogen or argon, but can also be performed in the air. However, when the organic compound layer is exposed to ambient light including ultraviolet to visible light while being exposed to the atmosphere, the organic compound in the organic compound layer causes a chemical reaction with oxygen and moisture in the atmosphere and deteriorates. There is a case. When the organic compound layer is deteriorated, the organic electronic device may be increased in voltage, and light emission efficiency and durability characteristics may be reduced. Therefore, when carrying out this step in an atmospheric environment, in order to prevent deterioration of the organic compound, the energy at the spectral edge on the short wavelength side of the ambient light is set to be higher than the excited singlet state of the organic compound contained in the organic compound layer. It is preferable to make it low. Specifically, the deterioration of the organic compound can be suppressed by using ambient light as a yellow fluorescent lamp or a red lamp used for semiconductor manufacturing. It is also possible to suppress the deterioration of the organic compound by shielding the organic compound layer so that light is not irradiated.

  You may have the process of drying the liquid containing water after washing | cleaning. For example, after two-fluid cleaning, it is preferable to perform spin drying by setting the substrate rotation speed to 500 rpm or more and 4000 rpm or less. The drying time is 30 seconds or more and 3 minutes or less, and the drying is performed under the condition that no water droplets remain on the substrate.

  Furthermore, the method for manufacturing an organic electronic device of the present invention may further include a step of heating under reduced pressure after cleaning. By heating, the liquid containing water used for cleaning can be efficiently removed from the organic electronic element.

  The heating temperature is preferably 50 ° C. or higher, more preferably 115 ° C. or higher. Moreover, it is more preferable that it is the range below the glass transition temperature of the organic compound which an organic electronic element has. That is, it is preferably 115 ° C. or higher and below the glass transition temperature of the organic compound included in the organic electronic element.

  The ALD protective layer refers to a protective layer formed by an atomic deposition method. The ALD protective layer is formed by removing moisture or impurities from the portion where the foreign compound is removed in the cleaning process and the organic compound layer or the upper electrode is exposed. Oxygen penetration can be suppressed.

  As the atomic layer deposition method ALD, there is known a method in which the substrate is left still and the atmosphere gas is changed. As the ALD protective layer of the present invention, Spatia-ALD which can be deposited at high speed by moving the substrate between different atmospheric gases can also be used.

As a constituent material of the ALD protective layer, aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO), titanium oxide (TiO ₂ ), zirconia oxide (ZrO ₂ ), or the like is used. A plurality of these constituent materials may be used to form a laminate. Moreover, it is good also as a multilayer film which repeatedly formed the laminated body into multiple times.

  The film thickness of the ALD protective layer is determined in consideration of moisture resistance, cost, tact and the like. The film thickness is preferably 5 nm or more and 500 nm or less.

  Since the atomic deposition method is a film forming method in which a single layer is formed, a dense film having a very high coverage can be obtained. Even when foreign matter having a diameter of several μm is present, it may exhibit good coverage without defects, which is preferable as a sealing layer for organic electronic elements.

As an example of a stationary ALD film formation method, a film formation method of aluminum oxide (Al ₂ O ₃ ) will be described below.

First, trimethylaluminum (TMA) is introduced into a reaction chamber in which a substrate is placed, thereby adsorbing a single layer of TMA on the substrate. Next, excess TMA in the reaction chamber is removed. Next, by introducing water vapor into the reaction chamber, the TMA single layer adsorbed on the substrate reacts with the water vapor to form an Al ₂ O ₃ single layer. Finally, one cycle of film formation is completed by removing the reaction product methane and excess water vapor. By repeating this cycle, the desired film thickness can be obtained.

  In the present invention, before the ALD protective layer is formed by the atomic layer deposition method, the foreign matter is removed by washing with a liquid containing water. When the foreign matter is removed, even if a protective layer or the like is subsequently formed, the newly generated gap in the gap is small. Therefore, it is possible to form an ALD protective film with fewer defects than when the level difference due to the foreign matter is large.

  When the first protective layer is formed by the atomic deposition method, the second ALD protective layer can be further formed after the ALD protective layer is washed. The method for forming the second ALD protective layer is the same as the method for forming the ALD protective layer. The second ALD protective layer may be the same as or different from the constituent material of the ALD protective layer.

The manufacturing method of the organic electronic device according to the present invention may include the following steps.
(A) Step of preparing a lower electrode (B) Step of forming an organic compound layer on the lower electrode (C) Step of washing the organic compound layer with a liquid containing water (D) Upper electrode on the organic compound layer (E) The step of cleaning the upper electrode with a liquid containing water (F) The step of forming a first protective layer in contact with the upper electrode (G) The first protective layer with a liquid containing water Step of cleaning (H) Step of forming an ALD protective layer on the first protective layer

  Note that (G) may be omitted, and (H) may be a step of forming an ALD protective layer on the upper electrode. In that case, the cleaning step is at least one of (C) and (E).

  Steps (C), (E), and (G) are cleaning steps. The present invention only needs to have at least one of these washing steps. Of course, you may have all the processes of (C), (E) and (G).

  Below, processes other than the washing | cleaning process and the (H) process are demonstrated among the manufacturing methods of the organic electronic element which concerns on this invention.

(A) Step of forming lower electrode A lower electrode is formed on a substrate. A substrate on which a lower electrode is formed in advance may be prepared. The substrate is formed of a material that can support the organic compound layer and the electrode, and glass, plastic, silicon, and the like are preferable. A switching element such as a TFT may be formed on the substrate.

  The lower electrode may be any conductive material. In particular, when light is extracted from the substrate side (bottom emission), from the viewpoint of translucency, transparent conductive oxides typified by ITO, semi-transparent metal or semi-transparent alloy, semi-transparent metal nanowires It is preferably formed of a conductive polymer such as PEDOT-PSS.

  When light is extracted from the side opposite to the substrate (top emission), it is preferably a reflective electrode formed of a metal or an alloy thereof so that the light emitted from the light emitting layer can be reflected to improve the light emission efficiency. Specifically, materials such as Al, Ag, Pt, Au, Cu, Pd, Ni, and Mo are suitable. The reflective electrode may be a laminate in which a metal layer and a transparent conductive oxide such as ITO are laminated.

  The lower electrode can be formed by a known method such as a vacuum deposition method or a sputtering method.

  The lower electrode can be formed at a predetermined position by patterning. As a method for patterning the lower electrode, a known method can be used. An insulating film may be formed on the edge portion of the lower electrode.

  Moreover, it is preferable to perform the process of removing the foreign material on the lower electrode, and the process of modifying the surface of the lower electrode after forming the pattern of the lower electrode. For example, argon plasma treatment, oxygen plasma treatment, UV irradiation treatment, heat treatment, and the like can be given. It is preferable to perform these treatments to adjust the charge injection property of the lower electrode and remove contamination on the lower electrode.

(B) Step of forming an organic compound layer on the lower electrode Next, an organic compound layer is formed on the lower electrode. As a method for forming the organic compound layer, a known technique such as a vacuum deposition method, an ink jet method, a spin coating method, or a nozzle coating method can be used. The organic compound layer may be a multilayer structure. Details of the organic compound layer will be described later.

(D) Step of forming upper electrode on organic compound layer Next, an upper electrode is formed on the organic compound layer. A known film forming technique can be used for forming the upper electrode. In particular, a resistance heating vapor deposition method, an induction heating vapor deposition method, an EB vapor deposition method, a sputtering method and the like in vacuum are preferable.

  The upper electrode is preferably formed so that the organic compound layer is not exposed on the surface. By not exposing the organic compound layer to the surface, it is possible to reduce the frequency of peeling of the organic compound layer when the upper electrode is washed with a liquid containing water. Further, by not exposing the organic compound layer to the surface, the cleaning conditions can be strengthened, so that foreign matters can be more effectively removed.

  The upper electrode may be any conductive material. In the case of bottom emission, it is preferably a reflective electrode formed of a highly reflective metal or an alloy thereof so that the light emitted from the light emitting layer can be reflected to increase the light emission efficiency. Specifically, materials such as Al, Ag, Pt, Au, Cu, Pd, Ni, Mo, and Mg are preferable, and Al is particularly preferable.

  In the case of top emission, a transparent conductive oxide typified by a translucent metal thin film or ITO can be used. As the translucent metal thin film, the same metal as the above-mentioned bottom emission upper electrode can be used. A laminate of a translucent metal thin film and a transparent conductive oxide may be used.

(F) Step of forming a first protective layer on the upper electrode The first protective layer is provided to protect the organic electronic element from moisture and oxygen that can permeate from the end and upper part of the film formation region. Is a layer. In the present invention, it is preferable that the first protective layer is formed so as to cover the organic compound layer and the upper electrode, and it is particularly preferable that the first protective layer be formed almost over the entire region excluding the region where the external connection terminal is provided.

  Examples of the constituent material of the first protective layer include silicon nitride, silicon oxide, and silicon nitride oxide. A plurality of these constituent materials may be used to form a laminate. As a method for forming the first protective layer, a sputtering method, a CVD method, or an ALD method can be used.

An example in which the first protective layer is formed by the VHF plasma CVD method will be described. First, it fixes so that the high frequency electrode of a deposited film formation apparatus and the ground electrode which opposes it may touch the back surface of a board | substrate. Next, the reaction space pressure between the high frequency electrode and the ground electrode is controlled to 100 Pa while flowing SiH ₄ gas, N ₂ gas, and H ₂ gas. Then, by supplying high-frequency power to the high-frequency electrode, the first protective layer can be deposited on the substrate.

It is also possible to form the first protective layer by an atomic deposition method. In this case, a film similar to the ALD protective layer can be formed, or a different film may be formed. As the constituent material, aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO), titanium oxide (TiO ₂ ), zirconia oxide (ZrO ₂ ), or the like is used. A plurality of these constituent materials may be used to form a laminate. Moreover, it is good also as a multilayer film which repeatedly formed the laminated body into multiple times.

  The thickness of the first protective layer is preferably 20 nm or more and 200 nm or less.

  In the organic electronic device manufactured in this way, foreign substances that can become defects in the protective layer are removed by washing, and the entry of moisture or oxygen is suppressed by the dense ALD protective layer. Therefore, it becomes a stable element with few occurrences of defects over a long period of time.

(Organic light emitting device according to this embodiment)
The following is an example of the organic electronic device, and an example of the function and specific material of each organic compound layer of the organic light emitting device will be described. As an element structure of the organic light emitting element according to the present embodiment, a multilayer element structure in which a functional layer of an organic compound shown below is laminated on a substrate can be given. Note that a layer having a light emitting material among the organic compound layers is a light emitting layer.
(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / electron injection layer / cathode (3) Anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode ( 4) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (5) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport Layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / electron block layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode

  However, these device configuration examples are only basic device configurations, and the configuration of the organic light emitting device using the compound according to the present invention is not limited to these as long as it has a light emitting layer.

  Further, the organic light emitting device in the present invention may have a configuration in which the lower electrode functions as an anode and the upper electrode functions as a cathode, or may have a configuration in which the lower electrode functions as a cathode and the upper electrode functions as an anode.

The hole injection layer is a layer that improves hole injection efficiency from the anode to the hole transport layer, and an electron acceptor material that can extract electrons from the hole transport material can be used. For example, an organic material such as a transition metal oxide such as MoO ₃ , a tetracyanoquinodimethane derivative, or a hexaazatriphenylene derivative can be used. Alternatively, a mixed film of a hole transporting material having a HOMO of 6 eV or less and the electron acceptor material may be used. Examples of hole transporting materials of 6 eV or less include triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly (vinylcarbazole), poly (thiophene), and other conductive polymers. It is not limited to.

  The hole transport layer is a layer that improves the efficiency of hole injection into the light emitting layer, and is selected in consideration of the HOMO of the light emitting layer. Examples of the hole transport layer include, but are not limited to, triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly (vinyl carbazole), poly (thiophene), and other conductive polymers. It is not something. Further, the hole transport layer may have a plurality of laminated structures, and an electron block layer for suppressing electron leakage from the light emitting layer may be interposed between the hole transport layer and the light emitting layer.

  The light emitting layer is a layer containing a substance having high light emitting property. Although a substance having a high light emitting property may be used alone, it is preferable to dope a host material with a small amount of a substance having a high light emitting property. Host materials include triarylamine derivatives, phenylene derivatives, condensed ring aromatic compounds (for example, naphthalene derivatives, phenanthrene derivatives, fluorene derivatives, chrysene derivatives, etc.), organometallic complexes (for example, tris (8-quinolinolato) aluminum, etc. Organic aluminum complexes, organic beryllium complexes, organic iridium complexes, organic platinum complexes, etc.) and poly (phenylene vinylene) derivatives, poly (fluorene) derivatives, poly (phenylene) derivatives, poly (thienylene vinylene) derivatives, poly (acetylene) derivatives Of course, the polymer derivatives are not limited to these.

  Examples of highly luminescent substances include triarylamine derivatives, phenylene derivatives, condensed ring aromatic compounds (for example, fluoranthene derivatives, benzofluoranthene derivatives, pyrene derivatives, chrysene derivatives, and diarylamine-substituted derivatives thereof), Examples thereof include fluorescent light-emitting materials such as stilbene derivatives and phosphorescent light-emitting materials such as organic metal complexes (for example, organic iridium complexes, organic platinum complexes, and rare earth metal complexes).

  A substance having a high light-emitting property is also called a guest material. Guest material. When the entire compound constituting the light emitting layer is 100% by weight, it is preferably 0.1% by weight or more and 30% by weight or less. The light emitting layer may emit any color. Specifically, it may be a primary color such as red, green, or blue, an intermediate color thereof, or white.

  The hole blocking layer has a HOMO level equal to or higher than the HOMO level of the light emitting layer host, and suppresses leakage of holes from the light emitting layer and injects electrons into the light emitting layer. As the hole blocking layer, a hydrocarbon aromatic material or a heterocyclic material such as a phenanthroline derivative, a pyridine derivative, or an oxadiazole derivative can be used.

  The electron transport layer is made of a material having a high electron transport property that can efficiently transport electrons to the hole blocking layer. The electron transporting material is selected in consideration of the balance with the hole mobility of the hole injection layer or the hole transport layer. Materials having electron injection performance or electron transport performance include condensed ring aromatic compounds (eg, naphthalene derivatives, phenanthrene derivatives, fluorene derivatives, chrysene derivatives, etc.), oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, triazines Derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, organoaluminum complexes, and the like are included, but of course not limited thereto.

  The electron injection layer is not particularly limited as long as it is a compound having a high electron donating property, but a metal complex compound is particularly preferable. The metal complex compound is a metal complex compound containing an alkali metal or alkaline earth metal atom, and an alkali metal complex compound is particularly preferable. It is preferable that the ligand of the metal complex compound has a molecular weight of 300 or more, is designed so that the thermal stability of the metal complex is high, and the solubility in water is low.

  Further, it may be composed of a mixed layer of an electron transporting organic compound and a metal complex compound. As the electron transporting material, a known electron transporting material can be used as the same material as the electron transporting layer or a different material. For example, a material having a heterocyclic ring such as phenanthroline, pyridine, or oxadiazole and having a high electron transporting property can be used as appropriate.

  The method for forming the mixed film of the electron transporting material and the metal complex is not particularly limited as long as the mixed film can be obtained, but a co-evaporation method in which two materials are deposited in vacuum is particularly preferable. . Alternatively, a solution in which an electron transporting material and a metal complex compound are dissolved may be applied.

  The metal complex compound particularly preferably has a lithium complex compound represented by the following general formula [1].

［１］

[1]

In the formula [1], R _{1 to} R ₁₆ are each independently selected from a hydrogen atom or a substituent. The substituent is a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl.

  Specific structural formulas of the lithium complex compound according to the present invention are exemplified below.

  Among the exemplified compounds, the compounds shown in Substituent Group A have a substituent on a phenyl group that does not have a bond with lithium. It is preferable that a phenyl group having no bond with lithium has a substituent because the compound has high stability. Since these lithium compounds have a sublimation property by having a substituent, they are preferable when forming a layer by vapor deposition. In fact, the sublimation temperature can be lowered by providing fluorine atoms or the like. Further, by suppressing the crystallinity by introducing a substituent, it is possible to suppress crystallization when an organic light-emitting element is manufactured.

  Among the exemplified compounds, the compounds shown in Group B have a substituent introduced into the pyrazole group bonded to lithium. When a substituent is provided on a pyrazole group bonded to lithium having a small ionization energy, the stability to water is further improved by surrounding the lithium metal with the substituent. Further, by suppressing the crystallinity by introducing a substituent, it is possible to suppress crystallization when an organic light-emitting element is manufactured.

  Among the exemplified compounds, the compounds shown in Group C have substituents introduced into both the pyrazole group and the phenyl group. When a substituent is provided on the pyrazole group bonded to lithium, the stability to water is further improved by surrounding the lithium metal with the substituent. By providing substituents in both the pyrazole group and the phenyl group, crystallinity is suppressed, so that crystallization can be suppressed even when the organic compound layer of the organic light-emitting element is formed by a coating method.

  By using the mixed film of the metal complex compound and the electron transporting material as the electron injection layer, the water resistance of the electron injection layer is improved.

(Organic photoelectric conversion element according to this embodiment)
An organic photoelectric conversion element, which is an example of an organic electronic element, will be described below.

As an element structure of the organic photoelectric conversion element according to the present embodiment, a multilayer element structure in which a functional layer of an organic compound shown below is laminated on a substrate can be given. In addition, the layer which has a photoelectric converting material among organic compound layers is a photoelectric converting layer.
(1) Lower electrode / photoelectric conversion layer / upper electrode (2) lower electrode / charge blocking layer / photoelectric conversion layer / upper electrode (3) lower electrode / photoelectric conversion layer / charge blocking layer / upper electrode (4) lower electrode / Charge block layer / photoelectric conversion layer / charge block layer / upper electrode

  However, these device configuration examples are only basic device configurations, and the configuration of the organic photoelectric conversion device using the compound according to the present invention is not limited to these as long as it has an organic photoelectric conversion layer. Absent.

(Organic photoelectric conversion layer)
The organic photoelectric conversion layer may be a layer having a single compound or a layer having a plurality of types of compounds. When it has a plurality of types of compounds, it may be formed from an electron-donating p-type organic semiconductor and an electron-accepting n-type organic semiconductor. The structure of the photoelectric conversion layer includes a planar heterojunction type in which a p-type organic semiconductor and an n-type organic semiconductor are planarly stacked, and a bulk heterostructure in which the p-type organic semiconductor and the n-type organic semiconductor are interlaced in the photoelectric conversion layer. Etc.

  Examples of the p-type organic semiconductor include, but are not limited to, triarylamine derivatives, phenylenediamine derivatives, carbazole derivatives, thiophene derivatives, phthalocyanine derivatives, and the like.

  Examples of the n-type organic semiconductor include fullerene derivatives, but are not limited thereto.

(Charge blocking layer)
The charge blocking layer is a layer that suppresses charge leakage from the electrode to the organic photoelectric conversion layer, and is selected in consideration of LUMO and HOMO of the photoelectric conversion layer. As the charge blocking layer, triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, naphthalene derivatives, phenanthrene derivatives, fluorene derivatives, chrysene derivatives, oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, Examples include, but are not limited to, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, and the like. Furthermore, the charge blocking layer may have a plurality of laminated structures.

  When it has a charge block layer, since the dark current of an organic photoelectric conversion element can be suppressed, it is preferable.

  The organic light emitting element according to this embodiment can be used for a display device, an illumination device, an exposure light source of an electrophotographic image forming apparatus, and a backlight of a liquid crystal display device.

  Moreover, the organic photoelectric conversion element which concerns on this embodiment can be used for an organic solar cell or an image pick-up element.

  In the following examples, optimum cleaning conditions were selected.

(Cleaning conditions)
In the present invention, it is preferable that the cleaning conditions are such that foreign matter can be effectively removed without causing film peeling. If the cleaning conditions are too strong, the deposited film may be damaged or the film may be peeled off. The following experiment was conducted as a specific example for determining the cleaning conditions. By performing this experiment, it is possible to determine appropriate cleaning conditions. In the actual process, the adhered foreign substances vary in material, size, etc., and the polyethylene particles used this time are not all substitutes, but it is possible to grasp the foreign substance removal rate and the tendency of film peeling.

(Conditions for cleaning the organic compound layer)
After forming the organic light emitting device up to the organic compound layer, 0.2 μm polystyrene particles were dispersed on the organic compound layer as simulated foreign substances. After spraying, the number of foreign matters was counted and the substrate was cleaned. By counting the number of foreign matters again after cleaning, the removal rate by cleaning was calculated from the number of foreign matters before and after cleaning. In addition, it was confirmed after cleaning whether film peeling occurred. In Table 1 below, ◯ represents no film peeling, and Δ represents partial film peeling. Although it is preferable that there is no film peeling, it is acceptable if it is about Δ in the table.

Table 1 shows the results when cleaning was performed by changing the N ₂ flow rate (L / min) while keeping the amount of water in two-fluid cleaning constant at 0.35 L / min.

When cleaning was performed with the N ₂ flow rate set to 70 L / min or more, the foreign matter removal rate could be increased, but film peeling might occur. The N ₂ flow rate is preferably 10 L / min or more and 60 L / min or less. Further, from the viewpoint of high foreign matter removal rate, the N ₂ flow rate is more preferably 20 L / min or more and 60 L / min or less. Moreover, it turned out that 0.2 L / min or more and 1.0 L / min or less are desirable as an amount of water from the experiment which changed the amount of water.

(Conditions for cleaning the upper electrode)
After film formation up to the upper electrode, 0.2 μm polystyrene particles were sprayed on the film as simulated foreign substances. After spraying, the number of foreign matters was counted and the substrate was cleaned. By counting the number of foreign matters again after cleaning, the removal rate by cleaning was calculated from the number of foreign matters before and after cleaning. In addition, it was confirmed after cleaning whether film peeling occurred.

Table 2 shows the results when cleaning was performed by changing the N ₂ flow rate (L / min) while keeping the amount of water for two-fluid cleaning constant at 0.35 L / min. ○ and Δ in the table represent the same meaning as in Table 1.

When cleaning was performed with the N ₂ flow rate set to 90 L / min, the foreign matter removal rate could be increased, but film peeling might occur. The N ₂ flow rate is desirably 20 L / min or more and 80 L / min or less. Further, from the viewpoint of high foreign matter removal rate, the N ₂ flow rate is more preferably 30 L / min to 80 L / min. Moreover, it turned out that 0.05 L / min or more and 2.0 L / min or less are desirable as an amount of water from the experiment which changed the amount of water.

(Conditions for cleaning the first protective layer)
After film formation up to the upper electrode, 0.2 μm polystyrene particles were sprayed on the film as simulated foreign substances. After spraying, 50 nm of SiN was deposited as a first protective layer. After the film formation, the number of foreign matters was counted and the substrate was cleaned. By counting the number of foreign matters again after cleaning, the foreign matter removal rate by cleaning was calculated from the number of foreign matters before and after cleaning. In addition, it was confirmed after cleaning whether film peeling occurred.

Table 3 shows the results when cleaning was performed by changing the N ₂ flow rate (L / min) while keeping the amount of water in two-fluid cleaning constant at 0.35 L / min. ○ and Δ in the table represent the same meaning as in Table 1.

When cleaning was performed with the N ₂ flow rate set at 180 L / min, the foreign matter removal rate could be increased, but film peeling sometimes occurred. The N ₂ flow rate is preferably 40 L / min or more and 160 L / min or less. Further, from the viewpoint of high foreign matter removal rate, the N ₂ flow rate is more preferably 60 L / min or more and 160 L / min or less. Moreover, it turned out that 0.05 L / min or more and 2.0 L / min or less are desirable as an amount of water from the experiment which changed the amount of water.

(Heating process to remove liquid containing water)
Thermal desorption gas analysis was performed on the desorption temperature of moisture from the organic compound layer. When the substrate on which the organic compound layer was formed was heated in vacuum after two-fluid cleaning, moisture desorption was observed at around 80 ° C. and around 115 ° C. Therefore, it is preferable that the temperature of the heating step for removing the liquid containing water is raised to 115 ° C. or higher.

Example 1
In this example, an organic light emitting device was fabricated by performing a step of washing the organic compound layer with a liquid containing water.

  In addition, the name of the process corresponds to A to H in the embodiment.

(A) Step of forming lower electrode A lower electrode was formed by depositing ITO on a glass substrate and performing patterning. At this time, the thickness of the lower electrode was set to 100 nm. Thereafter, UV ozone treatment was performed as a surface treatment of the lower electrode.

(B) Step of forming an organic compound layer Next, an organic compound shown below was deposited on the lower electrode by a vacuum vapor deposition method at a desired position using a mask to form an organic compound layer.

  Compound 1 was formed to 3 nm as a hole injection layer, Compound 2 was formed to 50 nm as a hole transport layer, and Compound 3 was formed to 10 nm as an electron block layer. Subsequently, the light-emitting layer was co-deposited so as to contain 1 wt% of the compound 5 as the light-emitting material in the compound 4 as the host material, and a film having a thickness of 20 nm was formed. Further, Compound 6 is 10 nm as the hole blocking layer, Compound 7 is 40 nm as the electron transport layer, and Compound 7 and Compound 8 are co-deposited at a weight concentration ratio of 1: 1 as the electron injection layer so as to be 15 nm. Films were formed in order.

(C) The process which wash | cleans an organic compound layer using the liquid containing water The board | substrate with which the organic compound layer was formed into a film | membrane was air-released, and it wash | cleaned on the following conditions. In addition, this process was performed under atmospheric yellow light from the air release after forming the organic compound layer until the cleaning was completed.

Two-fluid cleaning is used for cleaning, and the conditions for the two-fluid cleaning are as follows.
・ Water flow rate 0.34L / min, nitrogen flow rate 40L / min
・ Substrate rotation speed 150rpm
・ Washing time 40 seconds

Thereafter, the substrate was rotated at 1500 rpm and spin-dried for 150 seconds. Further, the cleaned substrate was transferred to a vacuum chamber, and the organic compound layer was heated with a halogen lamp heater for 20 minutes under a reduced pressure of 1 × 10 ⁻⁴ Pa so that the substrate temperature became 120 ° C.

(D) Step of forming the upper electrode on the organic compound layer Aluminum (Al) was formed as an upper electrode by vacuum deposition at a desired position using a mask to a thickness of 100 nm.

(F) Step of forming first protective layer in contact with upper electrode and (H) Step of forming second protective layer on first protective layer Next, a protective layer made of SiN was formed. In this example, since the step of washing the first protective layer was not performed, the steps of forming the first protective layer and the second protective layer were continuously performed. (D) A SiN film having a thickness of 2 μm is formed by CVD using SiH ₄ and N ₂ as a reaction gas on the substrate that has been processed up to the step, and then a silicon nitride film is patterned by photolithography to be used for external connection. The pad electrode was exposed.

  In addition, you may replace this process with the (H) process.

  An organic light emitting device was fabricated by the above process.

(Comparative Example 1)
As Comparative Example 1, an organic light emitting device was produced by a process without the step (C) in Example 1, that is, a process without performing the step of washing the organic compound layer.

(Evaluation of non-light emitting part of organic light emitting device)
The organic light emitting devices of Example 1 and Comparative Example 1 were put in an environment of 85 ° C. and 85% humidity for 18 hours to evaluate the generation density of the non-light emitting portion. As a result, in Comparative Example 1, the generation density of non-light emitting portions was 1.5 / cm ² , whereas in Example 1, it was 0.18 / cm ² , and the organic light-emitting device fabricated in Example 1 It was confirmed that the generation density of the non-light emitting portion could be suppressed.

  This is presumably because foreign substances are removed from the organic compound layer by the cleaning process, so that it is possible to suppress the entrance of water and oxygen from the outside into the protective layer.

(Example 2)
In Example 2, there is no step (C) in Example 1, and after (D) the step of forming the upper electrode on the organic compound layer in Example 1, (E) the upper electrode is washed with a liquid containing water. An organic light emitting device was manufactured by a process including steps. Hereinafter, the steps (A), (B), (D), and (F) in this example are the same as those in Example 1.

(E) The process of washing | cleaning an upper electrode with the liquid containing water The board | substrate with which the organic compound layer and the upper electrode were formed was air-released, and it wash | cleaned on the following conditions. In addition, this process was performed under atmospheric yellow light from the opening of the atmosphere after forming the upper electrode until the cleaning was completed.

The cleaning uses two-fluid cleaning, and the conditions for the two-fluid cleaning are as follows.
・ Water flow rate 0.34L / min, nitrogen flow rate 60L / min
・ Substrate rotation speed 500rpm
・ Washing time 40 seconds

Thereafter, the substrate was rotated at 1500 rpm and spin-dried for 150 seconds. Further, the cleaned substrate was transferred to a vacuum chamber, and the organic compound layer and the upper electrode were heated for 20 minutes with a halogen lamp heater so that the substrate temperature became 120 ° C. under a reduced pressure of 1 × 10 ⁻⁴ Pa.

(Evaluation of non-light emitting part of organic light emitting device)
The organic light-emitting devices of Example 2 and Comparative Example 1 were put in an environment having a temperature of 85 ° C. and a humidity of 85% for 18 hours to evaluate the generation density of the non-light emitting portion. As a result, in Comparative Example 1, the generation density of non-light emitting portions was 1.5 / cm ² , whereas in Example 2, the number was 0 / cm ² , and in the organic light-emitting device fabricated in Example 2, It was confirmed that the generation density of the non-light emitting portion could be suppressed.

  By providing the cleaning process as in the second embodiment, the generation of dark spots (DS) and the growth expansion can be suppressed. This is presumably because foreign substances are removed from the organic compound layer and the upper electrode by the cleaning process, so that it is possible to suppress the entry of water and oxygen from the outside into the ALD protective layer.

(Confirmation of ALD protective layer of foreign matter removal part)
In order to confirm the presence / absence of defects in the ALD protective layer in the foreign matter removing portion, the organic light emitting device of Example 2 was evaluated as follows. First, the position assumed as the foreign substance removal part of an organic light emitting element was specified by the transmitted light observation of an optical microscope (Olympus MX80).

  Next, FIB processing was performed using a FIB / SEM apparatus (NOVA600 NANOLAB manufactured by FEI Co., Ltd.) so as to expose the vertical cross section at the specified position. And the SEM observation of the cross-sectional part was performed using the same apparatus. As a result, it was observed that the organic compound layer and part of the upper electrode disappeared at the position assumed to be the foreign matter removing portion, and it was specified that this was a characteristic foreign matter removal trace by cleaning. It was found that no defect was generated in the protective layer above the foreign matter removal trace, and it functioned normally as a protective layer. In addition, although the foreign matter removal trace does not emit light, since the non-emitting region is about 800 nm, it has been confirmed that there is no problem in actual use.

(Example 3)
In Example 3, there is no step (C) in Example 1, and further includes step (F), and after step (F), (G) a step of washing the first protective layer with a liquid containing water. An organic light emitting device was manufactured by the provided process. In this embodiment, the steps (A), (B), (D), and (F) are the same as those in the first embodiment.

(G) The process which wash | cleans a 1st protective layer with the liquid containing water The board | substrate with which the organic compound layer, the upper electrode, and the 1st protective layer were formed into film | membrane was air-released, and it wash | cleaned on the following conditions. In addition, this process was performed under atmospheric yellow light from the air release after forming the first protective layer until the cleaning was completed.

Two-fluid cleaning is used for cleaning, and the conditions for the two-fluid cleaning are as follows.
・ Pure water flow rate 1.5L / min, nitrogen flow rate 160L / min
・ Substrate rotation speed 500rpm
・ Cleaning time 30 seconds

Thereafter, the substrate was rotated at 1500 rpm and spin-dried for 150 seconds. Furthermore, the cleaned substrate is transferred to a vacuum chamber, and the organic compound layer, the upper electrode, and the first protective layer are formed with a halogen lamp heater so that the substrate temperature becomes 120 ° C. under reduced pressure of 1 × 10 ⁻⁴ Pa. Was heated for 20 minutes.

  The step (H) may be provided after the step (G).

Example 4
In this example, an element was produced in the same manner as in Example 3 except that the thickness of the first protective layer and the cleaning conditions for two-fluid cleaning were changed.

The film thickness of the first protective layer in this example is 200 nm. The cleaning conditions of the two-fluid cleaning are N ₂ : 100 L / min and H ₂ O: 0.35 L / min.

(Example 5)
In this example, an element was produced in the same manner as in Example 3 except that the thickness of the first protective layer and the cleaning conditions for two-fluid cleaning were changed.

The film thickness of the first protective layer in this example is 100 nm. The cleaning conditions for the two-fluid cleaning are N ₂ : 80 L / min and H ₂ O: 0.5 L / min.

(Example 6)
In this example, an element was produced in the same manner as in Example 3 except that the thickness of the first protective layer and the cleaning conditions for two-fluid cleaning were changed.

The film thickness of the first protective layer in this example is 50 nm. The cleaning conditions for the two-fluid cleaning are N ₂ : 70 L / min and H ₂ O: 0.35 L / min.

(Example 7)
In this example, an element was produced in the same manner as in Example 3 except that the thickness of the first protective layer and the cleaning conditions for two-fluid cleaning were changed.

The film thickness of the first protective layer in this example is 20 nm. The cleaning conditions for the two-fluid cleaning are N ₂ : 50 L / min and H ₂ O: 0.3 L / min.

(Example 8)
The organic light emitting device of this example has a top emission configuration. The steps other than the step (A) and the step (D) in the fourth embodiment are the same as those in the fourth embodiment. Specifically, the lower electrode was changed to Ag (100 nm) / ITO (40 nm), and the upper electrode was changed to Ag (10 nm).

(Evaluation of non-light emitting part of organic light emitting device)
The organic light emitting devices of Examples 3 to 8 and Comparative Example 1 were put in an environment of 85 ° C. and 85% humidity for 18 hours to evaluate the generation density of the non-light emitting portion. The results are shown in Table 4.

  In the device manufactured in Example 3, the generation density of the non-light-emitting portion after 18 hours in the environment of 85 ° C. and 85% humidity was suppressed as compared with Comparative Example 1. This is because by providing a cleaning step, foreign matter is removed from the substrate, as a result of the occurrence of defects in the protective layer, it is possible to suppress the entry of water from the outside, it is conceivable that.

  In addition, in the devices manufactured in Examples 4 to 7, the first protective layer preferably has a thickness of 200 nm or less because the generation density of the non-light emitting portion is further suppressed.

  In Example 8 as well, the generation density of the non-light emitting portion after 18 hours was charged in an environment of temperature 85 ° C. and humidity 85% was suppressed. In the case of the top emission configuration, an upper electrode made of a thin film metal (for example, Al, Ag, AgMg, etc.) may be used as in Example 8, and the resistance may not be sufficient for cleaning without a protective layer. In that case, it is possible to dramatically improve the cleaning resistance by forming the first protective layer.

(Heating process)
Example 9
In this example, an organic light emitting device was produced in the same process except that the process (C) in Example 1 was different.

  In this example, in the step (C), the organic compound layer was washed with a liquid containing water, and then a heating step was provided. In the heating step, the organic compound layer was heated with a halogen lamp heater for 20 minutes so that the substrate temperature was 112.5 ° C.

(Example 10)
In this example, an organic light emitting device was produced in the same manner as in Example 9 except that the substrate temperature in the heating step in Example 9 was different.

  In this example, in the heating step, the organic compound layer was heated for 20 minutes with a halogen lamp heater so that the substrate temperature was 142.5 ° C.

(Comparison between Example 9 and Example 10)
A constant current of 80 mA / cm ² was applied to the organic light emitting devices of Example 9 and Example 10 to perform a durability test. Comparing the luminance reduction rate after 200 hours, Example 9 heated at 112.5 ° C. was 9.5%, but Example 10 heated at 142.5 ° C. was 4.3%. . This is because the organic light emitting device heated to 115 ° C. or higher is considered to have improved durability characteristics because moisture is removed more. Therefore, in order to obtain better durability characteristics, it is preferable to set the substrate temperature during heating to 115 ° C. or higher.

(Comparison of electron injection materials)
(Comparative Example 2)
An organic light emitting device was produced in the same process as Example 1 except that the process (B) was different. In this comparative example, an organic light-emitting device having a layer thickness of 15 nm was obtained by co-evaporating as an electron injection layer so that cesium carbonate was 3 vol% with respect to Compound 7.

(Comparison between Example 1 and Comparative Example 2)
A constant current of 100 mA / cm ² was applied to the organic light emitting devices of Example 1 and Comparative Example 2, and the driving voltage at that time was evaluated. In Example 1, the drive voltage was 5.7V, while in Comparative Example 10, it was 6.8V. This shows that the metal complex compound in the present invention is a material that has little influence upon washing and is excellent in water resistance.

  In addition to the manufacturing steps of the above-described embodiments, (H) a step of forming an ALD protective layer on the first protective layer can provide a more reliable organic electronic device.

For example, an ALD protective layer made of Al ₂ O ₃ is formed on the upper electrode. (D) Al ₂ O ₃ is deposited to a thickness of 50 nm by an atomic layer deposition method using TMA and water vapor as a reaction gas on the substrate after the steps up to the step, and thereafter, Al ₂ O ₃ is patterned by photolithography to externally The pad electrode for connection can be exposed.

  The present invention includes a step of cleaning at least one of the organic compound layer, the upper electrode, or the first protective layer with a liquid containing water, and further includes a step of forming an ALD protective layer. As a result, it is possible to provide a method for manufacturing an organic electronic device that removes foreign substances present in the device and hardly generates a moisture or oxygen infiltration path in the ALD protective layer.

1 Substrate 2 Lower electrode 3 Organic compound layer 4 Upper electrode 5 Foreign matter 6 Liquid containing water 7 Nozzle

Claims (14)

A step of forming a lower electrode, a step of forming an organic compound layer on the lower electrode, a step of forming an upper electrode on the organic compound layer, and a first protective layer on the upper electrode. Forming an ALD protective layer on the first protective layer by an atomic layer deposition method, comprising:
An organic electron comprising a step of washing at least one of the organic compound layer, the upper electrode, and the first protective layer with a liquid containing water after the step of forming the organic compound layer. Device manufacturing method. A step of forming a lower electrode, a step of forming an organic compound layer on the lower electrode, a step of forming an upper electrode on the organic compound layer, and an atomic layer of an ALD protective layer on the upper electrode A method of manufacturing an organic electronic device having a step of forming by a deposition method,
An organic electronic device comprising: a step of washing at least one of the organic compound layer, the upper electrode, and the ALD protective layer with a liquid containing water after the step of forming the organic compound layer Production method.   The method of manufacturing an organic electronic element according to claim 1, wherein the step of cleaning with the liquid containing water is a step of cleaning the first protective layer.   4. The method of manufacturing an organic electronic element according to claim 1, wherein a thickness of the first protective layer is 20 nm or more and 200 nm or less.   3. The method of manufacturing an organic electronic device according to claim 2, further comprising a step of forming an ALD protective layer different from the ALD protective layer on the ALD protective layer by an atomic deposition method.   6. The method for manufacturing an organic electronic device according to claim 1, wherein the step of cleaning with the liquid containing water is a step of cleaning the organic compound layer with a liquid containing water. .   2. The method of manufacturing an organic electronic device according to claim 1, wherein the step of cleaning with the liquid containing water is a step of cleaning the upper electrode with a liquid containing water.   The method of manufacturing an organic electronic device according to claim 1, wherein the step of cleaning with the liquid containing water is two-fluid cleaning.   9. The method of manufacturing an organic electronic device according to claim 8, wherein the two-fluid cleaning is two-fluid cleaning with nitrogen and water.   The method of manufacturing an organic electronic device according to claim 1, further comprising a step of heating the washed layer after the step of washing with the liquid containing water.   The method of manufacturing an organic electronic device according to claim 10, wherein the heating step is a step of heating under reduced pressure.   The method of manufacturing an organic electronic device according to claim 9, wherein the heating step is performed at a temperature of 115 ° C. or higher. The organic compound layer has an organic compound and an organometallic complex,
The method for producing an organic electronic device according to any one of claims 1 to 12, wherein the organometallic complex has an organometallic complex represented by the following general formula [1].

[1]
In the formula [1], R _{1 to} R ₁₆ are each independently selected from a hydrogen atom or a substituent. The substituent is a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl. The organic compound layer that is in contact with the upper electrode and different from the light emitting layer has an organic compound and an organometallic complex,
The method for producing an organic light-emitting element according to claim 5, wherein the organometallic complex is represented by the following general formula [1].

[1]
In the formula [1], R _{1 to} R ₁₆ are each independently selected from a hydrogen atom or a substituent. The substituent is a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl.

Images