WO2011052648A1 - 正孔注入輸送層を有するデバイス、及びその製造方法、並びに正孔注入輸送層形成用インク - Google Patents
正孔注入輸送層を有するデバイス、及びその製造方法、並びに正孔注入輸送層形成用インク Download PDFInfo
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- WO2011052648A1 WO2011052648A1 PCT/JP2010/069090 JP2010069090W WO2011052648A1 WO 2011052648 A1 WO2011052648 A1 WO 2011052648A1 JP 2010069090 W JP2010069090 W JP 2010069090W WO 2011052648 A1 WO2011052648 A1 WO 2011052648A1
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- WIPO (PCT)
- Prior art keywords
- layer
- transition metal
- hole
- hole injection
- transport layer
- Prior art date
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
Definitions
- the present invention relates to a device having a hole injecting and transporting layer including an organic device such as an organic electroluminescence element and a quantum dot light emitting element, a manufacturing method thereof, and an ink for forming a hole injecting and transporting layer.
- organic electroluminescence elements hereinafter referred to as organic EL elements
- organic transistors organic transistors
- organic solar cells organic semiconductors
- Other devices having a hole injecting and transporting layer include quantum dot light emitting elements and oxide compound solar cells.
- the organic EL element is a charge injection type self-luminous device using light emission generated when electrons and holes that have reached the light emitting layer are recombined.
- This organic EL element was developed in 1987 by T.W. W. Since Tang et al. Demonstrated that a device in which a thin film composed of a fluorescent metal chelate complex and a diamine-based molecule is laminated exhibits high-luminance light emission at a low driving voltage, it has been actively developed.
- the element structure of the organic EL element is composed of a cathode / organic layer / anode.
- This organic layer has a two-layer structure composed of a light emitting layer / a hole injection layer in the early organic EL element, but now, in order to obtain a high luminous efficiency and a long driving life, an electron injection layer / electron
- Various multilayer structures such as a five-layer structure including a transport layer / a light emitting layer / a hole transport layer / a hole injection layer have been proposed.
- These layers other than the light emitting layer such as the electron injection layer, the electron transport layer, the hole transport layer, and the hole injection layer have the effect of facilitating the injection and transport of charges to the light emitting layer, or block the electron current and the positive current by blocking. It is said that there are effects such as maintaining the balance of the hole current and suppressing diffusion of light energy excitons.
- Patent Document 1 For the purpose of improving charge transport capability and charge injection capability, attempts have been made to increase the electrical conductivity by mixing an oxidizing compound with a hole transport material (Patent Document 1 and Patent Document 2).
- an oxidizing compound that is, an electron-accepting compound
- a compound containing a counter anion such as a triphenylamine derivative and antimony hexafluoride or a carbon such as 7,7,8,8-tetracyanoquinodimethane is used.
- a compound having an extremely high electron-accepting property in which a cyano group is bonded to carbon of a carbon double bond is used.
- Patent Document 2 as an oxidizing dopant, a general oxidizing agent is exemplified, and a metal halide, Lewis acid, organic acid, and a salt of an arylamine and a metal halide or Lewis acid are exemplified.
- Patent Documents 3 to 6 a metal oxide that is a compound semiconductor is used as an oxidizing compound, that is, an electron-accepting compound.
- an oxidizing compound that is, an electron-accepting compound.
- a thin film is formed by vapor deposition using a metal oxide such as vanadium pentoxide or molybdenum trioxide, or molybdenum oxide and amine
- a mixed film is formed by co-evaporation with a low molecular weight compound.
- Patent Document 7 a solution in which oxovanadium (V) tri-i-propoxide oxide is dissolved is used as an oxidizing compound, that is, an electron-accepting compound, and a mixed coating film is formed with the hole-transporting polymer.
- Patent Document 8 A production method in which a charge transfer complex is formed as vanadium oxide by hydrolysis in water vapor later is mentioned.
- Patent Document 8 as an attempt to form a coating film of molybdenum trioxide, fine particles produced by physically pulverizing molybdenum trioxide are dispersed in a solution to prepare a slurry, which is then applied to inject holes. It describes that a long-life organic EL element is formed by forming a layer.
- an organic transistor is a thin film transistor using an organic semiconductor material composed of a ⁇ -conjugated organic polymer or a small organic molecule in the channel region.
- a general organic transistor includes a substrate, a gate electrode, a gate insulating layer, source / drain electrodes, and an organic semiconductor layer.
- the voltage (gate voltage) applied to the gate electrode 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.
- Patent Document 1 to Patent Document 9 Even if an oxidizing material as disclosed in Patent Document 1 to Patent Document 9 is used as the hole transporting material, it is difficult to realize a long-life element, or the life needs to be further improved. It is assumed that the oxidizing materials disclosed in Patent Documents 1, 2, and 9 have low oxidation ability to the hole transporting material or poor dispersion stability in the thin film. For example, when an oxide material composed of a cationic triphenylamine derivative and antimony hexafluoride used in both Patent Document 1 and Patent Document 2 is mixed with a hole transport material, a charge transfer complex is generated. , Antimony hexafluoride, the same number of free counter anion species as the charge transfer complex, is present in the thin film.
- the oxidizing material as disclosed in Patent Document 1 to Patent Document 9 is not sufficiently soluble in a solvent that dissolves at the same time as the hole transporting polymer compound formed into a film by a solution coating method,
- problems such as easy aggregation with only an oxidizing material and lack of versatility due to the limited types of solvents that can be used.
- molybdenum oxide which is an inorganic compound, has a relatively high characteristic, but is insoluble in a solvent and cannot be used with a solution coating method.
- Patent Document 7 discloses a charge transfer complex as a vanadium oxide which is hydrolyzed in water vapor after formation of a mixed coating film of oxovanadium (V) tri-i-propoxide oxide and a hole transporting polymer. A manufacturing method in which is formed.
- V oxovanadium
- Patent Document 7 since solidification is caused by a hydrolysis-polycondensation reaction, vanadium tends to aggregate, film quality control is difficult, and a good film cannot be obtained. Further, since oxovanadium (V) tri-i-propoxide oxide alone does not form a coating film, and is mixed with a hole transporting polymer, the coating composition of Patent Document 7 inevitably has a high organic component concentration.
- Patent Document 7 describes that a charge injection layer is produced by a screen printing method using a slurry in which molybdenum oxide fine particles having an average particle diameter of 20 nm are dispersed in a solvent.
- a charge injection layer is produced by a screen printing method using a slurry in which molybdenum oxide fine particles having an average particle diameter of 20 nm are dispersed in a solvent.
- the method of pulverizing the MoO 3 powder as in Patent Document 8 for example, to produce fine particles having a uniform particle size on a scale of 10 nm or less in response to a request to form a hole injection layer of about 10 nm, Actually it is very difficult.
- a hole injection layer or a hole transport layer containing molybdenum oxide of an inorganic compound is provided. Therefore, it is necessary to perform vapor deposition using a high-definition mask, and it becomes impossible to take advantage of the solution coating method from the viewpoint of cost and yield.
- molybdenum oxide being the inorganic compound is an oxide semiconductor of oxygen-deficient, unstable in electric conductivity but is Mo 2 O 5 having an oxidation number of +5 than MoO 3 having an oxidation number of +6 is a good conductor at room temperature in air
- the compounds that can be easily thermally deposited are limited to oxide compounds having a stable valence such as MoO 3 or MoO 2 .
- the film formability and the thin film stability are greatly related to the lifetime characteristics of the device. In general, the lifetime of an organic EL element is the luminance half-life when continuously driven by a constant current drive or the like, and an element having a longer luminance half-time has a longer driving lifetime.
- the present invention has been made in view of the above problems, and its main purpose is to provide a device that can form a hole injection transport layer by a solution coating method and that can achieve a long life while being easy to manufacture.
- the purpose is to do.
- the present inventors use a transition metal complex having a specific transition metal as a central metal in the hole injection transport layer, and obtain a reaction product of the transition metal complex.
- a transition metal complex having a specific transition metal as a central metal in the hole injection transport layer, and obtain a reaction product of the transition metal complex.
- the device of the present invention is a device having two or more electrodes opposed to each other on a substrate and a hole injecting and transporting layer disposed between the two electrodes, Whether the hole injecting and transporting layer contains a reaction product of a transition metal complex, and the central metal of the transition metal complex contains at least one transition metal selected from the group consisting of vanadium, rhenium and platinum. Or a mixture of molybdenum and at least one transition metal selected from the group consisting of vanadium, rhenium and platinum.
- the reaction product of the transition metal complex having the specific transition metal as the central metal used in the device of the present invention is different from the metal oxide of the inorganic compound, depending on the valence and ligand of the metal. Transportability can be controlled.
- the transition metal complex may contain an organic moiety in the ligand, so that the compatibility with the hole transporting compound that is an organic substance is improved and the adjacent organic The adhesion at the interface with the layer is also good.
- the transition metal complex is more reactive than a conventionally used metal complex such as copper phthalocyanine, and the reaction product of the transition metal complex is considered to easily form a charge transfer complex.
- the device of the present invention including the hole injecting and transporting layer containing the reaction product of the transition metal complex can realize a low voltage drive, high power efficiency, and long life device. Moreover, in the device of the present invention, by selecting the ligand type of the transition metal complex or modifying the ligand, solvent solubility, hydrophilicity / hydrophobicity, charge transportability, adhesion, etc. It is easy to make it multifunctional, for example, by adding the above functionality.
- the transition metal complex used in the hole injecting and transporting layer of the device of the present invention can be easily synthesized with a small number of synthesis steps by appropriate selection, so that a high-performance device can be produced at low cost.
- transition metal complexes used in the device of the present invention have solvent solubility or high compatibility with the hole transporting compound used together.
- the merit in the manufacturing process is great.
- the transition metal complex does not tend to agglomerate like, for example, a pigment and has an advantage of high yield because of its high stability in solution.
- the hole injection / transport layer is formed by a solution coating method, the hole injection / transport layer to the light emitting layer can be sequentially formed only on the substrate having a liquid repellent bank only by a coating process.
- the hole transport layer and the light emitting layer are formed by a solution coating method, and further the second electrode is deposited. Compared with such a process, there is an advantage that a device can be manufactured at a low cost and is simple.
- the reaction product of the transition metal complex is a transition metal oxide reacted with an organic solvent having a carbonyl group and / or a hydroxyl group from the viewpoint of reducing driving voltage and improving element lifetime. preferable.
- the hole injecting and transporting layer preferably contains at least the reaction product of the transition metal complex and a hole transporting compound from the viewpoint of further reducing driving voltage and device life.
- the hole injecting and transporting layer is a layer comprising a layer in which a layer containing a reaction product of the transition metal complex and a layer containing a hole transporting compound are laminated at least. May be.
- the hole injection transport layer includes a layer containing a reaction product of the transition metal complex and a layer containing at least the reaction product of the transition metal complex and a hole transporting compound. It may be a layer composed of at least laminated layers.
- the hole transporting compound is a hole transporting polymer compound from the viewpoint of further reducing driving voltage and device life.
- the device of the present invention is suitably used as an organic EL element containing an organic layer including at least a light emitting layer.
- a device manufacturing method is a device manufacturing method having two or more electrodes facing each other on a substrate and a hole injecting and transporting layer disposed between the two electrodes.
- the central metal includes at least one transition metal selected from the group consisting of vanadium, rhenium and platinum, or one or more transition metals selected from the group consisting of vanadium, rhenium and platinum and molybdenum.
- the device manufacturing method of the present invention it is possible to provide a device capable of forming a hole injecting and transporting layer by a solution coating method and facilitating the manufacturing process, while achieving a long life.
- the oxidation step may be performed after preparing the hole injection transport layer forming ink and before the step of forming the hole injection transport layer, or may be performed by hole injection transport. You may perform after the process of forming a layer. That is, as one aspect, the step of forming a hole injection transport layer containing the transition metal complex on any layer on the electrode, and at least the transition metal complex in the hole injection transport layer It has an oxidation step in which a part is a transition metal oxide. As another aspect, after the step of preparing the ink for forming the hole injection / transport layer and before the step of forming the hole injection / transport layer, the oxidation step is performed, and the oxidized hole injection / transport layer is formed. A step of forming a hole injecting and transporting layer containing a transition metal oxide on any layer on the electrode using a forming ink;
- a heating step and / or a light irradiation step and / or a step of applying active oxygen can be used as the oxidation step.
- the central metal contains at least one transition metal selected from the group consisting of vanadium, rhenium and platinum, or vanadium, rhenium and platinum. It contains a transition metal complex which is a mixture of at least one transition metal selected from the group consisting of molybdenum and an organic solvent having a carbonyl group and / or a hydroxyl group.
- the ink for forming a hole injection transport layer according to the present invention contains a transition metal oxide obtained by reacting the transition metal complex with an organic solvent having a carbonyl group and / or a hydroxyl group. This is preferable from the viewpoint of further reducing the decrease and the element life.
- the device of the present invention can achieve a long life while the manufacturing process is easy. According to the device manufacturing method of the present invention, it is possible to provide a device that can achieve a long life while the manufacturing process is easy. In addition, according to the ink for forming a hole injecting and transporting layer according to the present invention, it is possible to provide a device that can achieve a long life while the manufacturing process is easy.
- FIG. 1 is a conceptual cross-sectional view showing a basic layer configuration of a device according to the present invention. It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the organic EL element which is one Embodiment of the device which concerns on this invention. It is a cross-sectional schematic diagram which shows another example of the layer structure of the organic EL element which is one Embodiment of the device which concerns on this invention. It is a cross-sectional schematic diagram which shows another example of the layer structure of the organic EL element which is one Embodiment of the device which concerns on this invention. It is a cross-sectional schematic diagram which shows an example of the layer structure of the organic transistor which is another embodiment of the device which concerns on this invention. It is a cross-sectional schematic diagram which shows another example of the layer structure of the organic transistor which is another embodiment of the device which concerns on this invention.
- the device of the present invention is a device having two or more electrodes facing each other on a substrate and a hole injecting and transporting layer disposed between the two electrodes, the hole injecting and transporting layer having a transition Containing a reaction product of a metal complex, wherein the central metal of the transition metal complex contains at least one or more transition metals selected from the group consisting of vanadium, rhenium and platinum, or consists of vanadium, rhenium and platinum It is a mixture of one or more transition metals selected from the group and molybdenum.
- the hole injecting and transporting layer contains a reaction product of a transition metal complex having the specific transition metal as a central metal, thereby forming a charge transfer complex and improving hole injecting characteristics.
- the film is highly stable and has excellent adhesion to adjacent electrodes and organic layers, the lifetime of the element can be extended.
- the hole injecting and transporting layer can be formed using a solution coating method. In this case, a long life can be achieved while the manufacturing process is easy.
- the reaction product of the said transition metal complex used for the device of this invention can improve lifetime. That is, the transition metal complex is highly reactive, and can form a reaction product between the complexes through an oxidation-reduction reaction with an organic solvent used when forming a layer by a solution coating method, for example. Since the transition metal complex reaction product easily forms a charge transfer complex with the hole transporting compound or between the complex reaction products, the charge injecting and transporting capability of the hole injecting and transporting layer is improved. It is possible to improve well, and it is estimated that the lifetime can be improved. Further, unlike the oxide of an inorganic compound, the complex reaction product can control the charge injection property and the charge transport property by the metal valence and the ligand.
- the charge injection / transport capability of the hole injection / transport layer can be improved efficiently.
- the above transition metal complex can contain an organic part in the ligand, so that the compatibility with the hole transporting compound that is an organic substance is improved and the adjacent organic The adhesion at the interface with the layer is also good. Therefore, it is presumed that the device of the present invention provided with the hole injecting and transporting layer containing the reaction product of the transition metal complex can realize a device with low voltage driving, high power efficiency and particularly improved life.
- the hole injecting and transporting layer of the device of the present invention by selecting the type of ligand or modifying the ligand in the transition metal complex, solvent solubility, hydrophilicity / hydrophobicity, charge It is easy to make it multifunctional, such as adding functionality such as transportability or adhesion.
- the transition metal complex used in the hole injecting and transporting layer of the device of the present invention can be easily synthesized with a small number of synthesis steps by appropriately selecting it, so that a high-performance device can be produced at low cost.
- transition metal complexes used in the device of the present invention have solvent solubility or high compatibility with the hole transporting compound used together.
- the thin film can be formed by the solution coating method, the merit in the manufacturing process is great.
- the transition metal complex does not tend to aggregate like, for example, metal nanoparticles and pigments, and has an advantage of high yield because of high stability in the solution.
- the hole injection / transport layer is formed by a solution coating method, the hole injection / transport layer to the light emitting layer can be sequentially formed only on the substrate having a liquid repellent bank only by a coating process.
- the hole transport layer and the light emitting layer are formed by a solution coating method, and further the second electrode is deposited. Compared with such a process, there is an advantage that a device can be manufactured at a low cost and is simple.
- reaction product of the transition metal complex forms a charge transfer complex, for example, when the transition metal complex is mixed into a solution of the charge transport compound by 1H NMR measurement. This is suggested by observation of a phenomenon in which the shape and chemical shift value of the proton signal derived from the aromatic ring observed in the vicinity of 6 to 10 ppm is changed as compared with that before mixing the transition metal complex.
- the device according to the present invention is a device having two or more electrodes facing each other on a substrate and a hole injecting and transporting layer disposed between the two electrodes.
- the device according to the present invention includes an organic EL device, an organic transistor, a dye-sensitized solar cell, an organic thin film solar cell, an organic device including an organic semiconductor, a quantum dot light emitting device having a hole injection transport layer, and an oxide. System compound solar cells and the like are also included.
- FIG. 1 is a conceptual cross-sectional view showing the basic layer structure of an organic device according to the present invention.
- the basic layer configuration of the device of the present invention includes two electrodes (1 and 6) facing each other on a substrate 7, and at least a hole injection transport layer 2 disposed between the two electrodes (1 and 6). It has an organic layer 3.
- substrate 7 is a support body for forming each layer which comprises a device, and does not necessarily need to be provided in the surface of the electrode 1, and should just be provided in the outermost surface of the device.
- the hole injecting and transporting layer 2 contains at least a reaction product of the transition metal complex and is a layer responsible for injecting and / or transporting holes from the electrode 1 to the organic layer 3.
- the organic layer 3 is a layer that exhibits various functions depending on the type of device by being hole-injected and transported, and may be composed of a single layer or a multilayer.
- the organic layer further includes a layer that is the center of the function of the device (hereinafter referred to as a functional layer), and an auxiliary layer for the functional layer. Layers (hereinafter referred to as auxiliary layers).
- a hole transport layer further stacked on the surface of the hole injection transport layer corresponds to the auxiliary layer, and a light emitting layer stacked on the surface of the hole transport layer corresponds to the functional layer.
- the electrode 6 is provided in a place where the organic layer 3 including the hole injecting and transporting layer 2 exists between the opposing electrode 1. Moreover, you may have the 3rd electrode which is not shown in figure as needed. By applying an electric field between these electrodes, the function of the device can be expressed.
- FIG. 2 is a schematic cross-sectional view showing an example of a layer configuration of an organic EL element which is an embodiment of a device according to the present invention.
- a hole injection / transport layer 2 is laminated on the surface of the electrode 1, and a hole transport layer 4 a as an auxiliary layer and a light emitting layer 5 as a functional layer are laminated on the surface of the hole injection / transport layer 2.
- a hole injection / transport layer characteristic of the present invention is used at the position of the hole injection layer, in addition to improving the conductivity, the hole injection / transport layer forms a charge transfer complex to form a solution.
- FIG. 3 is a schematic cross-sectional view showing another example of the layer configuration of the organic EL element which is an embodiment of the device according to the present invention.
- a hole injection layer 4b is formed as an auxiliary layer on the surface of the electrode 1
- a hole injection transport layer 2 is laminated on the surface of the hole injection layer 4b
- a light emitting layer 5 is laminated as a functional layer.
- FIG. 4 is a schematic cross-sectional view showing another example of the layer structure of the organic EL element which is an embodiment of the device according to the present invention.
- the organic EL device of the present invention has a configuration in which a hole injection transport layer 2 and a light emitting layer 5 as a functional layer are sequentially laminated on the surface of an electrode 1.
- each of the hole injection transport layer 2, the hole transport layer 4a, and the hole injection layer 4b may be composed of a plurality of layers instead of a single layer. .
- the electrode 1 functions as an anode and the electrode 6 functions as a cathode.
- the organic EL device when an electric field is applied between the anode and the cathode, holes are injected from the anode into the light emitting layer 5 through the hole injection transport layer 2 and the hole transport layer 4, and electrons are transmitted from the cathode.
- holes and electrons injected inside the light emitting layer 5 are recombined to have a function of emitting light to the outside of the device.
- all the layers existing on at least one surface of the light emitting layer need to be transparent to light having at least a part of wavelengths in the visible wavelength range.
- an electron transport layer and / or an electron injection layer may be provided between the light emitting layer and the electrode 6 (cathode) as required (not shown).
- FIG. 5 is a schematic cross-sectional view showing an example of a layer structure of an organic transistor which is another embodiment of the device according to the present invention.
- the organic transistor is disposed on a substrate 7 between an electrode 9 (gate electrode), an opposing electrode 1 (source electrode) and electrode 6 (drain electrode), and the electrode 9, electrode 1, and electrode 6.
- An organic semiconductor layer 8 as an organic layer, and an insulating layer 10 interposed between the electrode 9 and the electrode 1 and between the electrode 9 and the electrode 6, and a hole injection transport layer on the surface of the electrode 1 and the electrode 6 2 is formed.
- the organic transistor has a function of controlling a current between the source electrode and the drain electrode by controlling charge accumulation in the gate electrode.
- FIG. 6 is a schematic cross-sectional view showing an example of another layer configuration of an organic transistor which is an embodiment of a device according to the present invention.
- the organic transistor is disposed on a substrate 7 between the electrode 9 (gate electrode), the opposing electrode 1 (source electrode) and electrode 6 (drain electrode), and the electrode 9, electrode 1, and electrode 6.
- the hole injecting and transporting layer 2 of the present invention is formed as an organic layer to form an organic semiconductor layer 8, and an insulating layer 10 is interposed between the electrode 9 and the electrode 1 and between the electrode 9 and the electrode 6.
- the hole injection transport layer 2 is an organic semiconductor layer 8.
- the layer structure of the device of the present invention is not limited to the above-described examples, and has substantially the same structure as the technical idea described in the claims of the present invention, and has the same functions and effects. Anything that achieves the above is included in the technical scope of the present invention.
- each layer of the device according to the present invention will be described in detail.
- the device of the present invention includes at least a hole injecting and transporting layer.
- the organic layer When the device of the present invention is an organic device and the organic layer is a multilayer, the organic layer further assists the layer serving as the center of the function of the device and the functional layer in addition to the hole injecting and transporting layer.
- the auxiliary layer which plays a role is included, those functional layers and auxiliary layers will be described in detail in specific examples of the device described later.
- the hole injecting and transporting layer in the device of the present invention includes at least one transition metal selected from the group consisting of vanadium, rhenium and platinum, or selected from the group consisting of vanadium, rhenium and platinum. It contains at least a reaction product of a transition metal complex which is a mixture of one or more transition metals and molybdenum.
- the hole injecting and transporting layer in the device of the present invention may be composed of only the reaction product of the transition metal complex, but may further contain other components. Among these, it is preferable to further contain a hole transporting compound from the viewpoint of further reducing the driving voltage and improving the device life.
- the reaction product of the transition metal complex that may be contained in the hole injecting and transporting layer of the present invention is a process for forming a hole injecting and transporting layer, for example, an ink for forming a hole injecting and transporting layer (application) Solution), or at the time of layer formation or after layer formation, during heating, during light irradiation, when active oxygen is acted on, when a device is driven, etc., and a reaction product produced by the reaction of the transition metal complex I mean.
- the hole injecting and transporting layer in the device of the present invention is composed of one mixed layer containing the reaction product of the transition metal complex and the hole transporting compound. Alternatively, it may be composed of a plurality of layers including the mixed layer.
- the hole injecting and transporting layer may be composed of a plurality of layers in which a layer containing a reaction product of the transition metal complex and a layer containing a hole transporting compound are stacked.
- the hole injecting and transporting layer is a layer in which a layer containing the reaction product of the transition metal complex and a layer containing at least the reaction product of the transition metal complex and a hole transporting compound are stacked. It may consist of.
- the transition metal complex used in the present invention refers to a compound in which a transition metal atom of a central metal and a ligand are bonded.
- the central metal is not particularly limited as long as it includes at least one transition metal selected from the group consisting of vanadium, rhenium and platinum, and may be a single type or a mixture of two or more types. Furthermore, the mixture which combined any 1 or more types of said 3 types and another metal may be sufficient.
- the ionization potential can be changed to optimize the carrier balance.
- the compound which combined the said 3 types and molybdenum is preferable from a viewpoint of ionization potential.
- the type of the ligand is appropriately selected and is not particularly limited.
- the ligand contains an organic part (carbon atom) in view of solvent solubility and adhesion with an adjacent organic layer. Moreover, it is preferable that a ligand decomposes
- Examples of the monodentate ligand include acyl, carbonyl, thiocyanate, isocyanate, cyanate, isocyanate, halogen atom and the like. Among these, hexacarbonyl which is easily decomposed at a relatively low temperature is preferable.
- the structure containing an aromatic ring and / or a heterocyclic ring include benzene, triphenylamine, fluorene, biphenyl, pyrene, anthracene, carbazole, phenylpyridine, trithiophene, phenyloxadiazole, and phenyltriazole. , Benzimidazole, phenyltriazine, benzodiathiazine, phenylquinoxaline, phenylene vinylene, phenylsilole, and combinations of these structures. Moreover, unless the effect of this invention is impaired, you may have a substituent in the structure containing an aromatic ring and / or a heterocyclic ring.
- substituents examples include a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a cyano group, and a nitro group.
- straight-chain or branched alkyl groups having 1 to 20 carbon atoms straight-chain or branched alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are preferable.
- a monodentate ligand or a bidentate ligand is preferable in terms of increasing the reactivity of the transition metal complex used in the present invention. If the complex itself becomes too stable, the reactivity may be poor.
- the reaction product of the transition metal complex used in the present invention is preferably a transition metal oxide reacted with an organic solvent having a carbonyl group and / or a hydroxyl group. Since the transition metal complex has high reactivity, in the process of forming the hole injection transport layer, for example, in the ink for forming the hole injection transport layer, or at the time of layer formation using the ink, heating, light irradiation, Alternatively, when active oxygen is allowed to act, when the organic solvent contained in the ink for forming a hole injection transport layer is an organic solvent having a carbonyl group and / or a hydroxyl group, an oxidation-reduction reaction is performed with the organic solvent, and at least a complex A part of becomes a transition metal oxide.
- the transition metal oxide preferably includes coexisting oxides of transition metal complexes having different oxidation numbers of the central metal. By including oxides of transition metal complexes with different oxidation numbers, the hole transport and hole injection properties are appropriately controlled by the balance of oxidation numbers, which improves drive voltage and device lifetime. It becomes possible to make it.
- the transition metal oxide may contain transition metal atoms and compounds of various valences, such as carbides and nitrides, depending on the processing conditions.
- the organic solvent having a carbonyl group and / or a hydroxyl group used in the present invention is not particularly limited as long as it can appropriately undergo an oxidation-reduction reaction with the transition metal complex.
- organic solvent having a carbonyl group and / or a hydroxyl group examples include aldehyde-based, ketone-based, carboxylic acid-based, ester-based, amide-based, alcohol-based, and phenol-based solvents having a boiling point of 50 ° C to 250 ° C. Are preferably used.
- organic solvent having a carbonyl group and / or a hydroxyl group examples include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isopropyl ketone, diisobutyl ketone, Ketone solvents such as acetonylacetone, isophorone, cyclohexanone; aldehyde solvents such as acetaldehyde, propionaldehyde, furfural, benzaldehyde; carboxylic acid solvents such as acetic acid, propionic acid, butyric acid, valeric acid; ethyl acetate, n-propyl acetate Ester solvents such as i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, ethyl benzoate, but
- Solvent for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, 1,2-butylene glycol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl
- alcohol solvents such as ether
- phenol solvents such as phenol, cresol, xylenol, ethylphenol, trimethylphenol, isopropylphenol, and t-butylphenol.
- the hole transporting compound used in the present invention can be appropriately used as long as it has a hole transporting property.
- the hole transportability means that an overcurrent due to hole transport is observed by a known photocurrent method.
- a high molecular compound is also preferably used.
- the hole transporting polymer compound refers to a polymer compound having a hole transporting property and having a weight average molecular weight of 2000 or more according to polystyrene conversion value of gel permeation chromatography.
- the hole transporting material is a stable coating film that is easily dissolved in an organic solvent and is difficult to aggregate. It is preferable to use a polymer compound that can be formed.
- the hole transporting compound is not particularly limited, and examples thereof include arylamine derivatives, anthracene derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives, and spiro compounds.
- arylamine derivatives include N, N′-bis- (3-methylphenyl) -N, N′-bis- (phenyl) -benzidine (TPD), bis (N- (1-naphthyl-N— Phenyl) benzidine) ( ⁇ -NPD), 4,4 ′, 4 ′′ -tris (3-methylphenylphenylamino) triphenylamine (MTDATA), 4,4 ′, 4 ′′ -tris (N- (2-naphthyl) ) -N-phenylamino) triphenylamine (2-TNATA) and the like, 4,4-N, N′-dicarbazole-biphenyl (CBP) and the like as the carbazole derivative, and N, N′-bis as the fluorene derivative Distyrylbenzene derivatives such as (3-methylphenyl) -N, N′-bis (phenyl) -9,9-dimethylfluorene (DMFL-TP
- Examples of the hole transporting polymer compound include a polymer containing an arylamine derivative, anthracene derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, spiro compound and the like in a repeating unit.
- polymer containing an arylamine derivative as a repeating unit examples include copoly [3,3′-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate (PC-TPD-DEG) as a non-conjugated polymer having the following structure:
- PC-TPD-DEG copoly [3,3′-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate
- PC-TPD-DEG polyethylene glycol
- Poly [N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) -benzidine] can be given as a conjugated polymer such as PTPDES and Et-PTPDK shown.
- polymer containing anthracene derivatives in the repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (9,10-anthracene)]. it can.
- polymer containing carbazoles in the repeating unit include polyvinyl carbazole (PVK).
- polymer containing thiophene derivatives in the repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (bithiophene)].
- polymer containing a fluorene derivative as a repeating unit poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec- Butylphenyl)) diphenylamine)] (TFB) and the like.
- polymer containing a spiro compound as a repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9′-spiro-bifluorene-2, 7-diyl)] and the like.
- These hole transporting polymer compounds may be used alone or in combination of two or more.
- the compound represented by the following general formula (1) tends to improve the adhesion stability with the adjacent organic layer, and the HOMO energy value emits light from the anode substrate. It is also preferable from the point of being between the layer materials.
- Ar 1 to Ar 4 may be the same as or different from each other, and are unsubstituted or substituted aromatic carbonized carbon atoms having 6 to 60 carbon atoms with respect to the conjugated bond.
- a hydrogen group or an unsubstituted or substituted heterocyclic group having 4 or more and 60 or less carbon atoms related to a conjugated bond, n is 0 to 10,000, m is 0 to 10,000, and n + m 10 to 20,000
- the arrangement of the two repeating units is arbitrary.
- the arrangement of the two repeating units is arbitrary, and for example, any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer may be used.
- the average of n is preferably 5 to 5000, and more preferably 10 to 3000.
- the average m is preferably 5 to 5000, and more preferably 10 to 3000.
- the average of n + m is preferably 10 to 10,000, and more preferably 20 to 6000.
- the aromatic hydrocarbon in the aromatic hydrocarbon group specifically includes, for example, benzene, fluorene, naphthalene, anthracene, combinations thereof, and derivatives thereof Furthermore, a phenylene vinylene derivative, a styryl derivative, etc. are mentioned.
- Specific examples of the heterocyclic ring in the heterocyclic group include thiophene, pyridine, pyrrole, carbazole, combinations thereof, and derivatives thereof.
- the substituent is a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
- the content of the hole transporting compound is 10 to 10 parts by mass with respect to 100 parts by mass of the reaction product of the transition metal complex.
- the amount of 10,000 parts by mass is preferable from the viewpoints of improving the hole injecting and transporting property, achieving high film stability, and achieving a long life.
- the content of the hole transporting compound is too small, it is difficult to obtain a synergistic effect obtained by mixing the hole transporting compound.
- the effect using the said transition metal complex will become difficult to be acquired.
- the hole injecting and transporting layer of the present invention may contain additives such as a binder resin, a curable resin, and a coating property improving agent as long as the effects of the present invention are not impaired.
- the binder resin include polycarbonate, polystyrene, polyarylate, and polyester.
- a material that is cured by heat or light a material in which a curable functional group is introduced into the molecule in the hole transporting compound, a curable resin, or the like can be used.
- examples of the curable functional group include acrylic functional groups such as acryloyl group and methacryloyl group, vinylene group, epoxy group, and isocyanate group.
- the curable resin may be a thermosetting resin or a photocurable resin, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, a polyester resin, a polyurethane resin, a silicon resin, and a silane coupling agent. be able to.
- the thickness of the hole injecting and transporting layer can be appropriately determined depending on the purpose and the adjacent layer, but is usually 0.1 to 1000 nm, preferably 1 to 500 nm.
- the work function of the hole injection transport layer is preferably 5.0 to 6.0 eV, more preferably 5.0 to 5.8 eV, from the viewpoint of hole injection efficiency.
- the hole injecting and transporting layer of the present invention can be formed by a solution coating method, and the manufacturing process is easy and the yield is high because a short circuit hardly occurs, and a long life is achieved by forming a charge transfer complex.
- the hole injecting and transporting layer of the present invention is prepared by a solution coating method using a solution (ink for forming a hole injecting and transporting layer) dissolved or dispersed in a solvent in which at least the transition metal complex is dissolved or dispersed well. It is preferable that it is formed.
- the hole injecting and transporting layer of the present invention comprises the transition metal complex and the hole transporting compound in a solvent in which both are well dissolved or dispersed.
- It is preferably formed by a solution coating method using a mixed solution.
- a solution coating method using a mixed solution.
- the reaction product of the transition metal complex interacts with the hole transporting compound in the solution, Since it becomes easy to form a charge transfer complex, it is possible to form a hole injecting and transporting layer having excellent hole transportability and stability over time of the film.
- the hole injecting and transporting layer in which the charge transfer complex is formed in this way tends to be insoluble in the solvent used when forming the hole injecting and transporting layer. Also in the case of forming a layer, the possibility of using the solution coating method without elution of the hole injection transport layer is widened.
- the solution coating method will be described below in the item of device manufacturing method.
- the substrate serves as a support for the device of the present invention, and may be, for example, a flexible material or a hard material.
- materials that can be used include glass, quartz, polyethylene, polypropylene, polyethylene terephthalate, polymethacrylate, polymethyl methacrylate, polymethyl acrylate, polyester, and polycarbonate.
- the thickness of the substrate is not particularly limited, but is usually about 0.5 to 2.0 mm.
- Electrode has two or more electrodes which oppose on a board
- the electrode is preferably formed of a metal or a metal oxide, and a known material can be appropriately employed. Usually, it can be formed of a metal such as aluminum, gold, silver, nickel, palladium, platinum, or a metal oxide such as an oxide of indium and / or tin.
- the electrode is often formed on the substrate by a method such as a sputtering method or a vacuum deposition method, but can also be formed by a wet method such as a coating method or a dipping method.
- the thickness of the electrode varies depending on the transparency required for each electrode. When transparency is required, it is desirable that the light transmittance in the visible wavelength region of the electrode is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 10 to 1000 nm, The thickness is preferably about 20 to 500 nm.
- a metal layer may be further provided on the electrode in order to improve the adhesion stability with the charge injection material.
- the metal layer refers to a layer containing a metal, and is formed from a metal or metal oxide used for the above-described normal electrode.
- the device of the present invention may have a conventionally known electron injection layer and / or electron transport layer between the electron injection electrode and the hole injection transport layer as necessary.
- Organic EL element As one Embodiment of the device of this invention, the organic EL element containing the organic layer containing the positive hole injection transport layer and light emitting layer of this invention at least is mentioned.
- each layer constituting the organic EL element will be described in order with reference to FIGS. (substrate)
- the substrate 7 becomes a support for the organic EL element, and may be a flexible material or a hard material, for example. Specifically, for example, those described in the description of the substrate of the device can be used.
- the substrate 7 needs to be made of a transparent material.
- the electrode 1 and the electrode 6 differ depending on the direction in which the light emitted from the light emitting layer 5 is extracted. Which electrode is required to have transparency or not, the electrode 1 is transparent when the light is extracted from the substrate 7 side. It is necessary to form the electrode 6 with a transparent material when it is necessary to form the electrode 6 and light is extracted from the electrode 6 side.
- the electrode 1 provided on the light emitting layer side of the substrate 7 acts as an anode for injecting holes into the light emitting layer, and the electrode 6 provided on the light emitting layer side of the substrate 7 injects electrons into the light emitting layer 5. Acting as a cathode.
- the anode and the cathode are preferably formed of the metals or metal oxides listed in the description of the electrode of the device.
- the hole injection transport layer 2, the hole transport layer 4a, and the hole injection layer 4b are appropriately formed between the light emitting layer 5 and the electrode 1 (anode) as shown in FIGS.
- a hole transport layer 4a may be further stacked on the hole injection transport layer 2 according to the present invention, and a light emitting layer may be stacked thereon, or as shown in FIG.
- the hole injecting and transporting layer 2 according to the present invention may be further laminated on the injection layer 4b, and the light emitting layer may be further laminated thereon.
- the hole injecting and transporting layer 2 may be laminated and a light emitting layer may be laminated thereon.
- the hole transport material used for the hole transport layer 4a is not particularly limited. It is preferable to use the hole transporting compound described in the hole injecting and transporting layer according to the present invention. Among them, the use of the same compound as the hole transporting compound used in the adjacent hole injection transport layer 2 according to the present invention improves the adhesion stability of the interface between the hole injection transport layer and the hole transport layer. Therefore, it is preferable because it contributes to a longer driving life.
- the hole transport layer 4a can be formed using a hole transport material in the same manner as the light emitting layer described later.
- the film thickness of the hole transport layer 4a is usually 0.1 to 1 ⁇ m, preferably 1 to 500 nm.
- the hole injection material used for the hole injection layer 4b is not particularly limited.
- Known compounds can be used. Examples thereof include phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, oxides such as aluminum oxide, amorphous carbon, polyaniline, and polythiophene derivatives.
- the hole injection layer 4b can be formed using a hole injection material in the same manner as the light emitting layer described later.
- the thickness of the hole injection layer 4b is usually 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
- HOMO work function
- the material constituting the hole injection transport layer As the reactant of the vanadium complex (work function 5.2 eV), TFB (work function 5.4 eV) as the material constituting the hole transport layer, and from the electrode 1 side toward the light emitting layer 5, It is preferable to arrange the layers so that the values of work functions increase in order.
- the work function or HOMO value was quoted from the measured value of photoelectron spectroscopy using a photoelectron spectrometer AC-1 (manufactured by Riken Keiki).
- the light emitting layer 5 is formed of a light emitting material between the substrate 7 on which the electrode 1 is formed and the electrode 6, as shown in FIGS.
- the material used for the light emitting layer of the present invention is not particularly limited as long as it is a material usually used as a light emitting material, and either a fluorescent material or a phosphorescent material can be used. Specific examples include materials such as dye-based light-emitting materials and metal complex-based light-emitting materials, and both low molecular compounds and high molecular compounds can be used.
- dye-based luminescent materials include arylamine derivatives, anthracene derivatives, (phenylanthracene derivatives), oxadiazole derivatives, oxazole derivatives, oligothiophene derivatives, carbazole derivatives, cyclopentadiene derivatives, silole derivatives, distyrylbenzene derivatives, Distyrylpyrazine derivatives, distyrylarylene derivatives, silole derivatives, stilbene derivatives, spiro compounds, thiophene ring compounds, tetraphenylbutadiene derivatives, triazole derivatives, triphenylamine derivatives, trifumanylamine derivatives, pyrazoloquinoline derivatives, hydrazone derivatives, pyras Examples include zoline dimer, pyridine ring compound, fluorene derivative, phenanthroline, perinone derivative, perylene derivative. These dime dimer, pyridine ring compound, fluorene derivative
- metal complex-based light-emitting materials examples include an aluminum quinolinol complex, a benzoquinolinol beryllium complex, a benzoxazole zinc complex, a benzothiazole zinc complex, an azomethylzinc complex, a porphyrin zinc complex, a europium complex, and the central metal such as Al, Zn, Be, etc.
- 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 can be given. These materials may be used alone or in combination of two or more.
- the high molecular weight light emitting material a material obtained by introducing the above low molecular weight material into the molecule as a straight chain, a side chain, or a functional group, a polymer, a dendrimer, or the like can be used.
- examples thereof include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinyl carbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, and copolymers thereof.
- a doping material may be added to the light emitting layer for the purpose of improving the light emission efficiency or changing the light emission wavelength.
- these may be included as a light emitting group in the molecular structure.
- doping materials include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacdrine derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, and fluorene derivatives. Can be mentioned.
- transduced the spiro group into these can also be used. These materials may be used alone or in combination of two or more.
- a phosphorescent dopant an organometallic complex having heavy metal ions such as platinum and iridium as a center and exhibiting phosphorescence can be used.
- Ir (ppy) 3 is used.
- the material of the light emitting layer 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.
- the hole injection / transport layer forms a charge transfer complex and is a non-aqueous solvent such as xylene used in the solution coating method.
- a material for the light emitting layer it is possible to use a polymer material that is easily dissolved in a non-aqueous solvent such as xylene and forms a layer by a solution coating method.
- a high molecular compound containing a fluorescent compound or a low molecular compound that emits fluorescence, or a high molecular compound containing a phosphor compound or a low molecular compound that emits phosphor can be preferably used.
- the light emitting layer can be formed using a light emitting material by a solution coating method, a vapor deposition method, or a transfer method.
- a solution coating method and the vapor deposition method the same method as described in the item of the device manufacturing method described later can be used.
- the transfer method for example, a light emitting layer previously formed on a film by a solution coating method or a vapor deposition method is bonded to the hole injection transport layer 2 provided on the electrode, and the light emitting layer 5 is heated to form the hole injection transport layer 2. It is formed by transferring it upward.
- the hole injecting and transporting layer side of the laminate laminated in the order of the film, the light emitting layer 5 and the hole injecting and transporting layer 2 may be transferred onto the electrode.
- the thickness of the light emitting layer is usually about 1 to 1000 nm, preferably about 20 to 500 nm.
- the process cost can be reduced when the light emitting layer is also formed by a solution coating method.
- Organic Transistor Another embodiment of the device according to the present invention is an organic transistor.
- each layer which comprises an organic transistor is demonstrated using FIG.5 and FIG.6. Since the hole injecting and transporting layer 2 is formed on the surfaces of the electrode 1 (source electrode) and the electrode 6 (drain electrode), the organic transistor of the present invention as shown in FIG.
- the hole injecting and transporting capacity between the two and the hole injecting and transporting layer of the present invention is high, and the film stability of the hole injecting and transporting layer of the present invention is high.
- the hole injection transport layer 2 of the present invention may function as the organic semiconductor layer 8 as shown in FIG. Further, as shown in FIG.
- the organic transistor of the present invention has a hole injecting and transporting layer 2 formed on the surfaces of an electrode 1 (source electrode) and an electrode 6 (drain electrode), and further, an organic semiconductor layer 8 as an electrode surface.
- the hole injecting and transporting layer 2 of the present invention may be formed of a material different from that of the hole injecting and transporting layer.
- a donor (p-type) low molecular or high molecular organic semiconductor material can be used as a material for forming the organic semiconductor layer.
- the organic semiconductor materials include porphyrin derivatives, arylamine derivatives, polyacene derivatives, perylene derivatives, rubrene derivatives, coronene derivatives, perylenetetracarboxylic acid diimide derivatives, perylenetetracarboxylic acid dianhydride derivatives, polythiophene derivatives, polyparaphenylene derivatives, Polyparaphenylene vinylene derivatives, polypyrrole derivatives, polyaniline derivatives, polyfluorene derivatives, polythiophene vinylene derivatives, polythiophene-heterocyclic aromatic copolymers and derivatives thereof, ⁇ -6-thiophene, ⁇ -4-thiophene, naphthalene oligoacene derivatives, Oligothiophene derivatives of
- porphyrin derivatives include metal phthalocyanines such as phthalocyanine and copper phthalocyanine.
- arylamine derivatives include m-TDATA.
- polyacene derivatives include naphthalene, anthracene, and naphthacene. And pentacene.
- the compound constituting the organic semiconductor layer 8 is the hole injecting and transporting layer of the present invention.
- a hole transporting compound especially a hole transporting polymer compound, improves the adhesion stability of the interface between the hole injecting and transporting layer 2 and the organic semiconductor layer 8 of the present invention and prolonging the driving life. It is preferable from the point of contribution.
- the carrier mobility of the organic semiconductor layer is preferably 10 ⁇ 6 cm / Vs or more, and particularly preferably 10 ⁇ 3 cm / Vs or more for an organic transistor from the viewpoint of transistor characteristics.
- the organic semiconductor layer can be formed by a solution coating method or a dry process, similarly to the light emitting layer of the organic EL element.
- 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.
- the substrate 7 serves as a support for the device of the present invention, and may be a flexible material or a hard material, for example. Specifically, the same substrate as that of the organic EL element can be used.
- the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are conductive materials. However, hole injection formed by adsorption of a compound coordinated with metal ions using the charge transport material according to the present invention. From the viewpoint of forming the transport layer 2, a metal or a metal oxide is preferable. Specifically, the same metal or metal oxide as the electrode in the above-mentioned organic EL element can be used, but platinum, gold, silver, copper, aluminum, indium, ITO and carbon are particularly preferable.
- 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.
- 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.
- 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.
- organic compounds examples include polyimides, polyamides, polyesters, polyacrylates, photocuring resins based on radical photopolymerization, photocationic polymerization, or copolymers containing acrylonitrile components, polyvinylphenol, polyvinyl alcohol, novolac resins, and cyanoethyl.
- a pullulan, a polymer body, a phosphazene compound including an elastomer body, and the like can be used.
- a hole injection / transport layer is also used.
- the hole injecting and transporting layer according to the present invention other configurations are not particularly limited, and may be the same as known configurations as appropriate.
- the device manufacturing method of the present invention is a method for manufacturing a device having two or more electrodes facing each other on a substrate and a hole injecting and transporting layer disposed between the two electrodes.
- the central metal includes at least one transition metal selected from the group consisting of vanadium, rhenium and platinum, or one or more transition metals selected from the group consisting of vanadium, rhenium and platinum and molybdenum.
- the hole injection transport layer is formed by a solution coating method using the hole injection transport layer forming ink as described above.
- a vapor deposition apparatus is not required when forming the hole injection transport layer, and coating can be performed without using mask vapor deposition, etc., and productivity is high.
- a device having high adhesion stability between the interface of the injection transport layer and the interface of the hole injection transport layer and the organic layer can be formed.
- the solution coating method means that the central metal contains at least one transition metal selected from the group consisting of vanadium, rhenium and platinum, or one type selected from the group consisting of vanadium, rhenium and platinum.
- a hole injection transport layer forming ink containing at least a transition metal complex, which is a mixture of the above transition metal and molybdenum, and an organic solvent having a carbonyl group and / or a hydroxyl group is prepared, and the ink is used as an underlying electrode. Or it is the method of apply
- the hole injection / transport layer forming ink is dissolved or dispersed by adding a hole transporting compound and additives such as a binder resin and a coating property improving agent that do not trap holes as necessary to a solvent. May be prepared.
- solution coating method examples include immersion methods, spray coating methods, spin coating methods, blade coating methods, dip coating methods, casting methods, roll coating methods, bar coating methods, die coating methods, and liquid dropping methods such as inkjet methods. It is done. When it is desired to form a monomolecular film, a dipping method or a dip coating method is preferably used.
- an organic solvent having a carbonyl group and / or a hydroxyl group capable of oxidation-reduction reaction with the transition metal complex is used.
- an organic solvent the same solvents as described above can be used.
- organic solvents having a carbonyl group and / or a hydroxyl group those which are dissolved or dispersed well with other components such as a hole transporting compound are selected and used as necessary.
- a layer containing a transition metal oxide having no solvent solubility is formed by an evaporation method by having an oxidation step in which at least a part of the transition metal complex is a transition metal oxide. It can be formed by using a solution coating method without using it.
- the hole injecting and transporting layer as a transition metal oxide, the hole injecting and transporting property can be appropriately changed while maintaining the adhesion with the adjacent organic layer. Is also possible.
- the oxidation step may be performed after preparing the hole injection transport layer forming ink and before the step of forming the hole injection transport layer, or the hole injection transport layer. You may perform after the process of forming.
- a hole injection transport layer forming ink containing the transition metal complex and an organic solvent having a carbonyl group and / or a hydroxyl group is prepared, and on any layer on the electrode,
- the method include a step of forming a hole injection / transport layer containing the transition metal complex and an oxidation step in which at least a part of the transition metal complex in the hole injection / transport layer is a transition metal oxide. . If it does in this way, the positive hole injection transport layer containing the reaction product of the said transition metal complex can be formed.
- the organic solvent in the layer containing the transition metal complex and the organic solvent is removed. It may be performed while drying.
- the oxidation step is carried out to form a transition metal oxide by oxidation.
- the manufacturing method which has the process of forming the positive hole injection transport layer containing the said transition metal oxide on any layer on the said electrode using the ink for positive hole injection transport layer formation containing is mentioned. If it does in this way, the positive hole injection transport layer containing the reaction product of the said transition metal complex can be formed. After forming the layer, an oxidation step may be further performed.
- the oxided hole injection transport layer forming ink can be obtained by performing a redox reaction between the transition metal and an organic solvent having a carbonyl group and / or a hydroxyl group.
- Examples of the means for oxidizing include a heating step, a light irradiation step, a step of applying active oxygen, and the like, and these may be used in combination as appropriate. Oxidation is preferably carried out in the presence of oxygen in order to efficiently oxidize.
- examples of the heating means include a method of heating on a hot plate and a method of heating in an oven. The heating temperature is preferably 50 to 250 ° C. Depending on the heating temperature, the reactivity of the transition metal complex, the interaction between the transition metal complexes, and the interaction of the transition metal complex with the hole-transporting compound are preferably adjusted accordingly.
- examples of the light irradiation means include a method of exposing to ultraviolet rays.
- the reactivity of the transition metal complex, the interaction between the transition metal complexes, and the interaction of the transition metal complex with the hole transporting compound are preferably adjusted accordingly.
- a method of generating active oxygen by using ultraviolet rays or a method of generating active oxygen by irradiating ultraviolet rays onto a photocatalyst such as titanium oxide is generated.
- the method of making it act is mentioned.
- the amount of active oxygen there is a difference in the reactivity of the transition metal complex, the interaction of the transition metal complex with the hole transporting compound, and the interaction between the transition metal complexes.
- Example 1 A laminate of a transparent anode on a glass substrate, a layer containing a reaction product (organic-inorganic complex) of vanadium (III) acetylacetonate as a hole injecting and transporting layer, and a layer containing a hole transporting compound; A hole transport layer, a light emitting layer, an electron injection layer, and a cathode were formed and laminated in this order, and finally sealed to prepare an organic EL device. The work was performed in a nitrogen-substituted glove box having a moisture concentration of 0.1 ppm or less and an oxygen concentration of 0.1 ppm or less except for the transparent anode and the hole injection transport layer.
- a thin film (thickness: 150 nm) of indium tin oxide (ITO) was used as a transparent anode.
- a glass substrate with ITO manufactured by Sanyo Vacuum Co., Ltd.
- the patterned ITO substrate was ultrasonically cleaned in the order of neutral detergent and ultrapure water, and then subjected to UV ozone treatment.
- the HOMO (work function) of ITO after UV ozone treatment was 5.0 eV.
- vanadium (III) acetylacetonate vanadium complex, manufactured by Sigma-Aldrich
- cyclohexanone a concentration of 0.4 mass%
- the hole injecting and transporting layer (1) forming coating solution was applied onto the cleaned anode by a spin coating method to form a hole injecting and transporting layer containing a vanadium complex.
- the coating solution for forming the hole injecting and transporting layer (1) it was dried at 200 ° C. for 30 minutes using a hot plate in order to evaporate the solvent.
- the thickness of the hole injection transport layer (1) after drying was 5 nm or less.
- TFB poly [(9,9-dioctylfluorenyl-2,7- Diyl) -co- (4,4 ′-(N- (4-sec-butylphenyl)) diphenylamine)] (TFB) thin film (thickness: 10 nm) was formed.
- a bis (2-methyl-8-quinolato) (p-phenylphenolate) aluminum complex (BAlq) thin film was formed as a hole blocking layer on the light emitting layer by vapor deposition.
- the BAlq thin film was formed in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) so as to have a film thickness of 15 nm by a resistance heating method.
- a tris (8-quinolinolato) aluminum complex (Alq 3 ) thin film was deposited on the hole blocking layer as an electron transporting layer.
- the Alq 3 thin film was formed in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) so as to have a film thickness of 15 nm by a resistance heating method.
- LiF thinness: 0.5 nm
- Al thinness: 100 nm
- a film was formed by resistance heating vapor deposition in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa).
- sealing was performed using a non-alkali glass and a UV curable epoxy adhesive in a glove box, and an organic EL device of Example 1 was produced.
- Example 2 For hole injection / transport layer (1) formation in Example 1 including pentacarbonylchlororhenium (I) (rhenium complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate An organic EL device of Example 2 was produced in the same manner as in Example 1 except that the coating solution was used.
- Example 3 For forming the hole injection / transport layer (1) in which the hole injection / transport layer in Example 1 contains platinum (II) acetylacetonate (platinum complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate An organic EL device of Example 3 was produced in the same manner as Example 1 except that the coating solution was used.
- Example 4 The hole injecting and transporting layer in Example 1 is a mixture of pentacarbonylchlororhenium (I) (Sigma-Aldrich) and molybdenum hexacarbonyl (Kanto Kagaku Co., Ltd.) instead of vanadium (III) acetylacetonate (
- An organic EL device of Example 4 was produced in the same manner as in Example 1 except that it was formed using a coating solution for forming a hole injection transport layer (1) containing a mixture of a rhenium complex and a molybdenum complex.
- the hole injecting and transporting layer (1) forming coating solution was prepared by dissolving the above two materials at a concentration of 0.2% by mass in cyclohexanone.
- a hole injection / transport layer (1) forming coating solution containing scandium acetylacetonate (scandium complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate is used as the hole injection / transport layer in Example 1.
- An organic EL device of Reference Example 1 was produced in the same manner as in Example 1 except that it was used.
- Example 1 an organic EL device of Comparative Example 1 was produced in the same manner as in Example 1 except that toluene, which is an aromatic solvent, was used instead of cyclohexanone as the solvent for dissolving the vanadium complex.
- Example 2 In Example 1, a vanadium oxide (V 2 O 5 ) thin film (thickness: 5 nm) was formed instead of forming a vanadium complex thin film as the hole injecting and transporting layer. 2 organic EL elements were produced. The vanadium oxide (V 2 O 5 ) thin film was formed by resistance heating vapor deposition in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa).
- the hole injecting and transporting layer in Example 1 contains cobalt (III) acetylacetonate (cobalt complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate.
- An organic EL device of Comparative Example 3 was produced in the same manner as in Example 1 except that the coating solution was used.
- the hole injecting and transporting layer in Example 1 contains copper (II) acetylacetonate (copper complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate.
- An organic EL element of Comparative Example 5 was produced in the same manner as in Example 1 except that the coating solution was used.
- Example 7 The hole injecting and transporting layer in Example 1 was prepared by applying a coating solution for forming a hole injecting and transporting layer (1) containing zinc acetylacetonate (zinc complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate.
- An organic EL device of Comparative Example 7 was produced in the same manner as in Example 1 except that it was used.
- Comparative Example 8 For forming the hole injection / transport layer (1) in which the hole injection / transport layer in Example 1 contains chromium (III) acetylacetonate (chromium complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate An organic EL device of Comparative Example 8 was produced in the same manner as in Example 1 except that the coating solution was used.
- chromium (III) acetylacetonate chromium complex, manufactured by Sigma-Aldrich
- Example 9 The hole injecting and transporting layer in Example 1 was prepared by applying a coating solution for forming the hole injecting and transporting layer (1) containing titanium isopropoxide (titanium complex, Sigma-Aldrich) instead of vanadium (III) acetylacetonate.
- An organic EL device of Comparative Example 9 was produced in the same manner as in Example 1 except that it was used.
- the hole injecting and transporting layer in Example 1 contains manganese (III) acetylacetonate (manganese complex, manufactured by Sigma-Aldrich) instead of vanadium (III) acetylacetonate.
- An organic EL device of Comparative Example 10 was produced in the same manner as in Example 1 except that the coating solution was used.
- HOMO work function
- the organic EL elements produced in the above examples and comparative examples all emitted green light derived from Ir (mppy) 3 .
- a spectroradiometer SR-2 manufactured by Topcon Co., Ltd. was driven at 10 mA / cm 2 to measure emission luminance and spectrum.
- the measurement results are shown in Table 1.
- the current efficiency was calculated from the drive current and the luminance.
- the lifetime characteristics of the organic EL element were evaluated by observing the luminance gradually decreasing with time by constant current driving.
- the time (hr.) Until the retention rate deteriorates to a luminance of 50% with respect to the initial luminance of 2000 cd / m 2 is defined as a lifetime (LT50).
- Example 1 and Comparative Example 1 the element of the hole injection transport layer of Example 1 obtained from the reaction product of the vanadium complex rather than the hole injection transport layer of Comparative Example 1 coated with the vanadium complex.
- the voltage was much lowered, the lifetime was long, and the device performance was high.
- the organic-inorganic composite obtained in the present invention was transformed into a material different from the vanadium complex, and a hole injection / transport layer having high hole injection property and excellent driving stability was formed. Show.
- Example 1 and Comparative Example 2 are compared, the element of the hole injecting and transporting layer of Example 1 obtained from the reaction product of the vanadium complex rather than the hole injecting and transporting layer of Comparative Example 2 of the deposited film of vanadium oxide.
- the hole injecting and transporting layer which is the organic-inorganic composite obtained in the present invention, has a higher hole injecting property and superior driving stability than the deposited film of vanadium oxide.
- Hole injection including at least one transition metal selected from the group consisting of vanadium, rhenium, and platinum as a central metal of the transition metal complex, or forming a reaction product using a mixture of rhenium and molybdenum All of the devices of Examples 1 to 4 including the transport layer had high characteristics.
- Electrode 2 Hole injection transport layer 3 Organic layer 4a Hole transport layer 4b Hole injection layer 5 Light emitting layer 6 Electrode 7 Substrate 8 Organic semiconductor layer 9 Electrode 10 Insulating layer
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Abstract
Description
特許文献1においては、酸化性化合物すなわち電子受容性化合物として、トリフェニルアミン誘導体と6フッ化アンチモン等の対アニオンを含む化合物や7,7,8,8-テトラシアノキノジメタン等の炭素-炭素二重結合の炭素にシアノ基が結合した電子受容性が極めて高い化合物が用いられている。
特許文献2においては、酸化性ドーパントとして、一般的な酸化剤が挙げられ、ハロゲン化金属、ルイス酸、有機酸、及びアリールアミンとハロゲン化金属又はルイス酸との塩が挙げられている。
特許文献7においては、酸化性化合物すなわち電子受容性化合物として、オキソバナジウム(V)トリ-i-プロポキシドオキシドを溶解させた溶液を用い、それと正孔輸送性高分子との混合塗膜の形成後に水蒸気中で加水分解させてバナジウム酸化物として、電荷移動錯体を形成させる作製方法が挙げられている。
特許文献8においては、三酸化モリブデンの塗膜形成の試みとして、三酸化モリブデンを物理的に粉砕して作製した微粒子を溶液に分散させてスラリーを作製し、それを塗工して正孔注入層を形成して長寿命な有機EL素子を作製することが記載されている。
成膜性や薄膜の安定性は素子の寿命特性と大きく関係する。一般的に有機EL素子の寿命とは、一定電流駆動などで連続駆動させたときの輝度半減時間とし、輝度半減時間が長い素子ほど長駆動寿命であるという。
すなわち、本発明のデバイスは、基板上に対向する2つ以上の電極と、そのうちの2つの電極間に配置された正孔注入輸送層を有するデバイスであって、
前記正孔注入輸送層が、遷移金属錯体の反応生成物を含有し、当該遷移金属錯体の中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物であることを特徴とする。
また、本発明のデバイスにおいては、前記遷移金属錯体の配位子の種類を選択したり配位子を修飾することにより、溶剤溶解性や親水性・疎水性、電荷輸送性、あるいは密着性などの機能性を付与するなど、多機能化することが容易である。
本発明のデバイスの正孔注入輸送層に用いられる前記遷移金属錯体は、適宜選択することにより合成ステップ数が少なく簡単に合成できるため、安価に高性能なデバイスを作製することができる。
中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物である遷移金属錯体と、カルボニル基及び/又は水酸基を有する有機溶媒とを含有する正孔注入輸送層形成用インクを調製する工程と、前記正孔注入輸送層形成用インクを用いて、前記電極上のいずれかの層上に正孔注入輸送層を形成する工程と、前記遷移金属錯体の少なくとも一部を遷移金属酸化物とする酸化工程とを有することを特徴とする。
すなわち、一態様としては、前記電極上のいずれかの層上に、前記遷移金属錯体を含有する正孔注入輸送層を形成する工程と、前記正孔注入輸送層中の当該遷移金属錯体の少なくとも一部を遷移金属酸化物とする酸化工程を有する。
別の一態様としては、前記正孔注入輸送層形成用インクを調製する工程後、正孔注入輸送層を形成する工程前に、前記酸化工程が実施され、酸化物化された正孔注入輸送層形成用インクを用いて、前記電極上のいずれかの層上に遷移金属酸化物を含有する正孔注入輸送層を形成する工程を有する。
本発明に係るデバイスの製造方法によれば、製造プロセスが容易でありながら、長寿命を達成可能なデバイスを提供することが可能である。
また、本発明に係る正孔注入輸送層形成用インクによれば、製造プロセスが容易でありながら、長寿命を達成可能なデバイスを提供することが可能である。
本発明のデバイスは、基板上に対向する2つ以上の電極と、そのうちの2つの電極間に配置された正孔注入輸送層を有するデバイスであって、前記正孔注入輸送層が、遷移金属錯体の反応生成物を含有し、当該遷移金属錯体の中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物であることを特徴とする。
また、本発明のデバイスの正孔注入輸送層によれば、上記遷移金属錯体において配位子の種類を選択したり配位子を修飾することにより、溶剤溶解性や親水性・疎水性、電荷輸送性、あるいは密着性などの機能性を付与するなど、多機能化することが容易である。
本発明のデバイスの正孔注入輸送層に用いられる上記遷移金属錯体は、適宜選択することにより合成ステップ数が少なく簡単に合成できるため、安価に高性能なデバイスを作製することができる。
本発明に係るデバイスは、基板上に対向する2つ以上の電極と、そのうちの2つの電極間に配置された正孔注入輸送層を有するデバイスである。
本発明に係るデバイスには、有機EL素子、有機トランジスタ、色素増感太陽電池、有機薄膜太陽電池、有機半導体を包含する有機デバイスのほか、正孔注入輸送層を有する量子ドット発光素子、酸化物系化合物太陽電池等も含まれる。
図1は本発明に係る有機デバイスの基本的な層構成を示す断面概念図である。本発明のデバイスの基本的な層構成は、基板7上に対向する2つの電極(1及び6)と、その2つの電極(1及び6)間に配置され少なくとも正孔注入輸送層2を含む有機層3を有する。
基板7は、デバイスを構成する各層を形成するための支持体であり、必ずしも電極1の表面に設けられる必要はなく、デバイスの最も外側の面に設けられていればよい。
有機層3は、正孔注入輸送されることにより、デバイスの種類によって様々な機能を発揮する層であり、単層からなる場合と多層からなる場合がある。有機層が多層からなる場合は、有機層は、正孔注入輸送層の他に更に、デバイスの機能の中心となる層(以下、機能層と称呼する。)や、当該機能層の補助的な層(以下、補助層と称呼する。)を含んでいる。例えば、有機EL素子の場合、正孔注入輸送層の表面に更に積層される正孔輸送層が補助層に該当し、当該正孔輸送層の表面に積層される発光層が機能層に該当する。
電極6は、対向する電極1との間に正孔注入輸送層2を含む有機層3が存在する場所に設けられる。また、必要に応じて、図示しない第三の電極を有していてもよい。これらの電極間に電場を印加することにより、デバイスの機能を発現させることができる。
図3は、本発明に係るデバイスの一実施形態である有機EL素子の層構成の別の一例を示す断面模式図である。本発明の有機EL素子は、電極1の表面に補助層として正孔注入層4bが形成され、当該正孔注入層4bの表面に正孔注入輸送層2、機能層として発光層5が積層された形態を有する。このように、本発明に特徴的な正孔注入輸送層を正孔輸送層の位置で用いる場合には、導電率の向上に加え、当該正孔注入輸送層は電荷移動錯体を形成して溶液塗布法に用いた溶媒に不溶になるので、上層の発光層を積層する際にも溶液塗布法を適用することが可能である。
図4は、本発明に係るデバイスの一実施形態である有機EL素子の層構成の別の一例を示す断面模式図である。本発明の有機EL素子は、電極1の表面に正孔注入輸送層2、機能層として発光層5が順次積層された形態を有する。このように、本発明に特徴的な正孔注入輸送層を1層で用いる場合には、工程数が削減されるというプロセス上のメリットがある。
なお、上記図2~図4においては、正孔注入輸送層2、正孔輸送層4a、正孔注入層4bのそれぞれが、単層ではなく複数層から構成されているものであっても良い。
素子の外部に光を放射するため、発光層の少なくとも一方の面に存在する全ての層は、可視波長域のうち少なくとも一部の波長の光に対する透過性を有することを必要とする。また、発光層と電極6(陰極)の間には、必要に応じて電子輸送層及び/又は電子注入層が設けられていてもよい(図示せず)。
上記、有機トランジスタは、ゲート電極における電荷の蓄積を制御することにより、ソース電極-ドレイン電極間の電流を制御する機能を有する。
以下、本発明に係るデバイスの各層について詳細に説明する。
本発明のデバイスは、少なくとも正孔注入輸送層を含む。本発明のデバイスが有機デバイスであって、有機層が多層の場合には、有機層は、正孔注入輸送層の他に更に、デバイスの機能の中心となる層や、当該機能層を補助する役割を担う補助層を含んでいるが、それらの機能層や補助層は、後述するデバイスの具体例において、詳細に述べる。
また、本発明の効果を損なわない限り、芳香環及び/又は複素環を含む構造に置換基を有していても良い。置換基としては、例えば、炭素数1~20の直鎖または分岐のアルキル基、ハロゲン原子、炭素数1~20のアルコキシ基、シアノ基、ニトロ基等が挙げられる。炭素数1~20の直鎖または分岐のアルキル基の中では、炭素数1~12の直鎖または分岐のアルキル基、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が好ましい。
なお、当該遷移金属酸化物には処理条件によって様々な価数の遷移金属原子や化合物、例えば炭化物や窒化物などが混在していても良い。
正孔輸送性化合物としては、低分子化合物の他、高分子化合物も好適に用いられる。正孔輸送性高分子化合物は、正孔輸送性を有し、且つ、ゲル浸透クロマトグラフィーのポリスチレン換算値による重量平均分子量が2000以上の高分子化合物をいう。本発明の正孔注入輸送層においては、溶液塗布法により安定な膜を形成することを目的として、正孔輸送性材料としては有機溶媒に溶解しやすく且つ化合物が凝集し難い安定な塗膜を形成可能な高分子化合物を用いることが好ましい。
また、正孔輸送性高分子化合物としては、例えばアリールアミン誘導体、アントラセン誘導体、カルバゾール誘導体、チオフェン誘導体、フルオレン誘導体、ジスチリルベンゼン誘導体、スピロ化合物等を繰り返し単位に含む重合体を挙げることができる。
nの平均は、5~5000であることが好ましく、更に10~3000であることが好ましい。また、mの平均は、5~5000であることが好ましく、更に10~3000であることが好ましい。また、n+mの平均は、10~10000であることが好ましく、更に20~6000であることが好ましい。
正孔注入輸送層において、前記正孔輸送性化合物の含有量が少なすぎると、正孔輸送性化合物を混合した相乗効果が得られ難い。一方、前記正孔輸送性化合物の含有量が多すぎると、上記遷移金属錯体を用いる効果が得られ難くなる。
また、上記正孔注入輸送層の仕事関数は5.0~6.0eV、更に5.0~5.8eVであることが、正孔注入効率の点から好ましい。
溶液塗布法は、下記、デバイスの製造方法の項目において説明する。
基板は、本発明のデバイスの支持体になるものであり、例えばフレキシブルな材質であっても、硬質な材質であってもよい。具体的に用いることができる材料としては、例えば、ガラス、石英、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリメタクリレート、ポリメチルメタクリレート、ポリメチルアクリレート、ポリエステル、ポリカーボネート等を挙げることができる。
これらのうち、合成樹脂製の基板を使用する場合には、ガスバリア性を有することが望ましい。基板の厚さは特に限定されないが、通常、0.5~2.0mm程度である。
本発明のデバイスは、基板上に対向する2つ以上の電極を有する。
本発明のデバイスにおいて、電極は、金属又は金属酸化物で形成されることが好ましく、公知の材料を適宜採用することができる。通常、アルミニウム、金、銀、ニッケル、パラジウム、白金等の金属、インジウム及び/又はスズの酸化物などの金属酸化物により形成することができる。
本発明においては、電極上に、電荷注入材料との密着安定性を向上させるために、更に金属層を有していても良い。金属層は金属が含まれる層をいい、上述のような通常電極に用いられる金属や金属酸化物から形成される。
本発明のデバイスは、必要に応じて、電子注入電極と正孔注入輸送層の間に、従来公知の電子注入層及び/又は電子輸送層を有していてもよい。
本発明のデバイスの一実施形態として、少なくとも本発明の正孔注入輸送層及び発光層を含む有機層を含有する、有機EL素子が挙げられる。
以下、有機EL素子を構成する各層について、図2~4を用いて順に説明する。
(基板)
基板7は、有機EL素子の支持体になるものであり、例えばフレキシブルな材質であっても、硬質な材質であってもよい。具体的には、例えば、上記デバイスの基板の説明において挙げたものを用いることができる。
発光層5で発光した光が基板7側を透過して取り出される場合においては、少なくともその基板7が透明な材質である必要がある。
電極1および電極6は、発光層5で発光した光の取り出し方向により、どちらの電極に透明性が要求されるか否かが異なり、基板7側から光を取り出す場合には電極1を透明な材料で形成する必要があり、また電極6側から光を取り出す場合には電極6を透明な材料で形成する必要がある。
基板7の発光層側に設けられている電極1は、発光層に正孔を注入する陽極として作用し、基板7の発光層側に設けられている電極6は、発光層5に電子を注入する陰極として作用する。
本発明において、陽極及び陰極は、上記デバイスの電極の説明において列挙した金属又は金属酸化物で形成されることが好ましい。
正孔注入輸送層2、正孔輸送層4a、及び正孔注入層4bは、図2~4に示すように、発光層5と電極1(陽極)の間に適宜形成される。図2のように、本発明に係る正孔注入輸送層2の上に更に正孔輸送層4aを積層し、その上に発光層を積層してもよいし、図3のように、正孔注入層4bの上に更に本発明に係る正孔注入輸送層2を積層し、その上に発光層を積層してもよいし、図4のように、電極1の上に、本発明に係る正孔注入輸送層2を積層しその上に発光層を積層してもよい。
正孔輸送層4aは、正孔輸送材料を用いて、後述の発光層と同様方法で形成することができる。正孔輸送層4aの膜厚は、通常0.1~1μm、好ましくは1~500nmである。
正孔注入層4bは、正孔注入材料を用いて、後述の発光層と同様方法で形成することができる。正孔注入層4bの膜厚は、通常1nm~1μm、好ましくは2nm~500nm、さらに好ましくは5nm~200nmである。
このような層構成の場合、電極1(UVオゾン洗浄直後の仕事関数5.0eV)と発光層5(例えばHOMO5.7eV)の間の正孔注入の大きなエネルギー障壁を、HOMOの値が階段状になるように補完可能で、正孔注入効率に非常に優れた正孔注入輸送層が得られる。
発光層5は、図2~4に示すように、電極1が形成された基板7と電極6との間に、発光材料により形成される。
本発明の発光層に用いられる材料としては、通常、発光材料として用いられている材料であれば特に限定されず、蛍光材料およびりん光材料のいずれも用いることができる。具体的には、色素系発光材料、金属錯体系発光材料等の材料を挙げることができ、低分子化合物または高分子化合物のいずれも用いることができる。
色素系発光材料としては、例えば、アリールアミン誘導体、アントラセン誘導体、(フェニルアントラセン誘導体、)、オキサジアゾール誘導体、オキサゾール誘導体、オリゴチオフェン誘導体、カルバゾール誘導体、シクロペンタジエン誘導体、シロール誘導体、ジスチリルベンゼン誘導体、ジスチリルピラジン誘導体、ジスチリルアリーレン誘導体、シロール誘導体、スチルベン誘導体、スピロ化合物、チオフェン環化合物、テトラフェニルブタジエン誘導体、トリアゾール誘導体、トリフェニルアミン誘導体、トリフマニルアミン誘導体、ピラゾロキノリン誘導体、ヒドラゾン誘導体、ピラゾリンダイマー、ピリジン環化合物、フルオレン誘導体、フェナントロリン類、ペリノン誘導体、ペリレン誘導体等を挙げることができる。またこれらの2量体や3量体やオリゴマー、2種類以上の誘導体の化合物も用いることができる。
これらの材料は単独で用いてもよく2種以上を併用してもよい。
金属錯体系発光材料としては、例えばアルミキノリノール錯体、ベンゾキノリノールベリリウム錯体、ベンゾオキサゾール亜鉛錯体、ベンゾチアゾール亜鉛錯体、アゾメチル亜鉛錯体、ポルフィリン亜鉛錯体、ユーロピウム錯体等、あるいは中心金属にAl、Zn、Be等または、Tb、Eu、Dy等の希土類金属を有し、配位子にオキサジアゾール、チアジアゾール、フェニルピリジン、フェニルベンゾイミダール、キノリン構造等を有する金属錯体を挙げることができる。
これらの材料は単独で用いてもよく2種以上を併用してもよい。
高分子系発光材料としては、分子内に上記低分子系材料を分子内に直鎖あるいは側鎖あるいは官能基として導入されたもの、重合体およびデンドリマー等を使用することができる。例えば、ポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリパラフェニレン誘導体、ポリシラン誘導体、ポリアセチレン誘導体、ポリビニルカルバゾール、ポリフルオレノン誘導体、ポリフルオレン誘導体、ポリキノキサリン誘導体、及びそれらの共重合体等を挙げることができる。
上記発光層中には、発光効率の向上や発光波長を変化させる等の目的でドーピング材料を添加してもよい。高分子系材料の場合は、これらを分子構造の中に発光基として含んでいても良い。このようなドーピング材料としては、例えばペリレン誘導体、クマリン誘導体、ルブレン誘導体、キナクドリン誘導体、スクアリウム誘導体、ポルフィリン誘導体、スチリル系色素、テトラセン誘導体、ピラゾリン誘導体、デカシクレン、フェノキサゾン、キノキサリン誘導体、カルバゾール誘導体、フルオレン誘導体を挙げることができる。また、これらにスピロ基を導入した化合物も用いることができる。これらの材料は単独で用いてもよく2種以上を併用してもよい。
また、りん光系のドーパントとして、白金やイリジウムなどの重金属イオンを中心に有し、燐光を示す有機金属錯体が使用可能である。具体的には、Ir(ppy)3、(ppy)2Ir(acac)、Ir(BQ)3、(BQ)2Ir(acac)、Ir(THP)3、(THP)2Ir(acac)、Ir(BO)3、(BO)2(acac)、Ir(BT)3、(BT)2Ir(acac)、Ir(BTP)3、(BTP)2Ir(acac)、FIr6、PtOEP等を用いることができる。これらの材料は単独で用いてもよく2種以上を併用してもよい。
発光層の膜厚は、通常、1~1000nm、好ましくは20~500nm程度である。本発明は、正孔注入輸送層を溶液塗布法で形成することが好適であるため、発光層も溶液塗布法で形成する場合はプロセスコストを下げることができるという利点がある。
本発明に係るデバイスの別の実施形態として、有機トランジスタが挙げられる。以下、有機トランジスタを構成する各層について、図5及び図6を用いて説明する。
図5に示されるような本発明の有機トランジスタは、電極1(ソース電極)と電極6(ドレイン電極)の表面に正孔注入輸送層2が形成されているため、それぞれの電極と有機半導体層との間の正孔注入輸送能力が高くなり、且つ本発明の正孔注入輸送層の膜安定性が高いため、長駆動寿命化に寄与する。
本発明の有機トランジスタは、図6に示されるような、本発明の正孔注入輸送層2が有機半導体層8として機能するものであっても良い。
また、本発明の有機トランジスタは、図5に示されるように電極1(ソース電極)と電極6(ドレイン電極)の表面に正孔注入輸送層2を形成し、更に有機半導体層8として電極表面に形成した正孔注入輸送層とは材料が異なる本発明の正孔注入輸送層2を形成してもよい。
上記有機半導体材料としては、ポルフィリン誘導体、アリールアミン誘導体、ポリアセン誘導体、ペリレン誘導体、ルブレン誘導体、コロネン誘導体、ペリレンテトラカルボン酸ジイミド誘導体、ペリレンテトラカルボン酸二無水化物誘導体、ポリチオフェン誘導体、ポリパラフェニレン誘導体、ポリパラフェニレンビニレン誘導体、ポリピロール誘導体、ポリアニリン誘導体、ポリフルオレン誘導体、ポリチオフェンビニレン誘導体、ポリチオフェン-複素環芳香族共重合体とその誘導体、α-6-チオフェン、α-4-チオフェン、ナフタレンのオリゴアセン誘導体、α-5-チオフェンのオリゴチオフェン誘導体、ピロメリト酸二無水物誘導体、ピロメリト酸ジイミド誘導体を用いることができる。具体的には、ポルフィリン誘導体としては例えばフタロシアニンや銅フタロシアニンなどの金属フタロシアニンを挙げることができ、アリールアミン誘導体としては例えばm-TDATAを用いることができ、ポリアセン誘導体としては、例えばナフタレン、アントラセン、ナフタセン、ペンタセンを挙げることができる。また、これらポルフィリン誘導体やトリフェニルアミン誘導体などにルイス酸や四フッ化テトラシアノキノジメタン(F4-TCNQ)、バナジウムやモリブデンなど無機の酸化物などを混合し、導電性を高くした層を用いることもできる。
また、有機半導体層は、上記有機EL素子の発光層と同様に、溶液塗布法またはドライプロセスにより形成することが可能である。
基板7は、本発明のデバイスの支持体になるものであり、例えばフレキシブルな材質であっても、硬質な材質であってもよい。具体的には、上記有機EL素子の基板と同様のもの用いることができる。
ゲート電極、ソース電極、ドレイン電極としては、導電性材料であれば特に限定されないが、本発明に係る電荷輸送材料を用いて、金属イオンが配位している化合物が吸着してなる正孔注入輸送層2を形成する点からは、金属又は金属酸化物であることが好ましい。具体的には、上述の有機EL素子における電極と同様の金属又は金属酸化物を用いることができるが、特に、白金、金、銀、銅、アルミニウム、インジウム、ITOおよび炭素が好ましい。
本発明のデバイスの製造方法は、基板上に対向する2つ以上の電極と、そのうちの2つの電極間に配置された正孔注入輸送層を有するデバイスの製造方法であって、中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物である遷移金属錯体と、カルボニル基及び/又は水酸基を有する有機溶媒とを含有する正孔注入輸送層形成用インクを調製する工程と、前記正孔注入輸送層形成用インクを用いて、前記電極上のいずれかの層上に正孔注入輸送層を形成する工程と、前記遷移金属錯体の少なくとも一部を遷移金属酸化物とする酸化工程とを有することを特徴とする。
加熱工程を用いる場合には、加熱手段としては、ホットプレート上で加熱する方法やオーブン中で加熱する方法などが挙げられる。加熱温度としては、50~250℃が好ましい。加熱温度により、前記遷移金属錯体の反応性や、当該遷移金属錯体同士の相互作用や、当該遷移金属錯体の正孔輸送性化合物に対する相互作用に違いが生じるため、適宜調節することが好ましい。
ガラス基板の上に透明陽極、正孔注入輸送層としてバナジウム(III)アセチルアセトナートの反応物(有機-無機複合体)を含有する層と正孔輸送性化合物を含有する層との積層体、正孔輸送層、発光層、電子注入層、陰極の順番に成膜して積層し、最後に封止して有機EL素子を作製した。透明陽極と正孔注入輸送層以外は、水分濃度0.1ppm以下、酸素濃度0.1ppm以下の窒素置換グローブボックス内で作業を行った。
続いて、上記正孔注入輸送層(1)形成用塗布溶液を、洗浄された陽極の上にスピンコート法により塗布して、バナジウム錯体を含有する正孔注入輸送層を形成した。正孔注入輸送層(1)形成用塗布溶液の塗布後、溶剤を蒸発させるためにホットプレートを用いて200℃で30分乾燥させた。乾燥後の正孔注入輸送層(1)の厚みは5nm以下であった。
次に、成膜した正孔輸送層の上に、発光層としてトリス[2-(p-トリル)ピリジン)]イリジウム(III)(Ir(mppy)3)を発光性ドーパントとして含有し、4,4’-ビス(2、2-カルバゾル-9-イル)ビフェニル(CBP)をホストとして含有した混合薄膜を塗布形成した。溶媒であるトルエンにCBPを1質量%、Ir(mppy)3を0.05質量%の濃度で溶解させた溶液を、スピンコート法により塗布して成膜した。インクの塗布後、溶剤を蒸発させるためにホットプレートを用いて100℃で30分乾燥させた。
次に、上記発光層の上に、正孔ブロック層としてビス(2-メチル-8-キノリラト)(p-フェニルフェノラート)アルミニウム錯体(BAlq)薄膜を蒸着形成した。BAlq薄膜は、真空中(圧力:1×10-4Pa)で抵抗加熱法により膜厚が15nmになるように形成した。
次に、上記正孔ブロック層の上に、電子輸送層としてトリス(8-キノリノラト)アルミニウム錯体(Alq3)薄膜を蒸着形成した。Alq3薄膜は、真空中(圧力:1×10-4Pa)で抵抗加熱法により膜厚が15nmになるように形成した。
次に、上記電子輸送層の上に、電子注入層としてLiF(厚み:0.5nm)、陰極としてAl(厚み:100nm)を順次成膜した。真空中(圧力:1×10-4Pa)で、抵抗加熱蒸着法により成膜した。
最後に陰極形成後、グローブボックス内にて無アルカリガラスとUV硬化型エポキシ接着剤を用いて封止し、実施例1の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにペンタカルボニルクロロレニウム(I)(レニウム錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、実施例2の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりに白金(II)アセチルアセトナート(白金錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、実施例3の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにペンタカルボニルクロロレニウム(I)(シグマ‐アルドリッチ社製)とモリブデンヘキサカルボニル(関東科学(株)製)の混合物(レニウム錯体とモリブデン錯体の混合物)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、実施例4の有機EL素子を作製した。正孔注入輸送層(1)形成用塗布溶液はシクロヘキサノン中に上記2種の材料をそれぞれ0.2質量%の濃度で溶解させて調製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにスカンジウムアセチルアセトナート(スカンジウム錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、参考例1の有機EL素子を作製した。
実施例1において、バナジウム錯体を溶解させる溶媒をシクロヘキサノンの代わりに芳香族系溶剤であるトルエンを使用した以外は、実施例1と同様にして、比較例1の有機EL素子を作製した。
実施例1において、正孔注入輸送層としてバナジウム錯体薄膜を形成する代わりに、酸化バナジウム(V2O5)薄膜(厚み:5nm)を形成した以外は、実施例1と同様にして、比較例2の有機EL素子を作製した。
酸化バナジウム(V2O5)薄膜は、真空中(圧力:1×10-4Pa)で、抵抗加熱蒸着法により成膜した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにコバルト(III)アセチルアセトナート(コバルト錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例3の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにニッケル(II)アセチルアセトナート(ニッケル錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例4の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりに銅(II)アセチルアセトナート(銅錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例5の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりに鉄(II)アセチルアセトナート(鉄錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例6の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりに亜鉛アセチルアセトナート(亜鉛錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例7の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにクロム(III)アセチルアセトナート(クロム錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例8の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにチタンイソプロポキシド(チタン錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例9の有機EL素子を作製した。
実施例1における正孔注入輸送層を、バナジウム(III)アセチルアセトナートの代わりにマンガン(III)アセチルアセトナート(マンガン錯体、シグマ‐アルドリッチ社製)を含む正孔注入輸送層(1)形成用塗布溶液を用いて形成した以外は、実施例1と同様にして、比較例10の有機EL素子を作製した。
シクロヘキサノン中の遷移金属錯体の状態を調べるために、1H-NMR測定及び13C-NMR測定をした。実施例実施例1~4、参考例1、並びに、比較例1および3~10で使用した正孔注入輸送層形成用塗布溶液を重クロロホルムに4倍に希釈し、核磁気共鳴装置(日本電子社製、JNU-LA400W 400 MHz)を用い測定した。
実施例1~4及び参考例1の溶液の1H-NMR測定では1.5-1.7ppmと2.0-2.2ppmの範囲とにシクロヘキサノンおよび遷移金属錯体では観察されない、シクロヘキサノンのC=O結合が還元されてアルコールあるいはオリゴマーかポリマーを形成していることを示唆するスペクトルが得られた。このうち、1.7-2.2ppmに現れるシクロヘキサノン溶媒に起因するピークを100と規格化した場合の1.5-1.7ppmのピーク量を求め、表1中に示した。その結果、実施例1~4、及び参考例1では有機-無機複合体からなる反応生成物が比較的多く形成され、一方比較例3~10では有機-無機複合体からなる反応生成物が殆ど形成されないことが示唆された。
また実施例1~4及び参考例1の溶液の13C-NMR測定で得られた結果から、いずれのサンプルからも元の遷移金属錯体を示すスペクトルは消失していることが確認された。一方、比較例1のトルエンに溶解させたバナジウム錯体では、バナジウム錯体が分解せずに溶解していることを示すスペクトルが得られた。
実施例1のバナジウム錯体を用いて形成された有機-無機複合体薄膜と、比較例1で得られたバナジウム錯体の薄膜と、比較例2で使用した酸化バナジウム(V2O5)薄膜について、光電子分光装置AC-1(理研計器製)を用いてHOMO(仕事関数)を測定した。バナジウム錯体から得られた有機-無機複合体で形成された薄膜のHOMOは5.2eVであり、バナジウム錯体のHOMOは5.0eVであり、酸化バナジウムのHOMOは5.4eVであった。
実施例1のバナジウム錯体を用いて形成された有機-無機複合体薄膜と、比較例1で得られたバナジウム錯体の薄膜と、比較例2で使用した酸化バナジウム(V2O5)薄膜について、X線光電子分光法にて価数を測定した。測定にはKratos社製ESCA-3400型を用いた。測定に用いたX線源としては、MgKα線を用いた。モノクロメーターは使用せず、加速電圧10kV、フィラメント電流20mAの条件で測定した。
比較例2の薄膜からはV2O5酸化数が+5であるバナジウムの2p3/2に帰属されるスペクトルが得られた(ピーク位置517eV)。一方、実施例1では、ピーク位置517eVに加えて、ショルダー上に516eV近辺にピークをもつスペクトルが得られた。この結果は、バナジウムの酸化数が+5と+4の複合体を形成している可能性を示している。また、比較例1のバナジウム錯体の薄膜では、514-515eVにピークを持つバナジウムの酸化数が+3を示すスペクトルが得られた。出発物質のバナジウム錯体の酸化数(+3)と同じことから、比較例1ではバナジウム錯体の反応生成物が生成されていないことが示唆された。
有機EL素子の寿命特性は、定電流駆動で輝度が経時的に徐々に低下する様子を観察して評価した。ここでは初期輝度2000cd/m2に対して保持率が50%の輝度に劣化するまでの時間(hr.)を寿命(LT50)とした。
実施例1~4の正孔注入輸送層形成用塗布溶液のNMR測定結果をみると、いずれも1.5-1.7ppmのピーク量が基準ピークの3%以上と大きく、遷移金属錯体とシクロヘキサノンが高活性に反応して有機-無機複合体が形成されていることを示す結果が得られた。これら実施例1~4においては、以下に示すとおり素子特性でも高特性が得られた。参考例1においても、1.5-1.7ppmのピーク量が基準ピークの3%以上と大きく、素子特性でも比較的高特性が得られた。
実施例1と比較例1を比較すると、バナジウム錯体を塗布した比較例1の正孔注入輸送層よりもバナジウム錯体の反応生成物から得られた実施例1の正孔注入輸送層の素子の方が、はるかに低電圧化し、長寿命であり、素子性能が高かった。この結果は、本発明で得られた有機-無機複合体がバナジウム錯体とは異なる物質に変質し、正孔注入性が高く、駆動安定性に優れた正孔注入輸送層が形成されたことを示している。
実施例1と比較例2を比較すると、バナジウム酸化物の蒸着膜の比較例2の正孔注入輸送層よりもバナジウム錯体の反応物から得られた実施例1の正孔注入輸送層の素子の方が低電圧化し、長寿命であり、素子性能が高かった。この結果は、本発明で得られた有機-無機複合体である正孔注入輸送層の方がバナジウム酸化物の蒸着膜に比べて正孔注入性が高く、駆動安定性に優れていることを示している。
遷移金属錯体の中心金属として少なくともバナジウム、レニウム、及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはレニウムとモリブデンとの混合物を用いて反応生成物を形成した正孔注入輸送層を含む実施例1~4の素子は、いずれも高特性であった。実施例1~4においては、上記特定の反応性が高い遷移金属錯体を用いたため、NMR測定の結果からも示唆されるように、有機-無機複合体からなる反応生成物が比較的多く形成されたことが推定される。
一方、NMR測定結果から有機-無機複合体からなる反応生成物が全く或いは殆ど形成されないことが示唆された正孔注入輸送層用塗布液を用いた、比較例1及び3~10の素子では、特性が低かった。比較例1及び3~10の素子では、有機-無機複合体からなる反応生成物が全く或いは殆ど形成されなかったことが推定される。
実施例1~4と比較例1及び3~10を比較すると、有機-無機複合体からなる反応生成物の形成が素子特性に影響していることが示唆された。
2 正孔注入輸送層
3 有機層
4a 正孔輸送層
4b 正孔注入層
5 発光層
6 電極
7 基板
8 有機半導体層
9 電極
10 絶縁層
Claims (15)
- 基板上に対向する2つ以上の電極と、そのうちの2つの電極間に配置された正孔注入輸送層を有するデバイスであって、
前記正孔注入輸送層が、遷移金属錯体の反応生成物を含有し、当該遷移金属錯体の中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物であることを特徴とする、デバイス。 - 前記遷移金属錯体の反応生成物が、カルボニル基及び/又は水酸基を有する有機溶媒と反応した遷移金属酸化物であることを特徴とする、請求の範囲第1項に記載のデバイス。
- 前記正孔注入輸送層は、前記遷移金属錯体の反応生成物及び正孔輸送性化合物を少なくとも含有することを特徴とする、請求の範囲第1項又は第2項に記載のデバイス。
- 前記正孔注入輸送層は、前記遷移金属錯体の反応生成物を含有する層と、正孔輸送性化合物を含有する層とが少なくとも積層された層からなることを特徴とする、請求の範囲第1項乃至第3項のいずれかに記載のデバイス。
- 前記正孔注入輸送層は、前記遷移金属錯体の反応生成物を含有する層と、前記遷移金属錯体の反応生成物及び正孔輸送性化合物を少なくとも含有する層とが少なくとも積層された層からなることを特徴とする、請求の範囲第1項乃至第4項のいずれかに記載のデバイス。
- 前記正孔輸送性化合物が、正孔輸送性高分子化合物であることを特徴とする、請求の範囲第3項乃至第5項のいずれかに記載のデバイス。
- 前記デバイスが、少なくとも発光層を含む有機層を含有する有機EL素子である、請求の範囲第1項乃至第6項のいずれかに記載のデバイス。
- 基板上に対向する2つ以上の電極と、そのうちの2つの電極間に配置された正孔注入輸送層を有するデバイスの製造方法であって、
中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物である遷移金属錯体と、カルボニル基及び/又は水酸基を有する有機溶媒とを含有する正孔注入輸送層形成用インクを調製する工程と、前記正孔注入輸送層形成用インクを用いて、前記電極上のいずれかの層上に正孔注入輸送層を形成する工程と、前記遷移金属錯体の少なくとも一部を遷移金属酸化物とする酸化工程とを有することを特徴とする、デバイスの製造方法。 - 前記電極上のいずれかの層上に、前記遷移金属錯体を含有する正孔注入輸送層を形成する工程と、前記正孔注入輸送層中の当該遷移金属錯体の少なくとも一部を遷移金属酸化物とする酸化工程を有することを特徴とする、請求の範囲第8項に記載のデバイスの製造方法。
- 前記正孔注入輸送層形成用インクを調製する工程後、正孔注入輸送層を形成する工程前に、前記酸化工程が実施され、酸化物化された正孔注入輸送層形成用インクを用いて、前記電極上のいずれかの層上に遷移金属酸化物を含有する正孔注入輸送層を形成する工程を有することを特徴とする、請求の範囲第8項に記載のデバイスの製造方法。
- 前記酸化工程が、加熱工程を含むことを特徴とする、請求の範囲第8項乃至第10項のいずれかに記載のデバイスの製造方法。
- 前記酸化工程が、光照射工程を含むことを特徴とする、請求の範囲第8項乃至第11項のいずれかに記載のデバイスの製造方法。
- 前記酸化工程が、活性酸素を作用させる工程を含むことを特徴とする、請求の範囲第8項乃至第12項のいずれかに記載のデバイスの製造方法。
- 中心金属が、少なくともバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属を含むか、或いはバナジウム、レニウム及び白金よりなる群から選択される1種以上の遷移金属とモリブデンとの混合物である遷移金属錯体と、カルボニル基及び/又は水酸基を有する有機溶媒とを含有することを特徴とする、正孔注入輸送層形成用インク。
- 前記遷移金属錯体と、カルボニル基及び/又は水酸基を有する有機溶媒とが反応した遷移金属酸化物を含有することを特徴とする、請求の範囲第14項に記載の正孔注入輸送層形成用インク。
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