JP2006019678A - Organic electronic device and organic electronic device manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronic device and its manufacturing method which forms a layer having a charge injecting function by the wet-type film forming method to provide a high charge, injection characteristic with a charge injection barrier lowered between electrodes and the organic layer. <P>SOLUTION: The organic electronic device has two or more electrodes facing each other and at least one organic layer disposed between the two of the electrodes on a substrate. It has a layer containing a reactive organic compound and/or its reaction product between at least one electrode and the organic layer containing a charge injection transport material, or contains a reactive organic compound and/or its reaction product, in at least one electrode and/or the organic layer adjacent to the electrode containing the charge injection transport material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic electronic device and a method for producing the same, and more particularly to an organic light emitting device such as an organic electroluminescent element, an organic electronic device such as an organic transistor and an organic solar cell, and a method for producing the same.

  Organic electronic devices are expected to expand to a wide range of basic elements and applications such as organic electroluminescent elements (hereinafter referred to as organic EL elements), organic light emitting devices, organic transistors, organic solar cells, and the like.

  An organic EL element is a charge injection type self-luminous device that utilizes light emission generated when electrons and holes that have reached a light emitting layer recombine. Such an organic EL element was developed in 1987 by T.W. W. Since Tang et al. Demonstrated that an element in which a thin film composed of a fluorescent metal chelate complex and a diamine-based molecule is laminated exhibits high-luminance emission at a low driving voltage, its development has been actively conducted.

  The element structure of the organic EL element is basically composed of a cathode / organic layer / anode, and the organic layer includes a two-layer structure including a light emitting layer and a hole injection layer, or an electron transport layer and a light emitting layer. A three-layer structure composed of a hole transport layer is common. In an organic EL element, it is necessary to efficiently and quickly supply charges (holes, electrons) to a light emitting material that becomes a light emission center. For this reason, a charge transport material can be contained in the light emitting layer, A hole transport layer is provided between the light emitting layer and an electron transport layer is provided between the cathode and the light emitting layer.

  In such an organic EL element, in order to obtain high luminous efficiency, it is necessary to efficiently inject charges (holes, electrons) from the electrode to the organic layer. Has a large energy barrier and cannot easily inject charges. Therefore, conventionally, the energy barrier between the electrode and the organic layer is reduced by providing a hole or electron injection layer between the cathode and the organic layer or optimizing the work function of the anode or the cathode.

  Specifically, for example, Mg or Li having a small work function is alloyed with relatively stable Ag or Al for the cathode and used as an electrode. However, in this case, Mg and Li, which have a small work function, are easily oxidized and unstable, so that element degradation occurs due to oxidation of the electrode and the function as a wiring material must be considered. Limited in

Therefore, in order to realize a low driving voltage without using a cathode having a small work function, an electron injection layer is provided between the cathode and the light emitting layer, and an alkali metal or alkaline earth metal is provided in the electron injection layer. The use of is being considered. For example, Patent Document 1 discloses that an electron injection layer contains an alkali metal compound that is an inorganic compound such as LiF or Li ₂ O. However, alkali metal compounds, which are inorganic compounds, must have a very thin film thickness due to their insulating properties, making it difficult to form films by vapor deposition, and it is difficult to obtain devices that exhibit stable performance even when used repeatedly. Met.

  For example, Patent Document 2 discloses that the electron injection layer is made of an alkali metal or alkaline earth metal organic salt or organometallic complex, and Patent Document 3 is made of an organometallic compound containing an alkali metal. Having an electron injection layer is disclosed, and Patent Document 4 discloses having a second cathode containing a metal carboxylic acid containing an alkali metal or an alkaline earth metal. In Patent Document 5, the organic layer in contact with the cathode electrode is composed of an organometallic complex compound containing at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions, and the cathode electrode is formed of the complex. It is disclosed that a metal ion contained in a compound consists of a metal that can be reduced to a metal in a vacuum. Further, Patent Document 6 has an organic compound layer doped with a metal that functions as a donor (electron donating) dopant at the interface of the cathode electrode, thereby lowering the energy barrier in electron injection and realizing a low driving voltage. It is disclosed. However, all of these need to be formed by vacuum vapor deposition, and time is required for the manufacturing process.

  In addition to the organic EL element, an organic solar cell is a typical example of an organic electronic device using an organic material having a certain degree of carrier mobility.

  In other words, the organic solar cell uses a mechanism opposite to that of the organic EL element. That is, the most basic configuration is the same as that of the organic EL element, and is a structure in which an organic thin film having a two-layer structure is sandwiched between electrodes (see Non-Patent Document 1). An electromotive force can be obtained by utilizing a photocurrent generated by absorbing light into the organic thin film. The current flowing at this time may be considered that carriers generated by light flow using the carrier mobility of the organic material. If the charge injection barrier between the organic material and the electrode is reduced, an electromotive force can be obtained more efficiently.

  An organic transistor, which is another typical example of an organic electronic device, is a thin film transistor using an organic semiconductor material composed of a π-conjugated organic polymer or an organic small molecule in a channel region. A general organic transistor includes a substrate, a gate electrode, a gate insulating layer, source / drain electrodes, and an organic semiconductor layer. In an organic transistor, by changing the voltage (gate voltage) applied to the gate electrode, the amount of charge at the interface between the gate insulating film and the organic semiconductor film is controlled, and the current value between the source electrode and the drain electrode is changed. Perform switching.

  However, when an organic semiconductor material used in the organic transistor is used, there is a large charge injection barrier with the source electrode or the drain electrode, which causes a problem in device driving. Further, if the charge injection barrier between the organic semiconductor layer and the source electrode or the drain electrode is reduced, it is expected that the on-current value of the organic transistor is improved and the device characteristics are stabilized.

  On the other hand, the light emitting layer or the above light emitting layer is formed by a wet film formation method (spin coating method, printing method, ink jet method, etc.) in which a high molecular organic compound having light emitting property, charge transporting property, etc. is dissolved or dispersed in a solvent and applied to a substrate. An organic electronic device such as an organic EL element in which a charge transport layer or the like is formed has been proposed. The wet film-forming method that applies to the substrate using a solvent does not require a large-scale vapor deposition device compared to the vacuum vapor deposition method, can be expected to simplify the manufacturing process, have high material utilization efficiency, and low cost. There is a merit that the area of the base material can be increased. Further, there is an advantage that materials such as RGB in an organic EL element can be easily applied in parallel.

Japanese Patent Laid-Open No. 09-17574 JP 2000-91078 A Japanese Patent Laid-Open No. 2000-24369 JP 2003-303691 A JP-A-11-233262 JP-A-10-270171 “App.Phys.Lett.”, (1986), Vol.48, Number 2, p.183-185 “App.Phys.Lett.”, (2003), Vol.83, Number 23, p.4695-4697 "Preliminary Proceedings of the 50th Applied Physics Related Conference", 2003, p.1404 “Synthetic Metals”, (1997), vol.85, p.1229-1232

  In Patent Document 5, alkali metals and alkaline earth metals are generally refractory metals at a reaction temperature at which a saturated vapor pressure is higher than that of a refractory metal such as Al and oxidation and reduction reactions occur. It is known that the compound can be reduced with Al, Si, Zr, etc., and when an organometallic complex having an alkali metal or an alkaline earth metal is used for the electron injection layer, the layer containing the alkali metal or the alkaline earth metal is used. If the heat-reducible material such as Al is vacuum-deposited as a cathode electrode, and these heat-reducible materials do not reduce the metal ions contained in the organometallic complex having alkali metal or alkaline earth metal to metal in vacuum It discloses a problem that good characteristics cannot be obtained. It has also been reported that carboxylates such as benzoic acid and acetic acid containing alkali metals and alkaline earth metals are decomposed by heat and deposited as alkali metals and alkaline earth metals alone when deposited by vapor deposition. (Non-patent Document 3).

  Moreover, although the material by a nonpatent literature 2 is proposed as a coating type electron injection layer, in the literature, Al which has heat reducing property is used as a cathode on the electron injection layer, and vacuum evaporation film-forming is used. Yes. The cathode using a metal having a low workability and a high work function on the coating type electron injection layer in this document has a problem that the characteristics do not appear.

  The organic salts and organic metal complexes having alkali metals and alkaline earth metals disclosed in Patent Documents 2 to 5 and Non-Patent Document 2 are all organic salts in which oxygen is directly bonded to alkali metals or alkaline earth metals. Or a metal-organic complex, or by vacuum-depositing a heat-reducing material such as Al on the organic salt or organic-metal complex containing the alkali metal or alkaline-earth metal as a cathode electrode. There is a problem that good characteristics as an element cannot be obtained unless the metal ions contained in the organometallic complex having a metal or an alkaline earth metal are reduced to a metal in a vacuum. This is because when an organic salt or organometallic complex in which oxygen is directly bonded to an alkali metal or alkaline earth metal is used, electrons localized on the oxygen are unlikely to be emitted to neutral organic materials. Even if these organic salts and organometallic complexes are in direct contact with the organic material, charge transfer is difficult to occur between the neutral organic material and the charge injection effect is low, and it is reduced to alkali metal or alkaline earth metal. This is thought to facilitate charge transfer with a neutral organic material. For this reason, in the prior art, there are restrictions on the formation method of the electron injection layer and / or the material and formation method of the adjacent electrode, and a layer containing an alkali metal or an alkaline earth metal by a wet film formation method that does not use a vapor deposition method. And the electrode could not be formed.

  As described above, the organic EL element has been described. Similarly, in light emitting electrochemical cells (LECs) and electrochemiluminescence (ECL) (for example, Non-Patent Document 4) which are organic light emitting devices other than the organic EL element, Similarly, in organic electronic devices such as organic transistors and organic solar cells, it is important that the charge injection barrier between the electrode and the organic layer is lowered and high charge injection efficiency is achieved. It is also important to be able to produce products efficiently.

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide a layer having a charge injection function, which has a high charge injection characteristic due to a decrease in the charge injection barrier between the electrode and the organic layer. An object of the present invention is to provide an organic electronic device that can be formed by a wet film forming method, and a method for manufacturing the same.

  A first aspect of an organic electronic device according to the present invention is an organic electronic device having, on a substrate, two or more electrodes facing each other and at least one organic layer disposed between the two electrodes. A layer containing a reactive organic compound and / or a reaction product thereof is provided between at least one electrode and an organic layer containing a charge injecting and transporting material.

  Moreover, the second aspect of the organic electronic device according to the present invention is an organic electronic device comprising, on a substrate, two or more electrodes facing each other and at least one organic layer disposed between the two electrodes. The device is characterized in that a reactive organic compound and / or a reaction product thereof are contained in at least one electrode and / or an organic layer adjacent to the electrode and containing a charge injecting and transporting material.

  In the present invention, the reactivity of the reactive organic compound means the reactivity with the charge injecting and transporting material. Therefore, the reaction product in the present invention refers to a reaction product obtained by a reaction between a reactive organic compound and a charge injecting and transporting material.

  In the first aspect, the organic electronic device according to the present invention has a layer containing a reactive organic compound and / or a reaction product thereof between at least one electrode and an organic layer containing a charge injecting and transporting material. In the second aspect, at least one electrode and / or the organic layer adjacent to the electrode and containing the charge injecting and transporting material contains the reactive organic compound and / or the reaction product thereof. The charge injection and transport material generated reacts with a reactive organic compound to generate radical anions and radical cations to increase the charge density, thus reducing the charge injection barrier between the electrode and the organic layer, and injecting charges efficiently. Will be able to.

  In addition, since the organic electronic device according to the present invention can perform a good charge injection function without using a vapor deposition method when the reactive organic compound is contained, the reactive organic compound is obtained by a wet film formation method. It can be contained. Furthermore, there are no restrictions on the material and forming method of the adjacent electrodes.

  The charge injecting and transporting material is preferably an electron injecting and transporting material from the viewpoint of electron injection between the electrode for transferring electrons and the organic layer.

  The reactive organic compound may have a reducing site or a proton accepting site to reduce a neutral charge injecting and transporting material or accepting a proton from the charge injecting and transporting material, resulting in neutral charge injection. Since the transport material can be in a radical anion state, that is, a carrier, an injection barrier from the electrode is lowered, and electron injection characteristics are improved.

  The charge of the reducing site or proton accepting site of the reactive organic compound may be neutral as a reaction product of the reactive organic compound.

  The electron affinity of the reducing site or proton accepting site of the reactive organic compound is smaller than the electron affinity of the charge injecting and transporting material. This means that the reducing site of the reactive organic compound has electrons in the charge injecting and transporting material. Or a proton-accepting site of the reactive organic compound from the charge injection / transport material is easy to accept a proton, easily forms a molecule in a radical anion state, and is preferable from the viewpoint of improving electron injection characteristics.

  In the reaction product, a part of the reactive organic compound forms a charge transfer complex. Further, in the reaction product, a part of the reactive organic compound forms a charge transfer material with a charge injection / transport material. Forming a complex is preferable from the viewpoint of improving charge injection characteristics.

  The reducing site or proton accepting site of the reactive organic compound is boron compound, silicon compound, nitrogen compound, phosphorus compound, sulfur compound, selenium compound, tellurium compound, hydrocarbon cyclic compound, nitrogen-containing cyclic compound, sulfur-containing cyclic Having at least one compound selected from the group consisting of a compound, a selenium-containing cyclic compound, a tellurium-containing cyclic compound, and a condensed polycyclic compound thereof, between the reactive organic compound and the charge injecting and transporting material. This is preferable from the viewpoint that reaction easily occurs and charge injection characteristics are improved.

  The reactive organic compound is selected from the group consisting of metal amide compounds, metal cyclopentadiene compounds, cyclopentadiene compounds, phenanthroline compounds, phenanthridine compounds, naphthalene compounds, bipyridyl compounds, phenylpyridine compounds, quinoline compounds, and pyridine compounds. At least one type is preferable from the viewpoint of improving charge injection characteristics.

  The reactive organic compound preferably contains a metal element from the viewpoint of stably forming a charge transfer complex and improving electron injection characteristics.

  As one aspect of the organic electronic device according to the present invention, an organic light emitting device containing a light emitting material may be used.

  In addition, the organic light emitting device includes a plurality of light emitting units including at least one light emitting layer between an anode electrode and a cathode electrode facing each other, and the light emitting unit is partitioned by a charge generation layer. An organic device comprising a reactive organic compound and / or a reaction product in a charge generation layer and / or an organic layer adjacent to the charge generation layer and containing a charge injecting and transporting material It may be a light emitting device. In this case, by stacking a plurality of light emitting units in series, it is possible to have characteristics that high luminance, high light emission efficiency (current efficiency), and long life can be obtained.

  On the other hand, in the first aspect of the method for producing an organic electronic device according to the present invention, two or more electrodes facing each other and at least one organic layer disposed between the two electrodes are provided on a substrate. The method of manufacturing an organic electronic device includes a step of forming a layer containing a reactive organic compound between at least one electrode and an organic layer containing a charge injecting and transporting material.

  In addition, a second aspect of the method for manufacturing an organic electronic device according to the present invention includes two or more electrodes facing each other on a substrate, and at least one organic layer disposed between the two electrodes. A method for producing an organic electronic device having a step of forming a layer containing a reactive organic compound as an organic layer containing a charge injecting and transporting material adjacent to at least one electrode and / or electrode. .

  Forming the layer containing the reactive organic compound by a wet film formation method does not require a vacuum apparatus, can simplify the manufacturing process, has high material utilization efficiency, is inexpensive, and has a large substrate. It is preferable from the viewpoint that areaization is possible.

  Further, the step of forming a reaction product between the reactive organic compound and the charge injecting and transporting material is that the neutral charge injecting and transporting material reacts with the reactive organic compound to cause the electrode and the organic layer to react with each other. This is preferable because the charge injection barrier is lowered and charges can be efficiently injected.

  The organic electronic device is an organic light emitting device having a plurality of light emitting units including at least one light emitting layer between an anode electrode and a cathode electrode facing each other, wherein the light emitting units are partitioned by a charge generation layer. In addition, it is preferable to have a step of forming a layer containing a reactive organic compound as the charge generation layer and / or the organic layer adjacent to the charge generation layer, from the viewpoint that charge injection characteristics can be improved.

  In the organic electronic device according to the present invention, the charge injection barrier between the electrode and the organic layer is lowered, the charge injection characteristic is high, and a layer having a charge injection function can be formed by a wet film formation method.

  In the present invention, not only the charge injecting and transporting layer but also all other layers such as other organic layers and electrodes can be formed by using the wet film forming method, so that a large-scale vapor deposition apparatus is not required as compared with the vacuum vapor deposition method. The production process can be simplified, the material utilization efficiency is high, the cost is low, the area of the substrate can be increased, and several layers such as RGB light emitting layers in an organic EL element are arranged in parallel. Thus, an organic electronic device having good element characteristics can be obtained because it has the merit that it can be easily applied to each other and has good charge injection efficiency.

  Above all, in the case of organic light-emitting devices, formation up to the cathode, which was difficult to achieve with conventional organic light-emitting devices, can be easily and efficiently produced by a wet process, and it is also good to use a metal with a large work function in the cathode. Organic light emission characteristics can be realized. In the present invention, there is no restriction on the material and forming method of the adjacent electrode, specifically, for example, a work having no heat reducing property on the organic layer containing the reactive organic compound formed by the wet film forming method. Even if an electrode using a metal having a large function is formed or the electrode is formed by coating, charge injection into the organic layer can be efficiently performed, and good device characteristics can be obtained. Furthermore, since the present invention does not require vapor deposition of an electrode material having thermal reducibility on the charge injection material, it can be suitably used for forming an electron injection / transport layer in the case of forming an organic EL device from a cathode. The present invention can also be suitably applied to a top emission (upper surface light emitting) device that uses the cathode as a transparent electrode and extracts light from the cathode side.

  The organic electronic device manufacturing method according to the present invention includes a step of forming a layer containing a reactive organic compound between at least one electrode and an organic layer containing a charge injecting and transporting material, or a reactive organic compound. By using at least one electrode and / or forming a layer adjacent to the electrode as an organic layer containing a charge injecting and transporting material, using only a step of forming a layer by a wet film formation method. The injection function can be improved.

  A first aspect of an organic electronic device according to the present invention is an organic electronic device having, on a substrate, two or more electrodes facing each other and at least one organic layer disposed between the two electrodes. A layer containing a reactive organic compound and / or a reaction product thereof is provided between at least one electrode and an organic layer containing a charge injecting and transporting material. The layer containing the reactive organic compound and / or reaction product thereof is adjacent to the organic layer containing at least one electrode and the charge injecting and transporting material, and the organic containing at least one electrode and the charge injecting and transporting material. It is preferably formed between the layers.

  Moreover, the second aspect of the organic electronic device according to the present invention is an organic electronic device comprising, on a substrate, two or more electrodes facing each other and at least one organic layer disposed between the two electrodes. The device is characterized in that a reactive organic compound and / or a reaction product thereof are contained in at least one electrode and / or an organic layer adjacent to the electrode and containing a charge injecting and transporting material.

  In the present invention, the charge injection / transport material is a material capable of stabilizing injection of electrons and / or holes from an electrode and transporting electrons and / or holes injected from an electrode. Electrons and / or hole injection properties having a function of stabilizing injection of electrons and / or holes from an electrode when an electric field is applied, and electrons having a function of transporting electrons injected from an electrode by the force of an electric field and / or Alternatively, it may have either one of hole transportability and may have both functions of electron and / or hole injection property and electron and / or hole transportability. The charge injecting and transporting material in the present invention includes so-called light emitting materials having electron and hole transporting properties.

  As described above, the reactivity of the reactive organic compound in the present invention means the reactivity with the charge injecting and transporting material. Therefore, the reaction product in the present invention refers to a reaction product obtained by a reaction between a reactive organic compound and a charge injecting and transporting material.

  In the first aspect, the organic electronic device according to the present invention has a layer containing a reactive organic compound and / or a reaction product thereof between at least one electrode and an organic layer containing a charge injecting and transporting material. In the second aspect, at least one electrode and / or the organic layer adjacent to the electrode and containing the charge injecting and transporting material contains the reactive organic compound and / or the reaction product thereof. The charge injection and transport material generated reacts with a reactive organic compound to generate radical anions and radical cations to increase the charge density, thus reducing the charge injection barrier between the electrode and the organic layer, and injecting charges efficiently. Will be able to.

  In addition, since the organic electronic device according to the present invention can perform a good charge injection function without using a vapor deposition method when the reactive organic compound is contained, the reactive organic compound is obtained by a wet film formation method. It can be contained. Furthermore, there are no restrictions on the material and forming method of the adjacent electrodes.

  In the organic electronic device of the first aspect, the layer containing the reactive organic compound and / or the reaction product thereof is exemplified as follows between the at least one electrode and the organic layer containing the charge injection / transport material. The electrode and / or the organic layer containing the charge injecting and transporting material may be formed so as to be adjacent to the entire surface, or the island may be formed on the organic layer containing the charge injecting and transporting material, You may form between the organic layers containing a charge injection transport material. Further, the reaction product is obtained by a reaction between the reactive organic compound and the charge injecting and transporting material in contact with the reactive organic compound, and therefore contains at least one electrode and the charge injecting and transporting material. It can be contained not only between the organic layer but also in the organic layer containing the charge injecting and transporting material.

  In the organic electronic device according to the second aspect, the reactive organic compound and / or the reaction product thereof may be dispersed in an organic layer containing a charge injecting and transporting material adjacent to the electrode. Alternatively, it may be dispersed in an electrode in contact with the organic layer and diffused during driving into the organic layer. Furthermore, it may be dispersed and contained in both the electrode and the organic layer containing the charge injecting and transporting material adjacent to the electrode.

<Reactive organic compound and reaction product>
Hereinafter, first, the reactive organic compound and reaction product used in the present invention will be described.
When the objective is to lower the barrier for injecting electrons from the electrode, the reactive organic compound preferably has a reducing site or a proton-accepting site. When the reactive organic compound has a reducing site or proton accepting site, the reactive organic compound and the charge injection / transport material may react to generate a radical anion. Since the charge density of the charge injecting and transporting material increases, an organic electronic device that injects electrons efficiently can be manufactured. Even if the alkali metal etc. is not reduced by the vapor deposition of the heat-reducible material or the electron injection material itself at the time of adjacent electrode layer formation as in the past, it is between the neutral charge injection transport material Therefore, it is possible to manufacture an organic electronic device having a good electron injection function without using a vapor deposition method.

  On the other hand, when it is intended to lower the hole injection barrier from the electrode, the reactive organic compound preferably has an oxidizing site or a proton donating site. When the reactive organic compound has an oxidizing site or proton donating site, the reactive organic compound reacts with the charge injection / transport material, and the neutral charge injection / transport material may generate a radical cation. Since the charge density of the charge injecting and transporting material is increased, an organic electronic device that efficiently injects holes can be manufactured.

  The reducing site or proton accepting site, oxidizing site or proton donating site of the reactive organic compound usually has a negative charge or a positive charge, but the charge becomes neutral due to the reaction with the charge injecting and transporting material. It is preferable that In this case, the charge density of the neutral charge injection / transport material is increased, and the charge injection efficiency is improved.

  Furthermore, it is preferable that the reactive organic compound reacts and a part of the reactive organic compound forms a charge transfer complex as the reaction product. Especially, it is preferable that a part of the reactive organic compound forms the charge transfer complex with the charge injecting and transporting material in the reaction product. When a part of the reactive organic compound forms a charge transfer complex, a new energy level is formed in the charge injecting and transporting material, and the charge barrier property is reduced by lowering the injection barrier from the electrode. This is because it improves.

  As the charge transfer complex, for example, the reducing site, proton accepting site, oxidizing site or proton donating site of the reactive organic compound reacts with the neutral charge injecting and transporting material, and the reactive organic compound The reducing site or proton accepting site or oxidizing site or proton donating site of the compound is neutral in charge, and the charge injecting and transporting material is a radical anion or radical cation, and the reducing site of the reactive organic compound or Examples include those in which a part of the reactive organic compound different from a proton accepting site, an oxidizing site, or a proton donating site forms a charge transfer complex with a radical anion or radical cation of the charge injecting and transporting material. .

  In the present invention, the formation of a charge transfer complex between a part of the reactive organic compound and the charge injecting and transporting material is measured by an absorption spectrometer (for example, UV-3100PC manufactured by SHIMAZU). In the absorption spectrum, it can be confirmed that a new absorption peak different from that of the reactive organic compound or the charge injection / transport material is generated on the long wavelength side.

  In addition, the formation of a charge transfer complex is compared with the fluorescence intensity and wavelength of the emission peak of the charge injecting and transporting material in the fluorescence spectrum measured by a fluorescence spectrometer (for example, F-4500 manufactured by HITACHI). This can be confirmed by observing a decrease in the fluorescence intensity of the emission peak or a shift of the emission peak. These methods for confirming the formation of a charge transfer complex can also be used as a guideline for selecting a combination of the charge injecting and transporting material and the reactive organic compound.

i) Reactive organic compound suitable for electron injection For the purpose of lowering the barrier of electron injection from the electrode, the reactive organic compound preferably has a reducing site or a proton-accepting site. Furthermore, it is preferable that the electron affinity of the reducing site or proton accepting site of the reactive organic compound is smaller than the electron affinity of the charge injection transport material. In this case, the reducing site of the reactive organic compound is likely to donate electrons to the charge injecting and transporting material, or the proton accepting site of the reactive organic compound is likely to accept protons from the charge injecting and transporting material. This is because generation of a radical anion state, that is, charge is easily generated, so that electron injection characteristics are improved.

  Furthermore, the electron affinity of the reducing site or proton accepting site of the reactive organic compound may be within the range of 1.0 eV of the value of the electron affinity of the charge injecting and transporting material. That is, a value obtained by subtracting the electron affinity of the reducing site or proton accepting site of the reactive organic compound from the value of the electron affinity of the charge injecting and transporting material may be ± 1.0 eV or less.

  The electron affinity of the reducing site or proton accepting site of the reactive organic compound is preferably 3.5 eV or less from the viewpoint of electron donation (generation of radical anion) to the charge injection transport material, and more preferably 3 0.0 eV or less is preferable.

  The reactive organic compound is preferably used as long as it has a reducing site or a proton-accepting site, and is not particularly limited. However, an organic salt or organometallic complex having a reducing site or a proton-accepting site is preferably used. it can. In the case of an organic salt or organometallic complex, the organic salt and / or organometallic complex dissociates and ions are polarized at the electrode interface, or the organic salt and / or organometallic complex intervene at the electrode interface. By forming an electric double layer and lowering the injection barrier, electrons can be injected efficiently.

  The reducing site or proton-accepting site is not particularly limited as long as it can reduce the charge injection / transport material or accept a proton from the charge injection / transport material. It can be described as (X-R) consisting of the other part (R). The negatively chargeable moiety (X) can be directly ionically or coordinately bonded to a different part (usually a positively chargeable part) from the reducing or proton accepting part of the reactive organic compound. It is an aromatic atomic group in which atoms or π electrons are delocalized.

  The atom constituting the reductive moiety or the proton-accepting moiety (X) that can be negatively charged can be bonded to other atoms because it tends to have the property of reducing the charge injecting and transporting material. The number of atoms is preferably larger than 2, and examples thereof include non-metallic elements of Group 16, Group 14, Group 15, and Group 16 other than oxygen. Specifically, for example, B, C, N, Si, P , S, Se, Te.

  In addition, as an aromatic atomic group in which the π electrons constituting the reductive site or the proton-accepting site (X) that can be negatively charged are delocalized, the charge injecting and transporting material can be reduced. At least one selected from the group consisting of hydrocarbon cyclic compounds, nitrogen-containing cyclic compounds, sulfur-containing cyclic compounds, selenium-containing cyclic compounds, tellurium-containing cyclic compounds, and condensed polycyclic compounds thereof The compound of this is mentioned. Specific examples of the aromatic atomic group in which the π electrons constituting the negatively charged moiety (X) are delocalized include, for example, cyclopentadiene, cycloheptatrium, phenanthroline, phenanthridine, naphthalene, Bipyridyl, phenylpyridine, quinoline, pyridine, pyrrole, thiophene, selenophene, cyclooctatetraene and the like can be mentioned.

  In the case where the negatively chargeable moiety (X) is composed of an atom or an aromatic atomic group, it becomes possible to bond more with a later-described electron-donating substituent or the like. The electron density of the portion (X) to be obtained is increased, and the reducing site can easily donate electrons to the neutral charge injection / transport material, or the proton accepting site from the neutral charge injection / transport material has a proton. It is presumed that it becomes easier to accept and has an excellent electron injection function.

  Therefore, the reducing site or proton-accepting site of the reactive organic compound includes boron compound, silicon compound, nitrogen compound, phosphorus compound, sulfur compound, selenium compound, tellurium compound, hydrocarbon cyclic compound, nitrogen-containing cyclic compound, From the viewpoint of charge injection characteristics, it is preferable to have at least one compound selected from the group consisting of sulfur cyclic compounds, selenium-containing cyclic compounds, tellurium-containing cyclic compounds, and condensed polycyclic compounds thereof.

  In particular, the reducing site or proton accepting site of the reactive organic compound is preferably a nitrogen compound, a cyclopentadiene compound, a phenanthroline compound, or a phenanthridine compound.

  The other portion (R) bonded to the negatively charged portion (X) of the reducing site or the proton accepting site is not particularly limited, but the other portion (R) may be a hydrogen atom. It preferably has at least one electron donating group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, and a hydroxyl group. In the case of having an electron donating group, the electron density of the portion (X) that can be negatively charged is increased, and the reducing site or proton accepting site can easily reduce the charge injecting and transporting material. This is because the characteristics are improved. In particular, it is preferable that the electron donating group is directly bonded to the portion (X) that can be negatively charged.

  Note that the alkyl group and aryl group include an alkoxy group, a hydroxyl group, and the like to which a substituent is further bonded. Examples of the alkyl group include a chain-like and branched-chain alkyl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Examples thereof include a tert-butyl group. An arylated alkyl group in which a hydrogen atom of an alkyl group is substituted with an aryl group is also included in the alkyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a tolyl group, a biphenyl group, and a triphenyl group. An alkylated aryl group in which the hydrogen atom of the aryl group is substituted with an alkyl group is also included in the aryl group. Examples of the alkoxy group include chain-like and branched-chain alkoxy groups. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group. And tert-butoxy group.

  The other part (R) bonded to the negatively charged part (X) of the reducing part or proton accepting part may be a low molecule or a polymer. . In the case of a low molecule, when the other part (R) is composed of the electron donating group, a case where it is composed of a low molecular material having the electron donating group is exemplified. Examples of the case where the other part (R) is a polymer include an embodiment in which a part (X) that can be negatively charged is bonded to the main chain, side chain, or branch chain of the polymer. The polymer includes a medium molecule such as a so-called dendritic multibranched molecular material (dendrimer), and the branch chain surrounds the core molecule three-dimensionally in the dendritic multibranched molecular material (dendrimer). A branched chain.

  The reducing site or proton accepting site is such that the other part (R) contains a charge injecting and transporting material, that is, the reducing site or proton accepting site of the reactive organic compound and the charge injecting and transporting material. It may have a structure in which materials are bonded.

  On the other hand, of the reactive organic compound suitable for electron injection, a part different from the reducing site or the proton accepting site is preferably a portion that can be positively charged. In this case, it becomes possible to form a charge transfer complex between the portion that can be positively charged and the reduced charge injecting and transporting material. From the viewpoint of stably forming a charge transfer complex and an electron injection function, the reactive organic compound preferably contains a metal element as a part different from the reducing site or the proton accepting site, It is preferable to include a metal element that can be a monovalent, divalent, or trivalent cation.

  The reactive organic compound suitable for electron injection preferably contains a metal having a low work function from the viewpoint of charge transfer complex formation, and contains a metal having a work function of 4.2 eV or less, and further containing a metal of 3.5 eV or less. Is preferred.

  On the other hand, from the viewpoint of easy handling, the reactive organic compound suitable for electron injection may contain a metal having a high work function such as a transition metal. This is because a reactive organic compound having a low work function is highly reactive with moisture and must be handled in an inert gas, but a metal having a high work function such as a transition metal can be handled stably in the atmosphere.

  Accordingly, the reactive organic compound suitable for electron injection preferably contains at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth elements, and transition metals.

  Examples of the alkali metal include Li, Na, K, Rb, and Cs. Examples of the alkaline earth metal include Mg, Ca, Sr, and Ba. Examples of rare earth elements include Sc, Y, and lanthanoid elements. Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.

  From the above, reactive organic compounds suitable for electron injection are metal amide compounds, metal cyclopentadiene compounds, cyclopentadiene compounds, phenanthroline compounds, phenanthridine compounds, naphthalene compounds, bipyridyl compounds, phenylpyridine compounds, quinolines among the above. It is preferable from the point which is at least 1 type selected from the group which consists of a compound and a pyridine compound from the point which is excellent in an electron injection function.

  The metal amide compound is a compound in which one hydrogen atom of ammonia or amine is substituted with a metal atom. In the case of a metal amide compound, the reducing site or proton accepting site is a nitrogen compound corresponding to the moiety (X) where N (nitrogen) can be negatively charged.

  Any derivative may be used as long as it is a metal amide compound, and any of the above moieties (R) bonded to nitrogen (X) can be used. Suitable electron donating groups possessed by the other moiety (R) include a hydrogen atom, an alkyl group, an aryl group and the like. Among these, an alkyl group and an aryl group are preferable because they can be dissolved in an organic solvent and have excellent organic salt stabilization and electron injection functions. Preferable metal amide compounds include those in which two alkyl groups and aryl groups are substituted with nitrogen. In addition, an alkyl group or an aryl group may be further bonded with an electron donating group such as an alkoxy group or a hydroxyl group. Further, the above polymer may be bonded to nitrogen directly or through a substituent such as an alkyl group or an aryl group.

  In particular, the metal amide compound is preferably an amide compound containing an alkali metal, an alkaline earth metal, or a rare earth element metal from the viewpoint of an electron injection function (charge transfer complex formation).

  Specific examples of the metal amide compound include lithium dialkylamides such as lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, and lithium dibutylamide, potassium dialkylamides such as potassium dimethylamide, potassium diethylamide, and potassium diisopropylamide. Examples thereof include sodium dialkylamides such as amide, sodium dimethylamide, sodium diethylamide and sodium diisopropylamide, rubidium dialkylamide, cesium dialkylamide and the like.

  The metal cyclopentadiene compound is a compound containing a metal and cyclopentadiene. In the case of a metal cyclopentadiene compound, the reducing site or proton accepting site is a cyclic hydrocarbon compound corresponding to the moiety (X) where cyclopentadiene can be negatively charged. The metal cyclopentadiene compound also includes a sandwich type compound in which a metal is sandwiched between at least two cyclopentadiene. The metal of the sandwich compound is not particularly limited. Examples of the sandwich compound include bis (cyclopentadienyl) cobalt, bis (cyclopentadienyl) vanadium, bis (cyclopentadienyl) magnesium, and bis ( And cyclopentadienyl) barium, bis (cyclopentadienyl) calcium, bis (cyclopentadienyl) hafnium, bis (cyclopentadienyl) chromium, and bis (cyclopentadienyldienyl) iron.

  (R) bonded to cyclopentadiene, which can be negatively charged moiety (X), may be a hydrogen atom, and cyclopentadiene can also be suitably used, but a compound in which R other than a hydrogen atom is bonded to cyclopentadiene. Can also be used favorably as a reducing site or proton accepting site. As R other than a hydrogen atom, an alkyl group is preferably used, and the number of alkyl groups bonded to cyclopentadiene is preferably large from the viewpoint of electron donating properties. Specific examples of the reducing site or proton accepting site include tetramethylcyclopentadiene, tetraethylcyclopentadiene, isopropylpentadiene, tert-butylcyclopentadiene and the like.

  In particular, the metal cyclopentadiene compound is preferably a metal cyclopentadiene compound containing an alkali metal, an alkaline earth metal, a rare earth metal, or a transition metal from the viewpoint of an electron injection function.

  Among metal cyclopentadiene compounds, those having an excellent electron injection function include, for example, cyclopentadienyl lithium derivatives such as tetramethylcyclopentadienyl lithium, tertbutylcyclopentadienyl lithium, and tetramethylcyclopentadienyl sodium. , Cyclopentadienyl sodium derivatives such as isopropylcyclopentadienyl sodium, cyclopentadienyl potassium derivatives such as tetramethylcyclopentadienyl potassium, bis (cyclopentadienyl) barium derivatives, tris (cyclopenta Dienyl) erbium derivatives, tris (cyclopentadienyl) cerium derivatives, tris (cyclopentadienyl) yttrium derivatives, tris (cyclopentadienyl) gadolinium, tris (cyclo And pentadienyl) europium derivatives and tris (cyclopentadienyl) samarium derivatives.

  The metal cyclopentadiene compound has been described above, but cyclic compounds such as cycloheptatrium, phenanthroline, phenanthridine, naphthalene, bipyridyl, phenylpyridine, quinoline, pyridine, pyrrole, thiophene, selenophene, and cyclooctatetraene are Since it becomes a metal ligand like pentadiene, for example, (naphthalene) calcium derivatives, (phenanthroline) yttrium derivatives, (phenanthroline) europium derivatives, (phenanthroline) samarium derivatives, (phenanthridine) calcium derivatives, (phenanthridine) ) Similar organometallic compounds using the above cyclic compounds as ligands instead of cyclopentadiene, such as yttrium derivatives, are suitable as reactive organic compounds suitable for electron injection Used.

ii) Reactive organic compounds suitable for hole injection When the objective is to lower the hole injection barrier from the electrode, the reactive organic compound may have an oxidizing site or a proton donating site. preferable. Furthermore, the electron affinity of the oxidizing site or proton donating site of the reactive organic compound is preferably within the range of 1.0 eV of the ionization potential value of the charge injection transport material. That is, the value obtained by subtracting the electron affinity of the oxidizing site or proton donating site of the reactive organic compound from the value of the ionization potential of the charge injection transport material is preferably ± 1.0 eV or less. In this case, the oxidizing site of the reactive organic compound easily accepts electrons from the charge injection / transport material, or the proton donating site of the reactive organic compound easily donates protons to the charge injection / transport material. This is because the hole injection characteristics are improved by the formation of the charge transfer complex.

  The electron affinity of the oxidizing site or proton donating site of the reactive organic compound is preferably 4.5 eV or more, more preferably 5.0 eV or more, from the viewpoint of electron transfer and charge transfer complex formation. preferable.

  The reactive organic compound suitable for hole injection can be applied the same concept as the reactive organic compound suitable for electron injection as described above.

  The reactive organic compound is preferably used as long as it has an oxidizing site or a proton donating site, and is not particularly limited. However, an organic salt or an organometallic complex having an oxidizing site or a proton donating site is preferably used. it can.

  The oxidizing site or the proton donating site is not particularly limited as long as it is a site that can oxidize the charge injection / transport material or donate a proton to the charge injection / transport material. It can be described as (YR ′) consisting of other portions (R ′). The positively chargeable moiety (Y) can be directly ionically or coordinately bonded to a part (usually a negatively charged part) different from the oxidizing or proton donating part of the reactive organic compound. It is an aromatic atomic group in which atoms or π electrons are delocalized.

  The atoms constituting the positively chargeable portion (Y) are group 13, group 14, group 15, and group 16 other than oxygen, since the charge injecting and transporting material is likely to be oxidized. Nonmetallic elements can be mentioned, and specific examples include B, C, N, Si, P, S, Se, and Te. Similarly, aromatic atomic groups in which π electrons constituting the positively chargeable portion (Y) are delocalized include hydrocarbon cyclic compounds, nitrogen-containing cyclic compounds, sulfur-containing cyclic compounds, and selenium-containing cyclic groups. Examples thereof include at least one compound selected from the group consisting of compounds, tellurium-containing cyclic compounds, and condensed polycyclic compounds thereof.

  The other portion (R ′) bonded to the positively chargeable portion (Y) is not particularly limited, but the other portion (R ′) includes a cyano group, a nitro group, a sulfo group, and a group 17 It preferably has at least one electron-accepting group selected from the group consisting of substituents containing elements.

  The other portion (R ′) bonded to the positively chargeable portion (Y) may be a low molecule or a polymer, and the same concept as in the above (R) is used. Applicable.

  On the other hand, among the reactive organic compounds suitable for hole injection, a part different from the oxidizing part or the proton donating part is preferably a part that can be negatively charged. In this case, it is possible to form a charge transfer complex between the portion that can be negatively charged and the oxidized charge injecting and transporting material. The reactive organic compound is selected from the group consisting of halogens and halogen compounds as a part different from the oxidizing site or proton donating site from the viewpoint of stably forming a charge transfer complex and hole injection function. It is preferable to contain at least one kind.

Examples of the halogen include F, Cl, Br, and I, and examples of the halogen compound include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , AsCl ₆ ⁻ , SbF ₆ ^{− and the} like.

Reactive organic compounds suitable for hole injection include, for example, arylamine derivatives such as triphenylammonium, trisbromophenylammonium, trischlorophenylammonium, trisfluorophenylammonium and the like, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and AsCl. Examples thereof include organic salts composed of combinations of ₆ ⁻ , SbF _{6 and the} like.

  Since the reactive organic compound used in the present invention as described above has the structure as described above, many of them are soluble in a solvent, and in that case, a layer can be formed using a wet film forming method.

I. Organic Light-Emitting Device Next, among the organic electronic devices according to the present invention, an organic light-emitting device characterized by containing a light-emitting material will be described below. An organic EL element will be described in detail as a specific example of the organic light emitting device, but the organic light emitting device in the present invention is not limited to the organic EL element, and light emitting electro that is an organic light emitting device other than the organic EL element. The present invention can also be applied to chemical cells (LECs) and electrochemiluminescence (ECL).

  The organic light-emitting device according to the first aspect of the present invention is an organic light-emitting device having, on a substrate, two opposing electrodes and an organic layer including at least one light-emitting layer between the two electrodes, It is characterized by having a layer containing a reactive organic compound and / or its reaction product between at least one electrode and an organic layer containing a charge injecting and transporting material.

  The organic light-emitting device according to the second aspect of the present invention is an organic light-emitting device having two electrodes facing each other and an organic layer including at least one light-emitting layer between the two electrodes on a substrate. The organic layer containing the charge injecting and transporting material adjacent to at least one electrode and / or the electrode contains a reactive organic compound and / or a reaction product thereof.

1 to 3 are schematic cross-sectional views showing examples of the layer structure of the organic EL element according to the present invention.
As shown in FIG. 1, an embodiment of the organic EL device of the present invention includes a hole injecting and transporting layer 3 that is an organic layer, light emission between an anode electrode 2 and a cathode electrode 6 formed on a substrate 1. The layer 4 and the electron injecting and transporting layer 5 are provided in this order.

  In another embodiment of the organic EL device of the present invention, as shown in FIG. 2, a light emitting layer 4 that is an organic layer is provided between an anode electrode 2 and a cathode electrode 6 formed on a substrate 1. It is provided.

  Furthermore, as shown in FIG. 3, another embodiment of the organic EL element includes an electron injecting and transporting layer 5 that is an organic layer, light emission between a cathode electrode 6 and an anode electrode 2 formed on a substrate 1. The layer 4 and the hole injection / transport layer 3 are provided in this order.

  In the organic light-emitting device according to the present invention, a layer containing a reactive organic compound and / or a reaction product thereof between at least one electrode and an organic layer containing a charge injecting and transporting material, which is the first aspect. Typically, in the case where the layer structure as shown in FIGS. 1 and 3 is employed, the hole injection / transport layer 3 and / or the electron injection / transport layer 5 are reactive between the electrode and the light emitting layer. As a result, the hole injection / transport layer 3 and / or the electron injection / transport layer 5, the interface between the hole injection / transport layer 3 and / or the electron injection / transport layer 5 and the light emitting layer 4, and further holes A case where a reaction product is contained at the interface between the injection transport layer 3 and / or the electron injection transport layer 5 and the cathode electrode 6 is mentioned.

  In the organic light-emitting device according to the present invention, a reactive organic compound and / or a reaction product thereof is formed in the second embodiment, at least one electrode and / or an organic layer adjacent to the electrode and containing a charge injecting and transporting material. First, in the case of taking a layer structure as shown in FIGS. 1, 2, and 3, the anode electrode 2 and / or the cathode electrode 6 contains a reactive organic compound. A reactive organic compound or an interface between the hole injecting and transporting layer 3 and / or the electron injecting and transporting layer 5 and the light emitting layer 4 and the hole injecting and transporting layer 3 and / or the electron injecting and transporting layer 5 and the light emitting layer 4 adjacent to the electrode The case where a reaction product is contained is mentioned.

  Furthermore, as a second embodiment, when the layer structure as shown in FIG. 2 is adopted, the light emitting layer 4 contains a reactive organic compound, and as a result, a reaction product is contained at the interface between the light emitting layer 4 and the electrode. There are cases.

  As a second embodiment, in the case of taking the layer structure as shown in FIGS. 1 and 3, the hole injection transport layer 3 and / or the electron injection transport layer 5 contains a reactive organic compound in the charge injection transport material. As a result, at the interface between the electrode and the hole injection / transport layer 3 and / or the electron injection / transport layer 5, or at the interface between the hole injection / transport layer 3 and / or the electron injection / transport layer 5 and the light emitting layer 4, The case where a reaction product is contained is mentioned. Note that this case also corresponds to the first aspect.

  Among these embodiments, a form in which a reaction product such as a charge transfer complex is formed at the electrode interface is preferable from the viewpoint of the charge injection function.

  In addition, the said structure is an illustration of the organic EL element which concerns on this invention, Comprising: It is not limited to these.

Hereinafter, each configuration of the organic EL element will be described.
1. Organic Layer The organic layer in the organic EL device according to the present invention is formed between the anode electrode 2 and the cathode electrode 6 described later.

  The organic layer constituting the organic EL device of the present invention is composed of one or more layers including at least the light emitting layer 4. Examples of the layer formed in the organic layer other than the light emitting layer include charge injection / transport layers such as the electron injection / transport layer 5 and the hole injection / transport layer 3.

(1) Light-Emitting Layer The light-emitting layer 4 that is an organic layer is a layer having a function of emitting light by providing a field for recombination of electrons and holes. The light emitting material is not particularly limited as long as it is a commonly used material, and examples thereof include a dye light emitting material, a metal complex light emitting material, and a polymer light emitting material. As described above, the light emitting material can be used as the charge injecting and transporting material in the present invention. The light emitting layer may further contain the reactive organic compound of the present invention and / or a reaction product thereof.

  When the light emitting layer further contains a reactive organic compound, the reactive organic compound is added to the main chain, side chain, or branch chain in addition to the reactive organic compound dispersed in at least one kind of light emitting material. The light emitting material may be contained.

  Examples of dye-based light-emitting materials include cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, Examples thereof include pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

  Examples of the metal complex light emitting material include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethylzinc complex, porphyrin zinc complex, europium complex, etc. Or a metal complex having a rare earth metal such as Tb, Eu, or Dy and having a oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, or the like as a ligand.

  Examples of the polymer light-emitting material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinylcarbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, and co-polymers thereof. A coalescence etc. can be mentioned.

An additive such as a doping agent may be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of the doping agent include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, fluorene derivatives, and the like. Can do. As the dopant, for example, an organic compound having the following structural formula may be used. For example, Ir (ppy) ₃ , (ppy) ₂ Ir (acac), Ir (BQ) ₃ , (BQ) ₂ Ir (acac), Ir (THP) ₃ , (THP) ₂ Ir (acac), Ir (BO) ) ₃ , (BO) ₂ (acac), Ir (BT) ₃ , (BT) ₂ Ir (acac), Ir (BTP) ₃ , (BTP) ₂ Ir (acac), mainly PtOEP However, organometallic complexes exhibiting phosphorescence can be used. Among them, Ir (ppy) ₃ is a compound that is effective as a constituent component of a low molecular carrier transport material or an organic light emitting layer.

  In the present invention, any of a low molecular compound or a high molecular compound that emits fluorescence or a low molecular compound or a high molecular compound that emits phosphorescence can be used as the light emitting material. When a light emitting layer is formed by a wet film formation method, a high molecular compound containing a fluorescent light emitting polymer compound or a low molecular compound emitting fluorescent light, a high molecular compound containing phosphorescent light emitting material or a low molecular compound emitting phosphorescent light Can be suitably used.

  The thickness of the light emitting layer is not particularly limited as long as it can provide a function of emitting light by providing a recombination field of electrons and holes, and can be, for example, about 1 nm to 200 nm. .

  Moreover, in the embodiment of the organic EL device of the present invention, it is possible to combine light emitting layers that emit different colors, and patterning is required when creating full-color and multi-color displays.

  The method for forming the light-emitting layer is not particularly limited as long as high-definition patterning is possible, and the light-emitting layer can be formed by a dry process such as a wet film formation method or a vapor deposition method. Examples of wet film forming methods include spin coating, casting, dipping, bar coating, blade coating, roll coating, gravure coating, flexographic printing, and spraying using a melt, solution, or mixed solution of materials. Examples of the coating method include a coating method and a die coating method, and a patterning method such as printing and ink jet. Among these, a spin coating method and an ink jet method are preferably used. In the present invention, it is preferable to form the light emitting layer using the wet film forming method in order to enjoy the advantages of the wet film forming method.

(2) Electron Injection / Transport Layer The electron injection / transport layer 5 is a layer that can stabilize the injection of electrons from the cathode electrode 6 or can stably transport the injected electrons into the light emitting layer 4. is there. An electron injection layer having a function of stabilizing injection of electrons from the cathode electrode 6 when an electric field is applied, and an electron transport layer having a function of transporting electrons injected from the cathode electrode 6 into the light emitting layer 4 by the force of the electric field It may be a case of having either of these, and may have the functions of both an electron injection layer and an electron transport layer. The electron injecting and transporting layer may consist of one layer or a plurality of layers. The electron injection / transport layer 5 is formed between the light emitting layer 4 and the cathode 6, for example, as shown in FIGS.

  In the present invention, when the embodiment of the layer configuration having the electron injecting and transporting layer 5 as shown in FIGS. 1 and 3 is taken, the electron injecting and transporting layer 5 may contain at least the reactive organic compound. From the viewpoint of excellent electron injection function and improved light emission characteristics. However, in the present invention, when the reactive organic compound is used only on the hole injecting and transporting side, the electron injecting and transporting layer 5 is formed using a conventionally used electron injecting and transporting material.

  The electron injecting and transporting layer 5 in the case where the reactive organic compound is included may be a layer formed using only the reactive organic compound, but the reactive organic compound is contained in another electron injecting and transporting material. It may be dispersed, or may contain a material in which the reactive organic compound is added to the main chain, side chain, or branch chain of another electron injecting and transporting material. Further, a layer formed by using the reactive organic compound alone and a layer made of another electron injecting and transporting material may be laminated.

  In the electron injecting and transporting layer 5, two or more kinds of the reactive organic compounds may be contained. When the electron injecting and transporting layer 5 contains two or more types of the reactive organic compounds, the electron injecting and transporting layer 5 may be formed as a laminate in which the two or more types of the reactive organic compounds are included in separate layers, or It may be formed as a mixed layer of the two or more reactive organic compounds.

  In addition, when it forms as a laminated body of the said 2 or more types of reactive organic compound, in the electron injection transport layer 5, the metal contained in the 2 or more types of said reactive organic compound is made into the work function of the cathode electrode 6. The light emitting layer 4 is appropriately selected from metals having a work function between LUMOs of the light emitting layer 4 so that the work functions and LUMO values do not overlap with each other, and two or more metals are selected from the cathode 6 side to the light emitting layer 4 which is an organic layer. In order to reduce the value of the work function of the metal, the layers are arranged so as to be fixed and stacked on different layers, and the energy levels of the metals having different work functions, etc. It is preferable to supplement a large energy gap between the cathode 6 and the light emitting layer 4 so as to be stepped.

  As the electron injection transport material, any material can be used without particular limitation as long as it can stably transport electrons injected from the cathode into the light emitting layer. It is preferable to select a material that can be used. In particular, examples of the material for forming the organic electron injecting and transporting layer include substances that easily form a stable radical anion state such as oxadiazoles, aluminum quinolinol complexes, and phenanthrolines. Specific examples include 1,3,4-oxadiazole derivatives, 1,2,4-triazole derivatives, imidazole derivatives, BCP (basocupron), Bpehn (vasophenanthroline), and the like.

  In the present invention, the electron injecting and transporting layer 5 includes the reactive organic compound, and the reactive organic compound is dispersed in another electron injecting and transporting material even when the reactive organic compound is used alone. Even when it is formed or added to the electron injecting and transporting material, it is preferably formed by a wet film forming method. As the wet film formation method, a method similar to that described in the light-emitting layer can be used.

  The solvent used for dissolving and dispersing the reactive organic compound and / or the other electron injecting and transporting material to form a solution is not particularly limited as long as it does not dissolve the lower organic layer. When the lower organic layer is formed with an aromatic solvent, the charge injecting and transporting layer can use an alcohol solvent, and when the lower organic layer is formed with water or an alcohol solvent, The charge injecting and transporting layer is preferably formed using an aromatic solvent.

  In addition, when the said reactive organic compound contains in the cathode electrode 6, the electron injection transport layer 5 should just contain the charge injection transport material at least, In this case, the electron injection transport layer 5 is the above-mentioned An electron injecting and transporting layer formed using another electron injecting and transporting material may be used.

  The film thickness of the electron injecting and transporting layer 5 is preferably from 0.1 nm to 100 nm, particularly preferably from 0.1 nm to 50 nm, from the viewpoint of electron injection efficiency.

  In particular, when the electron injecting and transporting layer 5 is a layer made of the reactive organic compound, the thickness is preferably 0.1 nm to 30 nm, and more preferably 0.1 nm to 10 nm.

  Further, whether the electron injection / transport layer 5 is a layer in which the reactive organic compound is dispersed in another electron injection / transport material or another electron injection / transport material added with the reactive organic compound, Or when it is a laminated body of the layer which contains the layer which consists of the said reactive organic compound, and another electron injection transport material, it is preferable that it is 0.1 nm-300 nm, and also it is preferable that it is 0.1 nm-100 nm. .

(3) Hole Injecting and Transporting Layer The hole injecting and transporting layer 3 can stabilize the injection of holes from the anode electrode 2 or stably transport the injected holes into the light emitting layer 4. It is a layer. A hole injection layer having a function of stabilizing injection of holes from the anode electrode 2 when an electric field is applied, and a function of transporting holes injected from the anode electrode 2 into the light emitting layer 4 by the force of the electric field. One of the hole transport layers may be provided, and the functions of both the hole injection layer and the hole transport layer may be provided. The hole injecting and transporting layer may consist of one layer or a plurality of layers. The hole injecting and transporting layer 3 is formed between the light emitting layer 4 and the anode electrode 2, for example, as shown in FIGS.

  In the present invention, when the embodiment of the layer configuration having the hole injection / transport layer 3 as shown in FIG. 1 or FIG. 3 is taken, the hole injection / transport layer 3 contains at least the reactive organic compound. Is preferable from the viewpoint of excellent hole injection function and improved light emission characteristics. However, in the present invention, when the reactive organic compound is used only on the electron injecting and transporting side, the hole injecting and transporting layer 3 is formed using a conventionally used hole injecting and transporting material.

  The aspect in which the hole injecting and transporting layer 3 includes the reactive organic compound is the same as the aspect in which the electron injecting and transporting layer 5 includes the reactive organic compound.

  The hole injecting and transporting material different from the reactive organic compound is not particularly limited as long as it is a material that can stably transport holes injected from the anode into the light emitting layer. For example, in addition to the compounds exemplified as the light emitting material for the light emitting layer, oxides such as phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, amorphous carbon, polyaniline, polythiophene And derivatives such as polyphenylene vinylene. Specifically, bis (N- (1-naphthyl-N-phenyl) benzidine (α-NPD), 4,4,4-tris (3-methylphenylphenylamino) triphenylamine (MTDATA), poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS), polyvinyl carbazole (PVCz), or the like can be used.

  As the method for forming the hole injecting and transporting layer, in the present invention, it is preferable to use the wet film forming method in order to enjoy the merits of the wet film forming method.

  The film thickness of the hole injecting and transporting layer 3 is preferably from 0.1 nm to 200 nm, particularly preferably from 0.1 nm to 100 nm, from the viewpoint of hole injection efficiency.

  In particular, when the hole injection transport layer 3 is a layer made of the reactive organic compound, the thickness is preferably 0.1 nm to 30 nm, and more preferably 0.1 nm to 10 nm.

  The hole injection / transport layer 3 is a layer in which the reactive organic compound is dispersed in another hole injection / transport material or a layer containing another hole injection / transport material added with the reactive organic compound. Or in the case of a laminate of a layer made of the reactive organic compound and a layer containing another hole injecting and transporting material, the thickness is preferably 0.1 nm to 300 nm, more preferably 0.1 nm to 100 nm. Preferably there is.

2. Electrode (1) Cathode electrode The cathode electrode 6 acts to inject electrons into the light emitting layer 4. The cathode electrode 6 needs to be formed of a transparent material when the light emitted from the light emitting layer 4 is extracted from the cathode side. In the present invention, since the reactive organic compound is used, the cathode electrode 6 has a good electron injection effect without using an alkali metal, an alkaline earth metal, or a rare earth element. The method is not limited.

  The cathode electrode 6 may contain the reactive organic compound as described above.

  In the present invention, the cathode electrode 6 is formed by a vacuum deposition method using a metal or a metal oxide usually used for forming an electrode of an organic EL element, and a stable metal having a work function of 4.2 eV or more. However, it can be suitably formed by a wet film formation method. This is because by using the reactive organic compound, excellent electron injection efficiency can be obtained without forming the cathode electrode 6 by a vacuum vapor deposition method using a thermally reducing material. When the cathode electrode 6 is formed by a wet film-forming method, a large-scale vapor deposition apparatus is not required as compared with the vacuum vapor deposition method, the production process can be simplified, the material utilization efficiency is high, and the cost is low. The substrate can have a large area, which is preferable.

  There is no particular limitation on the electrode material in the case of forming by a wet film forming method as long as the wet film forming method can be used. Metal fine particles, metal oxide fine particles, alloys containing low melting point metals and low melting point metals, conductive materials And high molecular weight polymers.

  As for the metal fine particles and metal oxide fine particles, electrodes can be formed by a wet film forming method using gravure printing or screen printing by dispersing metal fine particles or metal oxide fine particles in a solvent or a solvent and a binder. The metal fine particles and metal oxide fine particles are not particularly limited as long as they are fine particles, but metals that are difficult to oxidize are preferable because they are used as electrodes. Here, the fine particles are those having a particle size of 10 μm or less, and more preferably 1 μm or less. Furthermore, the nanoparticle of 100 nm or less which is a nanoparticle is preferable. This is because the smaller the particle size of the metal fine particles, the better the contact area with the organic layer and the bondability with the organic layer. However, if the particle size is too small, the nanoparticles will diffuse into the organic layer and cause leakage current. If the metal particle size is too large, the contact area with the organic layer will be small and good charge injection will occur. Since there is a possibility that it cannot be performed, the particle size is preferably about 5 nm to 1 μm.

  The metal fine particles and metal oxide fine particles may be mixed and laminated with particles having different particle diameters. For example, the organic layer interface may have a small particle size, and a large particle size may be stacked thereon. In addition, it is preferable to mix particles having different particle diameters because the contact between the particles and the contact area with the organic layer are improved.

  The metal fine particles and metal oxide fine particles are preferably made of at least one metal and containing at least a metal having a work function of 4.2 eV or more. This is because by using 4.2 eV or more, durability against oxidation as an electrode is improved, the stability of the electrode is increased, and element deterioration is less likely to occur. Examples of metals having a work function of 4.2 eV or more include Ag, Al, Au, Be, Bi, Co, Cr, Cu, Fe, Ga, Ir, Mo, Nb, Ni, Os, Pb, Pd, Pt, Sb, Sn, Ti, V, W etc. are mentioned.

  Examples of the metal oxide fine particles include ITO fine particles, IZO fine particles, and titania. Further, fine particles obtained by coating alloy fine particles, metal fine particles or metal oxide fine particles with metal as the metal fine particles and metal oxide fine particles may be used. Alternatively, the electrode may be formed by mixing and laminating a plurality of metal fine particles or metal oxide fine particles.

  The solvent for dispersing the metal fine particles and metal oxide fine particles is not particularly limited, but a solvent that does not dissolve the lower organic layer is preferable, and examples thereof include water, ethanol, isopropanol, benzene, toluene, and mixed solvents thereof. Can do.

  Examples of the binder for dispersing the metal fine particles and metal oxide fine particles include tetramethoxysilane, tetraethoxysilane, a conductive polymer described later, and an insulating polymer (polystyrene, PMMA).

  When the cathode electrode 6 is made of a molten metal or a molten alloy containing one or more metals selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium, it is formed by a wet film forming method. It is possible and preferred. One or more metals selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium or alloys containing these metals have a low melting point, and therefore are melted at a low temperature and coated on the organic layer. This is because the electrode layer can be densely formed. The melting point of the metal is not particularly limited as long as the organic layer does not deteriorate and denature, but it is preferable to form the electrode using a material having a melting point of 150 degrees or less. Further, by using these molten metals, the electrode becomes a mirror surface, and light generated in the organic layer is reflected by the mirror surface electrode, so that the light emission efficiency is improved. The melting point of the alloy can be changed and adjusted by arbitrarily changing the ratio of two or more metals. The metal used for the specific alloy is not particularly limited as long as it has a work function of 4.2 eV or more, and examples include alloys containing Zn, Ni, etc. in addition to bismuth, gallium, tin, lead, silver, and indium. .

  When the cathode electrode 6 is made of a binder containing one or more metals selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium, it can be formed by a wet film forming method. Possible and preferred. In this case, one or more metals selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium are dispersed in the binder in the form of fine particles or paste. The binder is preferably a conductive polymer described later.

  Further, the cathode electrode 6 has a mixed or laminated structure of molten metal or molten alloy containing one or more metals selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium and the metal fine particles. Good. Further, the cathode electrode 6 may have a mixed or laminated structure of a polymer material containing one or more metals selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium and the metal fine particles.

  On the other hand, examples of the conductive polymer include polyalkylthiophene derivatives, polyacetylene derivatives, polypyrrole derivatives, polyaniline derivatives, polythiophene derivatives, polysilane derivatives, and the like. The conductive polymer can be appropriately dissolved and dispersed in a solvent, and an electrode can be formed by a wet film formation method.

  The thickness of the cathode electrode 6 is preferably in the range of 50 nm to 50 μm, although it depends on the material. If the thickness of the cathode electrode 6 is less than 50 nm, the conductivity may be insufficient and the function as an electrode may not be exhibited.

(2) Anode electrode When light is extracted from the substrate 1 side, the anode electrode 2 must be formed of a transparent material. The anode electrode 2 provided on the light emitting layer side of the substrate 1 acts to inject holes into the light emitting layer 4.

  As described above, the anode electrode 2 may contain the reactive organic compound.

  The anode 2 constituting the organic EL element of the present invention is not particularly limited as long as it is made of a conductive material. For example, a metal such as Au, Ta, W, Pt, Ni, Pd, Cr, Cu, and Mo is used. Or an oxide or alloy thereof, or a laminated structure of these metal materials. Furthermore, conductive inorganic oxides such as In—Sn—O, In—Zn—O, Zn—O, Zn—O—Al, and Zn—Sn—O, α-Si, α-SiC, and the like can be used. . Furthermore, a molten metal, metal fine particles, and a conductive polymer that can be formed using a wet film formation method, which is preferably used for the above-described cathode, can also be used.

  Since the anode electrode 2 has a role of supplying holes to the organic layer, it is preferable to use a conductive material having a large work function. In particular, the anode electrode 2 may be formed of at least one kind of metal having a work function of 4.2 eV or more, or an alloy of these metals, or a substance included in the group consisting of conductive inorganic oxides. preferable. Furthermore, since the metal used for the anode electrode is easily oxidized when the work function is less than 4.5 eV, the work function is preferably 4.5 eV or more.

  The film thickness of the anode electrode 2 is preferably in the range of 40 to 500 nm, although it depends on the material. When the thickness of the anode 2 is less than 40 nm, the resistance may be increased. When the thickness exceeds 500 nm, a layer (holes) stacked thereon is formed due to a step existing at the end of the patterned anode 2. This is because the injection / transport layer 3, the light emitting layer 4, the electron injection / transport 5, and the cathode electrode 6) may be cut or disconnected, or the anode electrode 2 and the cathode electrode 6 may be short-circuited.

  The anode electrode 2 is formed using a wet film formation method when using a molten metal, metal fine particles, or a conductive polymer that can be formed using a wet film formation method, which is preferably used for the cathode described above. can do. When other metals are used, the anode electrode 2 can be formed using a dry process such as a sputtering method, a vacuum heating deposition method, an EB deposition method, or an ion plating method.

  As described above, the electrode of the organic light emitting device of the present invention can be formed. Among these, at least one of the anode electrode and the cathode electrode is formed by a wet film forming method. It is preferable from the point that the merit of the film forming method can be enjoyed. More preferably, it is preferable that the cathode electrode is formed by a wet film forming method from the viewpoint of the manufacturing process without requiring a vacuum apparatus.

  On the other hand, since both the anode electrode and the cathode electrode contain at least a metal having a work function of 4.2 eV or more, the stability of the electrode is increased, and the element is not easily deteriorated due to oxidation of the electrode. preferable.

  Further, both the anode electrode and the cathode electrode include at least one metal selected from the group consisting of bismuth, gallium, tin, lead, silver, and indium, so that the stability of the electrode is increased. Element deterioration due to electrode oxidation or the like is unlikely to occur, and the electrode on the side from which light is not extracted is preferable because it can be formed using a wet film formation method.

3. Substrate The substrates 1 disposed on both sides of the light emitting layer serve as a support for the organic EL element of the present invention, and may be, for example, a flexible material or a hard material. When light emitted from the light emitting layer 4 is extracted through the substrate 1 side, at least the substrate 1 needs to be made of a transparent material, but when light is extracted through the cathode side, At least the cathode side substrate (not shown) needs to be made of a transparent material.

  Specific examples of materials that can be used include glass, quartz, silicon wafers, glass on which TFTs (thin film transistors) are formed, and polymer base materials such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and polymethacrylate. , Polymethyl methacrylate, polymethyl acrylate, polyester, polycarbonate, polyimide, polyamideimide, polyethersulfone, polyetherimide, polyetheretherketone and the like.

  Among these, quartz, glass, silicon wafers, or super engineering plastics such as polyimide, polyamideimide, polyethersulfone, polyetherimide, and polyetheretherketone are preferable. This is because they have a heat resistance of 200 ° C. or higher, and the substrate temperature in the manufacturing stage can be increased in consideration of the process in the manufacturing process of the TFT of the active drive display device. However, in the case of using a polymer material, in order to prevent deterioration of the organic layer due to the gas generated from the substrate 1, at least the anode electrode 2 forming surface of the substrate 1 is made of silicon oxide, silicon nitride, or the like. It is desirable to provide a gas barrier layer.

  The thickness of such a base material 1 can be set in consideration of the material, the usage status of the organic light emitting device, and the like, and can be set to about 0.005 to 5 mm, for example.

  In addition, although the case where it has a positive hole injection transport layer and an electron injection transport layer other than a light emitting layer as an example of the organic EL element which concerns on this invention was shown in FIGS. 1-3, it has what kind of layer structure other than that. It may be. The organic EL element according to the present invention prevents recombination of holes or electrons, such as a carrier block layer, and further prevents the diffusion of excitons and confines excitons in the light emitting layer. Other functional layers such as a layer for increasing the thickness may be further provided. Specifically, for example, a hole blocking layer or an exciton diffusion layer may be provided between the electron injecting and transporting layer and the light emitting layer. The material used for these arbitrary layers is not particularly limited, and materials generally used for forming each layer can be used.

  As described above, the organic light emitting device of the embodiment having one light emitting unit including at least one light emitting layer among the organic light emitting devices according to the present invention has been specifically described. As the organic light emitting device according to the present invention, It is also possible to provide a serially stacked organic light emitting device in which two or more light emitting units are stacked in series so that the organic layer has two or more light emitting layers and the two or more light emitting layers emit light simultaneously. . In the case of such a serially stacked organic light emitting device, if all the layers are formed by vacuum deposition, the burden on the process is very large. Therefore, according to the present invention, at least a part of the layer forming step is wet-formed. By replacing the law, the efficiency of the process is dramatically improved. Therefore, as a preferred embodiment of the present invention, a serially stacked organic EL element is also included.

  That is, another embodiment of the organic light-emitting device according to the present invention is an organic light-emitting device having a plurality of light-emitting units including at least one light-emitting layer between the opposed anode electrode and the cathode electrode, An organic light emitting device in which a light emitting unit is partitioned by a charge generation layer, the reactive organic compound and / or the organic compound containing the charge injection transport material adjacent to the charge generation layer and / or the charge generation layer It is characterized by containing a reaction product.

  When the reactive organic compound is contained in the charge generation layer and / or the organic layer adjacent to the charge generation layer and containing the charge injecting and transporting material, as described above, the charge generation layer is transferred to each unit. The barrier for hole and electron injection is lowered, and the device characteristics are improved.

  Since the organic light emitting device has a relationship in which the luminance is improved in accordance with the current density and the element life is shortened in accordance with the current density, the single layer element having one conventional light emitting unit and the light emitting unit as in this embodiment are provided. When comparing an organic EL element composed of a plurality of serially stacked organic light-emitting devices, a serially stacked organic light-emitting device having a plurality of light-emitting layers has a lower current density of 1 / n of a conventional single-layer element. Necessary brightness can be obtained. Since the current density required to obtain the required constant luminance is 1 / n, the device lifetime of the serially stacked organic light emitting device is longer than that of the conventional single layer device. However, since n elements are connected in series, the driving voltage is increased n times. Further, in a series stacked organic light emitting device having a plurality of light emitting layers, light emitting units having different characteristics and emission colors can be stacked. As described above, the serially stacked organic light-emitting device can achieve a high-luminance and long-life device, and thus can be applied to a backlight of a personal computer or a lighting fixture.

  The serially stacked organic EL device as described above is a manufacturing method according to the present invention including a step of forming a layer containing a reactive organic compound as an organic layer adjacent to the charge generation layer and / or the charge generation layer. It is preferable to form by using.

Hereinafter, among the organic light-emitting devices according to the present invention, a series stacked organic EL element will be described.
FIG. 4 is a schematic cross-sectional view showing a serially stacked organic EL element which is an embodiment of the organic light-emitting device according to the present invention. On the substrate 1, in order, an anode electrode 2, a light emitting unit 10-1, a charge generating layer 11-1, a light emitting unit 10-2, a charge generating layer 11-2,..., A charge generating layer 11- (N-1) is repeated with the light emitting unit 10-n, and finally the cathode electrode 6 is laminated.

  In the present invention, the light emitting unit refers to a component excluding the anode and the cathode among the components constituting the organic EL element described above. Therefore, also in the serially stacked organic EL element according to the present invention, each light emitting unit can be formed in the same manner using the same material as that of the organic EL element having one light emitting unit described above. Forming by a wet film forming method using a material that can be formed by a wet film forming method as much as possible is preferable from the viewpoint that the advantages of the wet film forming method can be enjoyed.

  In the present invention, the charge generation layer 11 refers to a layer that injects holes in the cathode direction of the device and injects electrons in the anode direction when a voltage is applied. Also in the charge generation layer, it is preferable to form by a wet film forming method from the viewpoint that the advantages of the wet film forming method can be enjoyed.

  The charge generation layer 11 is not particularly limited as long as it plays the above role. In the present invention, the charge generation layer 11 can take an embodiment containing the reactive organic compound and an embodiment not containing the reactive organic compound.

  When the charge generation layer contains the reactive organic compound, it can be formed using the reactive organic compound alone. In this case, as in the case of the electron injecting and transporting layer, a laminate of two or more types of reactive organic compounds or a mixed layer of two or more types of reactive organic compounds may be used. Alternatively, the reactive organic compound may be mixed and formed by dispersing or adding to the material for forming the charge generation layer as described below.

The material for forming the charge generation layer is not particularly limited. For example, it is a conductive material such as one or more kinds of metal fine particles and / or metal oxide fine particles as exemplified in the cathode electrode, or 1.0 An electrically insulating material having a specific resistance of × 10 ² Ω · cm or more, preferably 1.0 × 10 ⁵ Ω · cm or more. In the case of an electrically insulating material having a specific resistance of 1.0 × 10 ² Ω · cm or more, preferably 1.0 × 10 ⁵ Ω · cm or more, it is preferable for preventing crosstalk with the electrode. As an electrically insulating material having a specific resistance of 1.0 × 10 ² Ω · cm or more, preferably 1.0 × 10 ⁵ Ω · cm or more, for example, an oxidation disclosed in JP-A-2003-272860 is disclosed. Examples include a laminate or a mixture of an arylamine compound that can form a charge transfer complex by a reduction reaction and a metal oxide or metal halide.

  In the present invention, the charge generation layer 11 has a laminate of a layer composed of one or more kinds of metal fine particles and / or metal oxide fine particles and a layer containing the reactive organic compound, or one or more kinds of metals. Having a mixed layer containing fine particles and / or metal oxide fine particles and the reactive organic compound protects the light emitting unit existing under the charge generating layer when forming the light emitting unit provided on the charge generating layer. It is preferable from the point.

  In the present invention, when the charge generating layer 11 does not contain the reactive organic compound, the charge generating layer 11 is formed using only the material forming the charge generating layer, and the reactive organic compound is Preferably, it is contained in an organic layer containing a charge injecting and transporting material adjacent to the charge generation layer. Since the organic layer adjacent to the charge generation layer is typically an electron injecting and transporting layer, a light emitting layer, a hole injecting and transporting layer or the like in the light emitting unit, in this case, the reactive organic compound is the above-mentioned 1 unit. It may be included in each layer in the same manner as described in the organic EL element. Note that, in the serial stacked organic EL element, even when the reactive organic compound is not included in the charge generation layer and / or the organic layer adjacent to the charge generation layer, for example, the reactive organic compound is included in the electrode. If so, it corresponds to the organic light emitting device according to the present invention.

  As described above, the organic light-emitting device of the present invention uses the reactive organic compound, so that an electron injection / transport layer, an organic salt and / or an organometallic complex used in a conventional electron injection material, Since it is not necessary to deposit an electrode material having heat reducing properties on the light emitting layer, the cathode electrode material is not limited.

  For this reason, the organic light-emitting device of the present invention can use the cathode electrode as a transparent electrode in a configuration in which the lower electrode on the substrate is an anode electrode and the upper electrode is a cathode electrode.

  The organic light-emitting device of the present invention can realize an excellent electron injection / transport function even when an organic EL element is formed on a substrate from a cathode. Therefore, the organic light-emitting device of the present invention can be suitably applied as an organic light-emitting device in which the cathode electrode is a lower electrode on a substrate and the anode electrode is an upper electrode. Here, the lower electrode is an electrode formed first, and the upper electrode is an electrode formed last. For example, in FIG. 1, the lower electrode is the anode 2 and the upper electrode is the cathode 6, and in FIG. The lower electrode is the cathode 6 and the upper electrode is the anode 2.

  The organic light-emitting device of the present invention can also be suitably applied as an element having a top emission (upper surface light emission) structure in which at least one of the anode electrode and the cathode electrode is formed of a transparent electrode and light is extracted from the upper part.

  Furthermore, the organic light-emitting device of the present invention can be suitably applied as a double-sided light-emitting device in which both the anode electrode and the cathode electrode are made of transparent electrodes.

  The organic light-emitting device of the present invention can form a layer having an electron injecting and transporting function by a wet film-forming method by using the reactive organic compound, and further, the cathode material and the cathode manufacturing method are not limited. Can also be formed by a wet film formation method. Therefore, all of the light emitting units and the upper electrode of the anode electrode and the cathode electrode may be manufactured under atmospheric pressure. In this case, a large-scale vapor deposition apparatus is not required at all, and the manufacturing process can be simplified. In view of the high material utilization efficiency, the cost is low, and the substrate can have a large area.

II. Organic Transistor Next, an organic transistor which is another example of the organic electronic device of the present invention will be described.
5-8 is a schematic sectional drawing which shows an example of the organic transistor which concerns on this invention.

  As a first embodiment of the organic transistor 20 according to the present invention, as shown in FIGS. 5 and 7, a gate electrode 22, a source electrode 25, a drain electrode 26, and a gate electrode, which are opposed to each other, are formed on a substrate 21. 22, an organic semiconductor layer 24 disposed between the source electrode 25 and the drain electrode 26, an insulating layer 23, and between the source electrode 25 and the organic semiconductor layer 24 and between the drain electrode 26 and the organic semiconductor layer 24. And those in which the charge injection layer 27 is formed.

  Further, as a second embodiment of the organic transistor 20 according to the present invention, as shown in FIGS. 6 and 8, on a substrate 21, there are a gate electrode 22, a source electrode 25, a drain electrode 26 facing each other, Examples include an organic semiconductor layer 24 disposed between the gate electrode 22, the source electrode 25, and the drain electrode 26, and an insulating layer 23.

  In the organic transistor according to the present invention, a layer containing a reactive organic compound and / or a reaction product thereof is provided between at least one electrode and an organic layer containing a charge injecting and transporting material, which is the first aspect. Typically, in the case where the layer structure as shown in FIGS. 5 and 7 is employed, at least one of the charge injection layers 27 contains a reactive organic compound, and as a result, at least the charge injection layers 27 On the other hand, there may be mentioned a case where a reaction product is contained at the interface between at least one of the charge injection layer 27 and the organic semiconductor layer 24 and further at the interface between at least one of the charge injection layer 27 and the electrode.

  In the organic transistor according to the present invention, a reactive organic compound and / or a reaction product thereof is provided in the second embodiment, which is at least one electrode and / or an organic layer containing a charge injecting and transporting material adjacent to the electrode. First, when the layer structure as shown in FIGS. 5, 6, 7 and 8 is taken, the source electrode 25 and / or the drain electrode 26 contains a reactive organic compound. In some cases, the interface between the electrode and the charge injection layer 27 or the organic semiconductor layer 24 or the charge injection layer 27 or the organic semiconductor layer 24 adjacent to the electrode contains a reactive organic compound or a reaction product.

  Furthermore, as a second aspect, in the case of taking the layer structure as shown in FIGS. 6 and 8, the organic semiconductor layer 24 contains a reactive organic compound, and as a result, reacts at the interface between the organic semiconductor layer 24 and the electrode. The case where a product is contained is mentioned.

  Further, as a second aspect, in the case where the layer configuration as shown in FIGS. 5 and 7 is adopted, the charge injection layer 27 is formed by containing a reactive organic compound in the charge injection transport material, and as a result, the electrode And the charge injection layer 27 and the interface between the charge injection layer 27 and the organic semiconductor layer 24 may contain reaction products. Note that this case also corresponds to the first aspect.

  The organic transistor of the present invention contains the reactive organic compound, thereby reducing the charge injection barrier between the source electrode 25 and the drain electrode 26 and the organic semiconductor layer 24, thereby reducing the HOMO value that is difficult to oxidize. A large (for example, about 6 eV) organic semiconductor material can be used for element driving without any problem. Further, by reducing the charge injection barrier between the organic semiconductor layer and the source electrode or the drain electrode, the on-current value of the organic transistor is improved and the organic semiconductor layer is hardly oxidized, so that the element characteristics are stabilized.

1. Charge Injection Layer The charge injection layer 27 is formed so as to function as a hole injection layer when the organic semiconductor layer 24 is a p-type semiconductor and as an electron injection layer when it is an n-type semiconductor. It is necessary to select the material. In the case of the hole injection layer, it is preferable to form a layer in the same manner as the hole injection transport layer of the organic EL element described above. In the case of the electron injection layer, the electron injection transport of the organic EL element described above is preferable. It is preferable to form a layer similarly to the layer.

2. Organic Semiconductor Layer The carrier mobility of the organic semiconductor layer, which is an organic layer, is 10 ⁻⁶ cm / Vs or more, particularly 10 ⁻³ cm / Vs or more for an organic transistor. To preferred.

  As a material for forming the organic semiconductor layer, a donor or acceptor low molecular or high molecular organic semiconductor material can be used.

  Examples of organic semiconductor materials having donor properties include acene molecular materials, metal phthalocyanines, thiophene oligomers, and regioregular poly (3-alkylthiophenes), and examples of acceptor organic semiconductor materials include fullerene and hexadecafluorocopper phthalocyanine. be able to. Moreover, the organic-semiconductor material of Unexamined-Japanese-Patent No. 2004-6754 can also be used suitably.

  The organic semiconductor layer can be formed by wet coating or a dry process.

3. Substrate, Electrode, and Insulating Layer The substrate, gate electrode, source electrode, drain electrode, and insulating layer are not particularly limited, and can be formed using the following materials, for example.

(1) Substrate The substrate 21 serves as a support for the organic device of the present invention, and may be, for example, a flexible material or a hard material. Specifically, the same substrate as that of the organic EL element can be used.

(2) Electrode The gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are conductive materials. Specifically, the same metal or metal oxide as the electrode in the organic EL element described above can be used, but platinum, gold, silver, copper, aluminum, indium, ITO, and carbon are particularly preferable.

(3) Insulating layer Various insulating materials can be used for the insulating layer that insulates the gate electrode, and an inorganic oxide or an organic compound can be used. In particular, an inorganic oxide having a high relative dielectric constant is preferable. Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  Examples of the organic compound used for the insulating layer include polyimide, polyamide, polyester, polyacrylate, photo radical polymerization system, photo cation polymerization system photo-curing resin, or copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, And phosphazene compounds including novolak resins, cyanoethyl pullulan, polymers, and elastomers.

  In addition, although the case where it has a positive hole injection layer and an electron injection layer other than an insulating layer and an organic-semiconductor layer as an example of the organic transistor which concerns on FIG. You may have. The organic transistor according to the present invention further includes other functional layers such as a layer for preventing surface contamination of the gate electrode when forming a drain electrode and a source electrode on the gate insulating layer, such as an interlayer insulating layer. It may be provided. The material used for these arbitrary layers is not particularly limited, and materials generally used for forming each layer can be used.

III. Organic Solar Cell FIGS. 9 and 10 are schematic cross-sectional views illustrating an example of an organic solar cell according to the present invention.
As shown in FIG. 9, an embodiment of the organic solar cell of the present invention includes a hole injection layer 33, which is an organic layer, between a first electrode 32 and a second electrode 37 formed on a substrate 31. A hole transport layer 34, an electron transport layer 35, and an electron injection layer 36 are provided in this order.

  Further, in another embodiment of the organic solar cell of the present invention, as shown in FIG. 10, a hole which is an organic layer is formed between the first electrode 32 and the second electrode 37 formed on the substrate 31. The transport layer 34 and the electron transport layer 35 are provided in this order.

  In the organic solar cell according to the present invention, a layer containing a reactive organic compound and / or a reaction product thereof between at least one electrode and an organic layer containing a charge injecting and transporting material, which is the first aspect. In the case of having a layer structure as shown in FIG. 9, typically, the hole injection layer 33 and / or the electron injection layer 36 contains a reactive organic compound, and as a result, hole injection is performed. The layer 33 and / or the electron injection layer 36, the interface between the hole injection layer 33 and / or the electron injection layer 36 and the hole transport layer 34 and / or the electron transport layer 35, and further the hole injection layer 33 and / or the electron There is a case where a reaction product is contained at the interface between at least one of the injection layer 36 and the electrode.

  Further, in the organic solar cell according to the present invention, a reactive organic compound and / or a reaction product thereof is formed in at least one electrode and / or an organic layer adjacent to the electrode and containing a charge injecting and transporting material. First, in the case of taking a layer structure as shown in FIGS. 9 and 10, the first electrode 32 and / or the second electrode 37 contains a reactive organic compound. The interface between the hole injection layer 33 and / or the electron injection layer 36 and the hole transport layer 34 and / or the electron transport layer 35, the hole injection layer 33 and / or the electron injection layer 36 and the hole transport layer adjacent to the electrode 34 and / or the electron transport layer 35 may contain a reactive organic compound or a reaction product.

  Furthermore, as a second embodiment, when the layer configuration as shown in FIG. 10 is adopted, a reactive organic compound is contained in the hole transport layer 34 and / or the electron transport layer 35, and as a result, the hole transport layer 34. And / or the case where a reaction product is contained in the interface of the electron carrying layer 35 and an electrode is mentioned.

  Further, as a second aspect, when the layer structure as shown in FIG. 9 is adopted, the hole injection layer 33 and / or the electron injection layer 36 are formed by containing the reactive organic compound in the charge injection / transport material. As a result, the interface between the electrode and the hole injection layer 33 and / or the electron injection layer 36 or the interface between the hole injection layer 33 and / or the electron injection layer 36 and the hole transport layer 34 and / or the electron transport layer 35 is obtained. In the case of containing a reaction product. Note that this case also corresponds to the first aspect.

  In the organic solar cell of the present invention, the charge injection barrier between the electrode and the organic layer is reduced by containing the reactive organic compound. As a result, the organic solar cell of the present invention can efficiently extract internal charges, and can efficiently obtain an electromotive force.

  The substrate 31, the first electrode 32, the second electrode 37, the hole transport layer 34 that is an organic layer, and the electron transport layer 35 are not particularly limited, and can be formed using, for example, the following materials.

1. Substrate The substrate 31 serves as a support for the organic electronic device of the present invention, and may be a flexible material or a hard material, for example. Specifically, the same substrate as the substrate of the organic EL element can be used.

2. Electrode The first electrode 32 is not particularly limited as long as it is a conductive material. Specifically, the same conductive material as the anode electrode in the organic EL element described above can be used. It is preferable to select appropriately in consideration of the irradiation direction of light, the work function of the material forming the second electrode, and the like. When the substrate is a light receiving surface, the first electrode is preferably a transparent electrode, and in this case, a material generally used as a transparent electrode can be used. Specifically, In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, and the like can be given.

  The second electrode 37 is not particularly limited as long as it is a conductive material. Specifically, the same conductive material as the cathode electrode in the organic EL element described above can be used. When the substrate is a light receiving surface, the first electrode is a transparent electrode. In such a case, the second electrode layer may not be transparent. When an electrode having a high work function is used as the first electrode, conventionally, a material having a low work function has been used for the second electrode. However, in the present invention, a metal having a high work function because of high charge injection efficiency. Can be used to form the electrode. The second electrode may be composed of a single layer or may be laminated using materials having different work functions.

3. Hole transport layer and electron transport layer The material for forming the hole transport layer 34 is not particularly limited as long as it has a function as an electron donor. Specific examples include polyphenylene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polysilane and derivatives thereof, polyalkylthiophene and derivatives thereof, porphyrin derivatives, phthalocyanine derivatives, and organometallic polymers.

On the other hand, the material for forming the electron transport layer 35 is not particularly limited as long as it has a function as an electron acceptor. Specifically, CN-poly (phenylene-vinylene), MEH-CN-poly (phenylene-vinylene), -CN group or -CF ₃ group-containing polymer, -CF ₃ substituted polymer, poly (fluorene) derivative, fullerene derivatives such as C _60, may be mentioned carbon nanotubes, perylene derivatives, polycyclic quinone, a material quinacridone.

4). Hole injection layer and electron injection layer As the hole injection layer 33 and / or the electron injection layer 36, a charge injection transport material in the case where the reactive organic compound is contained in the charge injection transport material is used as a hole injection layer When the layer 33 is formed, a material for forming the hole transport layer 34 can be used, and when the electron injection layer 36 is formed, a material for forming the electron transport layer 35 can be used. .

  In addition, in FIG. 9, FIG. 10, although the case where it had a hole injection layer and an electron injection layer other than a hole transport layer and an electron transport layer as an example of the organic solar cell concerning this invention was mentioned, Any layer structure may be used. In the case of the above example, the photoelectric conversion layer that contributes to the charge separation of the organic solar cell and has the function of transporting the generated electrons and holes toward the electrodes in the opposite directions, the hole transport layer and the electron transport layer. However, the photoelectric conversion layer has at least one of a hole transport layer functioning as an electron donor or an electron transport layer functioning as an electron acceptor, or both of an electron donor and an electron acceptor. The case where it consists of an electron hole transport layer which has these functions is mentioned.

<Method for manufacturing organic electronic device>
Next, the manufacturing method of the organic electronic device according to the present invention will be described.
A first aspect of a method for producing an organic electronic device according to the present invention is an organic having two or more electrodes facing each other and at least one organic layer disposed between the two electrodes on a substrate. In the method of manufacturing an electronic device, the method includes a step of forming a layer containing a reactive organic compound between at least one electrode and an organic layer containing a charge injecting and transporting material.

  In addition, a second aspect of the method for manufacturing an organic electronic device according to the present invention includes two or more electrodes facing each other on a substrate, and at least one organic layer disposed between the two electrodes. A method for producing an organic electronic device having a step of forming a layer containing a reactive organic compound as an organic layer containing a charge injecting and transporting material adjacent to at least one electrode and / or electrode. .

  The organic electronic device manufacturing method according to the present invention includes a step of forming a layer containing a reactive organic compound between at least one electrode and an organic layer containing a charge injecting and transporting material, or a reactive organic compound. It is possible to improve the charge injection function by having a step of forming a layer containing a layer as an organic layer containing a charge injection / transport material adjacent to at least one electrode and / or the electrode. That is, in the method for manufacturing an organic electronic device according to the present invention, the charge injection / transport material that has been neutral can react with the reactive organic compound to increase the charge density. Electronic devices can be manufactured. Since charge transfer is easily performed between the neutral charge injection and transport material, the material and formation method for forming the charge injection layer and the electrode layer adjacent thereto are not limited as in the past, and the vapor deposition method should be used. It is possible to manufacture an organic electronic device having a good charge injection function.

  Therefore, in the method for producing an organic electronic device according to the present invention, the layer containing the reactive organic compound can be formed by a wet film forming method, which is preferable. In the case of using a wet film forming method, a large-scale vapor deposition apparatus is unnecessary, the manufacturing process can be simplified, the material utilization efficiency is high, the cost is low, and the base material can be enlarged.

  Examples of wet film forming methods include spin coating, casting, dipping, bar coating, blade coating, roll coating, gravure coating, flexographic printing, and spraying using a melt, solution, or mixed solution of materials. Examples of the coating method include a coating method, and a patterning method such as printing or inkjet. Among these, the spin coating method and the ink jet method are preferably used from the viewpoint of the manufacturing process.

  In the manufacturing method of the organic electronic device according to the present invention, it is preferable that the reactive organic compound and the charge injecting and transporting material further include a step of forming a reaction product.

  The step of forming the reaction product by the reactive organic compound and the charge injecting and transporting material may include a heating step after forming the layer containing the reactive organic compound layer. It is preferable to have a heating process from the point which accelerates | stimulates formation of the said reaction product. In this case, the term “after formation of the layer containing the reactive organic compound layer” may or may not be immediately after. As a specific example that may not be immediately after, for example, a case where a light emitting layer containing at least the reactive organic compound is formed, a cathode electrode is further formed, and a heating step is provided after the cathode electrode is formed.

  In the heating step, it is preferable to heat to 80 to 250 ° C., and further to 80 to 100 ° C., for example, solvent removal and film quality stability by heating above the glass transition temperature (but below the decomposition temperature). It is preferable from the point. Moreover, as a heating means, an infrared heater, a hot plate, a clean oven, a vacuum oven, etc. can be used, for example.

  The organic electronic device according to the first aspect is preferably manufactured by using the method for manufacturing the organic electronic device according to the first aspect of the present invention. In particular, the reactive organic compound and the charge injecting / transporting material are It is preferable to manufacture using the manufacturing method of the organic electronic device of the 1st aspect which further has the process of forming a reaction product.

  The organic electronic device of the second aspect is preferably manufactured by using the method for manufacturing the organic electronic device of the second aspect according to the present invention, and in particular, the reactive organic compound and the charge injecting and transporting material are It is preferable to manufacture using the manufacturing method of the organic electronic device of the 2nd aspect which further has the process of forming a reaction product.

  Other steps in the method for producing an organic electronic device according to the present invention are not particularly limited.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example.

Example 1
(Formation of anode)
A transparent glass substrate (non-alkali glass NA35 manufactured by NH Techno Glass Co., Ltd.) having a length and width of 40 mm × 40 mm and a thickness of 0.7 mm was prepared as a base material. A thin film (thickness 130 nm) of (IZO) was formed by sputtering. In the above IZO thin film formation, a mixed gas of Ar and O ₂ (volume ratio Ar: O ₂ = 100: 1) was used as the sputtering gas, and the pressure was 0.1 Pa and the DC output was 150 W.

   Next, a photosensitive resist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto the anode, mask exposure, development (using NMD3 (developer) manufactured by Tokyo Ohka Kogyo Co., Ltd.), and etching are performed. Then, the anode was patterned.

(Formation of hole injection transport layer)
Next, the transparent glass substrate provided with the anode and the insulating layer is washed, subjected to UV ozone treatment, and then in the air, the polyethylene dioxythiophene represented by the following structural formula is formed on the transparent glass substrate so as to cover the anode. -Polystyrene sulfonate (PEDOT-PSS) was apply | coated by the spin coat method, and it dried and formed the positive hole injection transport layer (thickness 80nm).

（但し、ｎは１０，０００〜５００，０００である。）

(However, n is 10,000 to 500,000.)

(Formation of light emitting layer)
Poly (9,9 dioctylfluorene- represented by the following structural formula (2) on the hole injection transport layer in a low oxygen (oxygen concentration 1 ppm or less) and low humidity (water vapor concentration 1 ppm or less) glove box A polymer (5BTF8) composed of (co-benzothiazole) (F8BT) and poly (9,9 dioctylfluorene) (PF8) was synthesized, applied by spin coating, and dried to form a light emitting layer (thickness 80 nm). . The polymer (5BTF8) is a light emitting material in which F8BT and PF8 are blended at a weight ratio of 5:95.

（但し、ｎは１００，０００〜１，０００，０００である。）

(However, n is 100,000 to 1,000,000.)

(Electron injection transport layer)
Furthermore, a layer made of lithium diisopropylamide having a thickness of 3 nm was formed on the light emitting layer by a spin coating method to form an electron injecting and transporting layer.

(Formation of cathode)
On the electron injecting and transporting layer, Au was deposited as a cathode with a thickness of 150 nm to form a cathode. The deposition conditions were a degree of vacuum of 5 × 10 ⁻⁵ Pa and a film formation rate of 2 to 3 liters / second.

Thereafter, sealing was performed with alkali-free glass in a glove box in a low oxygen (oxygen concentration 1 ppm or less) and low humidity (water vapor concentration 1 ppm or less) state.
As described above, an anode patterned in a line shape having a width of 2 mm, an electron injecting and transporting layer formed in a line shape having a width of 2 mm so as to be orthogonal to the anode, and a cathode, and four light emitting areas (area: 4 mm ² ) An organic EL device having the above was produced.

(result)
A current density of about 110 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 12000 cd / m ² . From these results, it has been clarified that good device characteristics can be obtained even when an electron injecting and transporting layer made of lithium diisopropylamide is formed by coating and a metal having a large work function is used as the cathode.

(Comparative Example 1)
An organic EL device was produced in the same manner as in Example 1 without forming the electron injecting and transporting layer. A current density of about 50 mA / cm ² was obtained when a voltage of 13 V was applied to the organic EL element. The luminance observed from the anode side was about 3 cd / m ² . From this result, it was clarified that the absence of the electron injection transport layer made of lithium diisopropylamide has a large electron injection barrier from the cathode to the light emitting layer, and the current-voltage characteristics are lowered.

(Example 2)
In the same manner as in Example 1, the layers up to the electron injecting and transporting layer were formed. Thereafter, a cathode was formed using a metal composed of gallium: indium: tin (weight ratio 50:25:25). This alloy was melted and coated by heat treatment to form a predetermined cathode pattern.
A current density of about 100 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 10,000 cd / m ² . From this result, it has been clarified that good device characteristics can be obtained even when an electron injecting and transporting layer made of lithium diisopropylamide is formed by coating and then the cathode is formed by coating.

Example 3
An organic EL device was produced in the same manner as in Example 1 except that an electron injecting and transporting layer made of lithium tetramethylcyclopentadiene was formed. A current density of about 50 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 5000 cd / m ² . From this result, it has been clarified that good device characteristics can be obtained even when an electron injecting and transporting layer made of lithium tetramethylcyclopentadiene is formed by coating and a metal having a large work function is used as the cathode.

Example 4
As an electron injecting and transporting layer, an organic EL device was produced in the same manner as in Example 1 except that a layer was formed by mixing lithium diisopropylamide (weight ratio 1: 1) with polyvinyl alcohol as a polymer compound. A current density of about 70 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 7000 cd / m ² . From this result, it has been clarified that good device characteristics can be obtained even when an electron injecting and transporting layer containing lithium diisopropylamide is formed by coating and a metal having a large work function is used as the cathode.

(Example 5)
Similarly to Example 1, an electron injecting and transporting layer made of lithium diisopropylamide was formed. Thereafter, an Ag paste (Fujikura Kasei Dotite, for inorganic EL) was formed to a thickness of 3 μm by screen printing.
A current density of about 10 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 100 cd / m ² . From this result, it has been clarified that good device characteristics can be obtained even when an electron injecting and transporting layer made of lithium diisopropylamide is formed by coating and a metal having a large work function is applied as a cathode.

(Comparative Example 2)
Without forming the electron injecting and transporting layer made of lithium diisopropylamide, a cathode was formed on the light emitting layer with Ag paste in the same manner as in Example 5 to produce an organic EL device. A current density of about 10 mA / cm ² was obtained when a voltage of 20 V was applied to the organic EL element. The luminance observed from the anode side was about 20 cd / m ² . From this result, it was clarified that the absence of the electron injection transport layer made of lithium diisopropylamide has a large electron injection barrier from the cathode to the light emitting layer, and the current-voltage characteristics are lowered.

(Comparative Example 3)
An organic EL device was produced in the same manner as in Example 1 using lithium ethoxide (CH ₃ CH ₂ OLi) as the electron injecting and transporting layer. A current density of about 13 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 85 cd / m ² . From this result, it has been clarified that in the injection material in which oxygen is directly bonded to the alkali metal in the electron injection transport layer, the electron injection barrier from the cathode to the light emitting layer is large and the current-voltage characteristics are deteriorated.

(Example 6)
(Formation of hole injection transport layer)
As the anode transparent electrode, an ITO glass substrate on which ITO (indium-tin oxide, manufactured by Asahi Glass Co., Ltd.) having a sheet resistance of 15Ω / □ is formed, and polyethylenedioxythiophene-polystyrene sulfonate (PEDOT-PSS) on the anode is used. The hole injection transport layer (thickness 80 nm) was formed by coating and drying.

(Formation of light emitting layer)
A polymer (5BTF8) composed of poly (9,9 dioctylfluorene-co-benzothiazole) (F8BT) and poly (9,9 dioctylfluorene) (PF8) is synthesized on the hole injecting and transporting layer, and formed by coating. It dried and formed the light emitting layer (80 nm in thickness). The polymer (5BTF8) is a light emitting material in which F8BT and PF8 are blended at a weight ratio of 5:95.

(Formation of an electron injecting and transporting layer; a layer containing a reactive organic compound)
Further, pentamethylcyclopentadienyl lithium was formed on the light emitting layer by coating so as to have a thickness of 3 nm to form an electron injecting and transporting layer made of the reactive organic compound according to the present invention.

(Formation of cathode)
On the electron injecting and transporting layer, Ag was deposited as a cathode with a thickness of 100 nm to form a cathode. The deposition conditions were a degree of vacuum of 5 × 10 ⁻⁵ Pa and a film formation rate of 2 to 3 liters / second.
Then, sealing was performed with glass in a glove box in a low oxygen (oxygen concentration 1 ppm or less) and low humidity (water vapor concentration 1 ppm or less) state.

As described above, an organic EL device having an anode patterned in a line shape having a width of 2 mm and a cathode formed in a line shape having a width of 2 mm so as to be orthogonal to the anode, and having four light emitting areas (area 4 mm ² ). Was made.

A current density of about 100 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 10,000 cd / m ² . From this result, when an electron injecting and transporting layer made of the reactive organic compound is formed, good electron injecting characteristics can be obtained even if the cathode is made of a metal having a large work function and no heat reducing property. It was revealed.

(Example 7)
An organic EL device was produced in the same manner as in Example 6 except that an electron injecting and transporting layer composed of the reactive organic compound according to the present invention was formed by applying tris (butylcyclopentadienyl) yttrium to a thickness of 3 nm. did.

A current density of about 100 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 9000 cd / m ² . From this result, when an electron injecting and transporting layer made of the reactive organic compound is formed, good electron injecting characteristics can be obtained even if the cathode is made of a metal having a large work function and no heat reducing property. It was revealed.

(Example 8)
An organic EL device was produced in the same manner as in Example 6 except that bis (cyclopentadienyl) magnesium was formed by coating to form a thickness of 3 nm to form an electron injecting and transporting layer made of the reactive organic compound according to the present invention. .

A current density of about 80 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 7000 cd / m ² . From this result, when an electron injecting and transporting layer made of the reactive organic compound is formed, good electron injecting characteristics can be obtained even if the cathode is made of a metal having a large work function and no heat reducing property. It was revealed.

Example 9
An organic EL device was produced in the same manner as in Example 6 except that bis (cyclopentadienyl) strontium was formed to a thickness of 3 nm by coating to form an electron injecting and transporting layer made of the reactive organic compound according to the present invention. .

A current density of about 90 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 9000 cd / m ² . From this result, when an electron injecting and transporting layer made of the reactive organic compound is formed, good electron injecting characteristics can be obtained even if the cathode is made of a metal having a large work function and no heat reducing property. It was revealed.

(Example 10)
An organic EL element was fabricated in the same manner as in Example 6 except that tris (tetramethylcyclopentadienyl) europium was formed to a thickness of 3 nm by coating to form an electron injecting and transporting layer made of the reactive organic compound according to the present invention. Produced.

A current density of about 100 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 9000 cd / m ² . From this result, when an electron injecting and transporting layer made of the reactive organic compound is formed, good electron injecting characteristics can be obtained even if the cathode is made of a metal having a large work function and no heat reducing property. It was revealed.

(Example 11)
An organic EL device was formed in the same manner as in Example 6 except that tris (tetramethylcyclopentadienyl) cobalt was formed to a thickness of 3 nm by coating to form an electron injecting and transporting layer made of the reactive organic compound according to the present invention. Produced.

A current density of about 80 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 7000 cd / m ² . From this result, when an electron injecting and transporting layer made of the reactive organic compound is formed, good electron injecting characteristics can be obtained even if the cathode is made of a metal having a large work function and no heat reducing property. It was revealed.

(Comparative Example 4)
An organic EL device was produced in the same manner as in Example 6 without forming an electron injecting and transporting layer made of the reactive organic compound. A current density of about 50 mA / cm ² was obtained when a voltage of 10 V was applied to the organic EL element. The luminance observed from the anode side was about 1000 cd / m ² . From this result, it has been clarified that the absence of the electron injecting and transporting layer made of the reactive organic compound has a large electron injecting barrier from the cathode to the light emitting layer, and the current-voltage characteristics are lowered.

(Example 12)
In the same manner as in Example 6, the electron injecting and transporting layer was formed. Thereafter, a cathode was formed using a metal composed of gallium: indium: tin (weight ratio 50:25:25). This alloy was melted and coated by heat treatment to form a predetermined cathode pattern.

A current density of about 70 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 5000 cd / m ² . From this result, it has been clarified that good device characteristics can be obtained even when the electron injecting and transporting layer made of the reactive organic compound is formed by a wet film forming method and then the cathode is formed by a wet film forming method. .

(Example 13)
The light emitting layer was formed in the same manner as in Example 6. Tris (butylcyclopentadienyl) yttrium was dispersed in an Ag paste at a weight ratio (Ag: reactive organic compound) of 97: 3, and a cathode was formed on the light emitting layer by coating.

A current density of about 50 mA / cm ² was obtained when a voltage of 6 V was applied to the organic EL element. The luminance observed from the anode side was about 4000 cd / m ² . From this result, it was found that good device characteristics can be obtained even when the cathode containing the reactive organic compound is formed by a wet film-forming method.

(Example 14)
The light emitting layer was formed in the same manner as in Example 6. Thereafter, tris (butylcyclopentadienyl) yttrium was dispersed in the ITO fine particle paste, and a charge generation layer containing a reactive organic compound was formed on the light emitting layer by coating. Thereafter, a hole injection transport layer (PEDOT-PSS) was formed to 80 nm and a light emitting layer (5BTF8) was formed to 80 nm again. 3 nm of tris (butylcyclopentadienyl) yttrium was formed as an electron injection transport layer, and then patterned by coating using an alloy of gallium: indium: tin (weight ratio 50:25:25) as a cathode electrode. A cathode was formed.

A current density of about 80 mA / cm ² was obtained when a voltage of 15 V was applied to the organic EL element. The luminance observed from the anode side was about 16000 cd / m ² . From this result, it was revealed that good charge injection characteristics can be obtained in an organic EL element having a plurality of light emitting units.

It is sectional drawing which shows an example of the organic EL element of this invention. It is sectional drawing which shows another example of the organic EL element of this invention. It is sectional drawing which shows another example of the organic EL element of this invention. It is sectional drawing which shows another example of the organic EL element of this invention. It is sectional drawing which shows an example of the organic transistor of this invention. It is sectional drawing which shows another example of the organic transistor of this invention. It is sectional drawing which shows another example of the organic transistor of this invention. It is sectional drawing which shows another example of the organic transistor of this invention. It is sectional drawing which shows an example of the organic solar cell of this invention. It is sectional drawing which shows another example of the organic solar cell of this invention.

DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Anode electrode 3 ... Hole injection transport layer 4 ... Light emitting layer 5 ... Electron injection transport layer 6 ... Cathode electrode 20 ... Organic transistor 21 ... Substrate 22 ... Gate electrode 23 ... Insulating layer 24 ... Organic semiconductor layer 25 ... Source electrode 26 ... Drain electrode 27 ... Charge injection layer
31 ... Substrate 32 ... First electrode 33 ... Hole injection layer 34 ... Hole transport layer 35 ... Electron transport layer 36 ... Electron injection layer 37 ... Second electrode

Claims (18)

  An organic electronic device having two or more electrodes facing each other and at least one organic layer disposed between the two electrodes on the substrate, the organic electronic device including at least one electrode and a charge injecting and transporting material An organic electronic device comprising a layer containing a reactive organic compound and / or a reaction product thereof between the organic layer and the organic layer.   An organic electronic device having two or more opposing electrodes and at least one organic layer disposed between two electrodes on a substrate, the organic electronic device being adjacent to at least one electrode and / or electrode An organic electronic device comprising a reactive organic compound and / or a reaction product thereof in an organic layer containing a charge injecting and transporting material.   The organic electronic device according to claim 1, wherein the charge injection / transport material is an electron injection / transport material.   The organic electronic device according to claim 1, wherein the reactive organic compound has a reducing site or a proton accepting site.   5. The organic electronic device according to claim 1, wherein a charge of a reducing site or a proton accepting site of the reactive organic compound is neutral.   6. The organic electronic device according to claim 1, wherein the electron affinity of the reducing site or proton accepting site of the reactive organic compound is smaller than the electron affinity of the charge injecting and transporting material.   The organic electronic device according to claim 1, wherein the reaction product is formed by forming a part of the reactive organic compound as a charge transfer complex.   8. The organic electronic device according to claim 1, wherein the reaction product is formed by forming a part of the reactive organic compound and a charge transfer complex with a charge injection / transport material.   The reducing site or proton accepting site of the reactive organic compound is boron compound, silicon compound, nitrogen compound, phosphorus compound, sulfur compound, selenium compound, tellurium compound, hydrocarbon cyclic compound, nitrogen-containing cyclic compound, sulfur-containing cyclic It has at least 1 sort (s) of compounds selected from the group which consists of a compound, a selenium-containing cyclic compound, a tellurium-containing cyclic compound, and these condensed polycyclic compounds. Organic electronic devices.   The reactive organic compound is selected from the group consisting of metal amide compounds, metal cyclopentadiene compounds, cyclopentadiene compounds, phenanthroline compounds, phenanthridine compounds, naphthalene compounds, bipyridyl compounds, phenylpyridine compounds, quinoline compounds, and pyridine compounds. The organic electronic device according to claim 1, wherein the organic electronic device is at least one kind.   The organic electronic device according to claim 1, wherein the reactive organic compound contains a metal element.   12. The organic light-emitting device according to claim 1, wherein the organic electronic device contains a light-emitting material.   An organic light emitting device having a plurality of light emitting units including at least one light emitting layer between an opposing anode electrode and cathode electrode, wherein the light emitting units are partitioned by a charge generation layer, wherein the charge generation 13. The organic light-emitting device according to claim 12, wherein a reactive organic compound and / or a reaction product thereof is contained in the organic layer adjacent to the layer and / or the charge generation layer and containing the charge injection / transport material. .   In a method of manufacturing an organic electronic device having two or more electrodes facing each other and at least one organic layer disposed between the two electrodes on a substrate, a layer containing a reactive organic compound, A method for producing an organic electronic device, comprising a step of forming between at least one electrode and an organic layer containing a charge injecting and transporting material.   In a method of manufacturing an organic electronic device having two or more electrodes facing each other and at least one organic layer disposed between the two electrodes on a substrate, a layer containing a reactive organic compound, A method for producing an organic electronic device, comprising the step of forming an organic layer containing a charge injecting and transporting material adjacent to at least one electrode and / or an electrode.   16. The method for producing an organic electronic device according to claim 14, wherein the layer containing the reactive organic compound is formed by a wet film forming method.   The method for producing an organic electronic device according to claim 14, further comprising a step of forming a reaction product between the reactive organic compound and the charge injecting and transporting material. The organic electronic device is an organic light emitting device having a plurality of light emitting units including at least one light emitting layer between an anode electrode and a cathode electrode facing each other, wherein the light emitting units are partitioned by a charge generation layer. 18. The organic electron according to claim 14, further comprising a step of forming a layer containing a reactive organic compound as the charge generation layer and / or an organic layer adjacent to the charge generation layer. Device manufacturing method.

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