WO2011013761A1 - 正孔注入輸送層用デバイス材料、正孔注入輸送層形成用インク、正孔注入輸送層を有するデバイス、及びその製造方法 - Google Patents
正孔注入輸送層用デバイス材料、正孔注入輸送層形成用インク、正孔注入輸送層を有するデバイス、及びその製造方法 Download PDFInfo
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- WO2011013761A1 WO2011013761A1 PCT/JP2010/062824 JP2010062824W WO2011013761A1 WO 2011013761 A1 WO2011013761 A1 WO 2011013761A1 JP 2010062824 W JP2010062824 W JP 2010062824W WO 2011013761 A1 WO2011013761 A1 WO 2011013761A1
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- WIPO (PCT)
- Prior art keywords
- layer
- hole injection
- transport layer
- transition metal
- organic
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Images
Classifications
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- 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
- 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
- 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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
-
- 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
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
Definitions
- the present invention relates to a device material for a hole injecting and transporting layer having wettability changed by energy irradiation and having a hole injecting and transporting property, an ink for forming a hole injecting and transporting layer using the device material, and a hole injecting and transporting
- the present invention relates to a device having a layer and a manufacturing method thereof.
- Organic electroluminescence elements hereinafter referred to as organic EL elements
- organic transistors organic solar cells
- organic semiconductors organic semiconductors
- quantum dot light emitting elements oxidation Development to a wide range of basic elements and applications such as physical compound solar cells is expected.
- the organic EL element is a charge injection type self-luminous device that utilizes light emission generated when electrons and holes that have reached the light emitting layer recombine.
- the element structure of the organic EL element is currently a five-layer structure comprising an electron injection layer / electron transport layer / light emitting layer / hole transport layer / hole injection layer in order to obtain high light emission efficiency and a long driving life.
- Various multilayer structures 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 an effect of facilitating the injection and transport of charges to the light-emitting layer, or are blocked by blocking the electron current. It is said that there are effects such as maintaining the balance of the hole current and suppressing diffusion of light energy excitons.
- Patent Documents 1 to 4 For the purpose of improving the charge transport ability and the charge injection ability, an attempt has been made to increase the electrical conductivity by mixing an oxidizing compound with a hole transport material.
- a metal oxide that is a compound semiconductor is used as 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 a mixed film is formed by co-evaporation of molybdenum oxide and an amine-based low molecular compound.
- Non-Patent Document 1 as an attempt to form a coating film of vanadium pentoxide, a solution in which oxovanadium (V) tri-i-propoxide oxide was dissolved as an oxidizing compound, that is, an electron accepting compound, was used. There is a production method in which a charge transfer complex is formed as vanadium oxide by hydrolysis in water vapor after formation of a mixed coating film with a pore-transporting polymer.
- a charge transfer complex is formed as vanadium oxide by hydrolysis in water vapor after formation of a mixed coating film with a pore-transporting polymer.
- vanadium 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.
- Non-Patent Document 1 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 Non-Patent Document 1 necessarily has an organic component concentration. The concentration of vanadium, which is high and is considered to be an effective component for the lifetime of the device, is insufficient. As described above, Non-Patent Document 1 requires further improvement in life characteristics and device characteristics.
- Patent Document 5 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 is described to form a layer.
- Patent Documents 1 to 5 and Non-Patent Document 1 are used as the hole transporting material, it is difficult to realize a long-life element or it is necessary to further improve the lifetime. there were.
- the metal oxides disclosed in Patent Documents 1 to 4 although the hole injection characteristics are improved to some extent, the adhesion at the interface with the adjacent organic compound layer is insufficient, which adversely affects the life characteristics. it is conceivable that.
- Patent Document 5 describes that a charge injection layer was produced by screen printing using a slurry in which molybdenum oxide fine particles having an average particle diameter of 20 nm were dispersed in a solvent.
- the method of pulverizing the MoO 3 powder as in Patent Document 5 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. Further, it is very difficult to stably disperse molybdenum oxide fine particles produced by pulverization in a solution without agglomeration.
- the solution of the fine particles is unstable, only a film with large irregularities and poor smoothness can be formed during the production of the coating film, which causes a short circuit of the device.
- the thin film can be formed only by the vapor deposition method, there is a problem that the advantages of the solution coating method cannot be utilized even if the light emitting layer is separately formed by a solution coating method such as an ink jet method. That is, in order not to impair the liquid repellency of the partition walls (banks) between the light emitting layers by the lyophilic molybdenum oxide, a hole injection layer or a hole transport layer containing molybdenum oxide of an inorganic compound is provided.
- 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.
- a light emitting layer or the like is patterned.
- Various patterning methods such as a method of evaporating a material through a shadow mask, a method of coating with an ink jet, a method of transferring a luminescent dye, a flexographic printing method, and a gravure printing method have been proposed as a patterning method for the light emitting layer and the like.
- a partition in order to obtain a high-definition fine pattern, a partition (bank) is formed, and the partition surface is subjected to ink repellent treatment by plasma treatment such as fluorine gas (for example, see Patent Document 6).
- the heat resistance of the ink repellent treatment is low, and problems occur in subsequent processes.
- the relatively high temperature (for example, 200 ° C.) heating applied when forming a layer in the opening of the partition wall after the ink repellent treatment causes fluorine introduced into the partition wall to desorb, and the partition wall portion becomes ink-philic.
- the characteristics of the device were lowered because the layers could not be laminated.
- many liquid repellent materials have the same problems as described above because fluorine is easily detached by heating at a relatively high temperature and is not resistant. .
- the top of the partition wall is ink repellent, but the side surface cannot be made ink-philic.
- the contact angle of the liquid is lowered at the portion where the photocatalyst action due to energy irradiation is applied or the portion irradiated with vacuum ultraviolet light. It utilizes the change in wettability. That is, the part that has been subjected to the action of the photocatalyst associated with energy irradiation or the part that has been irradiated with the vacuum ultraviolet light becomes a lyophilic region, and the part that does not have the action of the photocatalyst associated with energy irradiation or the part that is not irradiated with the vacuum ultraviolet light. It is used to be a liquid repellent region.
- a light emitting layer or the like is formed on a portion that has been subjected to the action of a photocatalyst accompanying energy irradiation or a portion that has been irradiated with vacuum ultraviolet light.
- the layer whose wettability changes has hole transporting properties, the material deteriorates in the part where the action of the photocatalyst due to the energy irradiation or the part irradiated with the vacuum ultraviolet light is deteriorated. There was a problem that transportability and the like were impaired.
- the method using the above photocatalyst and the method using vacuum ultraviolet light can form a pattern due to the difference in wettability only by energy irradiation, the labor required for patterning of the light emitting layer and the like can be largely omitted.
- This is a useful method in terms.
- the material has high resistance to energy irradiation such as ultraviolet light and does not impair hole injecting and transporting properties, and heating There was no material in which the lyophilic and lyophobic patterning properties were not impaired during the process.
- the present invention has been made in view of the above problems, wettability is changed by energy irradiation, process resistance is high, and has excellent hole injecting and transporting properties. Hole injection is performed by a solution coating method. It is an object of the present invention to provide a device material for a hole injection transport layer capable of forming a transport layer, and an ink for a hole injection transport layer using the device material. Another object of the present invention is to form a pattern composed of a lyophilic region and a liquid repellent region by using the above-described device material for a hole injection / transport layer, thereby being laminated on the hole injection / transport layer. It is an object of the present invention to provide a device capable of patterning a layer and achieving a long lifetime and a manufacturing method thereof.
- an organic-transition metal oxide complex which is a reaction product of an organic transition metal complex having a fluorine-containing organic compound attached to the surface, is a photocatalyst.
- the wettability can be changed by the action and irradiation with vacuum ultraviolet light, the process resistance is high, and the layer can be formed by the solution coating method, and the manufacturing process is easy.
- the present invention has been completed. That is, the hole injection / transport layer device material of the present invention is characterized in that a fluorine-containing organic compound is attached to the surface of an organic-transition metal oxide composite that is a reaction product of an organic transition metal complex. To do.
- the transition metal in the transition metal oxide contained in the organic-transition metal oxide composite is selected from the group consisting of molybdenum, tungsten, and vanadium. It is preferable that at least one kind of metal is included from the viewpoint of lowering the driving voltage and improving the element life.
- the organic-transition metal oxide complex is a reaction product of the organic transition metal complex and an organic solvent. This is preferable from the viewpoint of improving the life.
- the organic-transition metal oxide composite contains two or more transition metal oxides having the same transition metal but different oxidation numbers. It is preferable from the viewpoint of lowering and improving the device life.
- the fluorine-containing organic compound contains a fluorinated alkyl group from the viewpoint of good change in wettability by energy irradiation and excellent patterning. preferable.
- the hole injection / transport layer forming ink of the present invention is characterized by containing the hole injection / transport layer device material according to the present invention and an organic solvent.
- the ink dissolves or disperses an organic transition metal complex and a fluorine-containing organic compound containing a linking group capable of linking with a transition metal and / or transition metal oxide in an organic solvent having a carbonyl group and / or a hydroxyl group.
- the transition metal in the organic transition metal complex is preferably oxidized.
- the ink for forming a hole injecting and transporting layer of the present invention has an effect of linking an organic-transition metal oxide complex, which is a reaction product of an organic transition metal complex, with a transition metal and / or transition metal oxide. It may contain a fluorine-containing organic compound containing a linking group and an organic solvent. Furthermore, the ink for forming a hole injection transport layer of the present invention includes an organic transition metal complex, a fluorine-containing organic compound containing a linking group capable of linking with a transition metal and / or a transition metal oxide, a carbonyl group, and / or Alternatively, it may contain an organic solvent having a hydroxyl group.
- a first embodiment of 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.
- a hole injection transport layer forming step for forming a hole injection transport layer containing the device material for hole injection transport layer according to the present invention on the substrate on which the first electrode layer is formed in a pattern, After disposing a photocatalyst-containing layer substrate on which a photocatalyst-containing layer containing at least a photocatalyst is formed on the substrate, with a gap that can act as a photocatalyst associated with energy irradiation with respect to the hole injecting and transporting layer, And a wettability change pattern forming step of forming a wettability change pattern having changed wettability on the surface of the hole injecting and transporting layer by irradiating energy in a pattern.
- the second embodiment of the device manufacturing method according to the present invention is a device manufacturing method including two or more electrodes facing each other on a substrate and a hole injecting and transporting layer disposed between the two electrodes.
- a method A hole injection transport layer forming step of forming a hole injection transport layer containing the device material for hole injection transport layer according to the present invention on the substrate on which the electrode layer is formed in a pattern, And a wettability changing pattern forming step of forming a wettability changing pattern having changed wettability on the surface of the hole injecting and transporting layer by irradiating the pattern with vacuum ultraviolet rays.
- the hole injecting and transporting layer contains a material to which the lyophobic fluorine-containing organic compound is attached.
- a great difference in wettability can be produced between the irradiated portion and the non-irradiated portion.
- a wettability change pattern is formed, and the wettability difference of this wettability change pattern is determined.
- a patterned layer can be easily laminated on the hole injecting and transporting layer.
- the organic-transition metal oxide composite contained in the device material for hole injection / transport layer according to the present invention contained in the hole injection / transport layer has wettability. Since it has resistance to ultraviolet light used in the change pattern forming step, it has the merit that excellent hole injecting and transporting properties are not deteriorated and not impaired even after the wettability changing pattern forming step.
- the device material for a hole injecting and transporting layer according to the present invention is resistant to heating at a relatively high temperature (for example, 200 ° C.), the wettability change pattern is not impaired during the heating process, and the hole injecting and transporting layer is not damaged. A process of laminating many layers in a pattern is possible. Furthermore, since the device material for a hole injection transport layer according to the present invention has high heat resistance and light resistance and is hardly deteriorated, the lifetime of the device manufactured by the manufacturing method of the present invention is also improved.
- the hole injection transport layer forming step includes a step of applying the hole injection transport layer forming ink according to the present invention, the manufacturing process is easy, and It is preferable from the viewpoint of good hole injecting and transporting properties. Furthermore, the hole injection / transport layer forming step preferably includes a step of heating or light irradiation in the presence of oxygen from the viewpoint of improving the hole injection / transport property.
- the partition part formation process which forms partition parts, such as an insulating layer and a partition.
- the substrate on which the first electrode layer is formed is a translucent substrate, and the partition portion is irradiated in the wettability change pattern forming step.
- a partition that reflects or absorbs energy rays, and in the wettability change pattern forming step, the wettability change is performed on the surface of the hole injecting and transporting layer by irradiating the energy from the translucent substrate side. It is preferable to form a wettability change pattern.
- the partition that reflects or absorbs the irradiated energy rays performs the same function as the mask, and irradiates the hole injection / transport layer with energy in a pattern without using a separate mask. It is possible.
- the device material for the hole injection / transport layer used in the hole injection / transport layer of the present invention has high transmittance, and the device characteristics are not easily deteriorated even by UV irradiation. It becomes possible.
- the method of irradiating energy in a pattern may be a method of irradiating energy using a mask, or ultraviolet.
- a method of irradiating energy by scanning a laser in a pattern may be used.
- a first embodiment of 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,
- the hole injecting and transporting layer contains the device material for hole injecting and transporting layer according to the present invention, and the fluorine-containing organic compound of the device material for hole injecting and transporting layer in the surface layer part of the hole injecting and transporting layer is It is characterized by being decomposed and removed.
- a second embodiment of 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,
- a partition is provided between the patterns of the first electrode layer on the substrate on which the first electrode layer is formed in a pattern, and is continuous on the first electrode layer and the partition in the opening of the partition.
- a hole injection transport layer In the hole injecting and transporting layer on the first electrode layer in the opening of the partition part and on the side part of the partition part, at least part of the device material for hole injecting and transporting layer according to the present invention contains fluorine.
- the organic compound is decomposed and removed, and the hole injection / transport layer on the top of the insulating layer contains the device material for a hole injection / transport layer according to the present invention.
- the hole injecting and transporting layer contains the device material for hole injecting and transporting layer according to the present invention from which at least a part of the fluorine-containing organic compound is decomposed and removed, and thus the manufacturing process is easy.
- the device of the present invention can be obtained by the device manufacturing method according to the present invention.
- 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.
- hole injection changes in wettability due to energy irradiation has high process resistance, has excellent hole injection / transport properties, and can form a hole injection / transport layer by a solution coating method. It is possible to provide a transport layer device material and a hole injection transport layer ink using the device material. According to the method for manufacturing a device according to the present invention, a good wettability change pattern of the hole injection transport layer can be used while the manufacturing process is easy, and an excellent hole injection transport layer can be obtained. It is possible to provide a device that can achieve a long lifetime.
- the device according to the present invention has an excellent hole injecting and transporting property and can achieve a long life while having a simple manufacturing process.
- FIGS. 2A to 2C are process diagrams showing another example of the device manufacturing method of the present invention.
- FIGS. 2A to 2C are process diagrams showing another example of the device manufacturing method of the present invention.
- FIG. 3A to FIG. 3C are process diagrams showing another example of the device manufacturing method of the present invention.
- 4A to 4C are process diagrams showing another example of the device manufacturing method of the present invention.
- FIG. 5 is a schematic cross-sectional view showing an example of a part of a device substrate of the device according to the present invention.
- 6 (A) to 6 (B) are schematic sectional views showing examples of the photocatalyst-containing layer substrate used in the present invention.
- FIG. 7B are schematic cross-sectional views showing examples of part of a device substrate of the device according to the present invention.
- FIG. 8 is a schematic sectional view showing an example of the device of the present invention.
- FIG. 9 is a schematic cross-sectional view showing another example of the device of the present invention.
- FIG. 10 is a schematic cross-sectional view showing an example of the organic EL element of the present invention.
- FIG. 11 is a schematic cross-sectional view showing an experiment of wettability change in the organic EL element of the present invention.
- 12 (A) to 12 (B) are examples of an ITO substrate on which an insulating layer and a partition wall used in the present invention are formed.
- FIG. 12 (A) is a partially enlarged schematic sectional view
- FIG. 13 is a 1H NMR spectrum of fluorine-containing organic compound F-1 obtained in Synthesis Example 1.
- FIG. 14 is a 1H NMR spectrum of fluorine-containing organic compound F-2 obtained in Synthesis Example 2.
- FIG. 15 is a 1H NMR spectrum of fluorine-containing organic compound F-3 obtained in Synthesis Example 3.
- FIG. 16 is a 1H NMR spectrum of fluorine-containing organic compound F-4 obtained in Synthesis Example 4.
- the device material for hole injection / transport layer of the present invention has a fluorine-containing organic compound attached to an organic-transition metal oxide composite that is a reaction product of an organic transition metal complex. It is characterized by that.
- the device material for a hole injection / transport layer of the present invention is an organic-transition metal oxide composite having a fluorine-containing organic compound attached to the surface thereof, so that the action of a photocatalyst associated with energy irradiation, irradiation with vacuum ultraviolet light, etc.
- the wettability changes from lyophobic to lyophilic by being able to decompose and remove the fluorine-containing organic compound adhering to the surface.
- the part that has been subjected to the action of the photocatalyst associated with the energy irradiation or the part that has been irradiated with the vacuum ultraviolet light becomes a lyophilic region, and the action of the photocatalyst associated with the energy irradiation.
- the portion that does not reach or the portion that is not irradiated with vacuum ultraviolet light is the liquid repellent region.
- the device material for hole injecting and transporting layer of the present invention decomposes and removes the fluorine-containing organic compound adhering to the surface by the action of a photocatalyst accompanying irradiation of energy or irradiation of vacuum ultraviolet light, but the organic transition metal complex
- the organic-transition metal oxide composite itself which is a reaction product of the above, is resistant to ultraviolet light and relatively high-temperature heating, and therefore has excellent hole injection / transport properties possessed by the organic-transition metal oxide composite.
- the device material for a hole injection / transport layer of the present invention has a merit that it undergoes a treatment such as a photocatalytic treatment for decomposing fluorine to be oxidized to increase the ionization potential and improve the hole injection property.
- the device material for a hole injecting and transporting layer according to the present invention is an organic-transition metal oxide composite and includes at least a fluorine-containing organic compound on the surface, unlike the case of using an inorganic compound molybdenum oxide. Since the organic portion is contained, the adhesion at the interface with the adjacent organic layer is also improved.
- a fluorine-containing organic compound in at least the surface layer part of the hole injecting and transporting layer using the device material for hole injecting and transporting layer of the present invention is decomposed into a lyophilic region, and another organic layer is laminated. Therefore, the influence of the liquid repellency derived from the fluorine-containing organic compound is eliminated at the interface with the adjacent organic layer, and the adhesion at the interface is excellent.
- an organic-transition metal oxide complex that is a reaction product of an organic transition metal complex is considered to have a high reactivity of the contained transition metal oxide and easily form a charge transfer complex. Therefore, the hole injection / transport layer device material of the present invention can form a hole injection / transport layer that can realize a low voltage drive, high power efficiency, and long-life device.
- the organic-transition metal oxide composite used in the device material for a hole injection / transport layer of the present invention is a composite of an organic substance and a transition metal oxide, unlike the case where an inorganic compound such as molybdenum oxide is used.
- the surface contains an organic portion containing at least a fluorine-containing organic compound, the solvent has dispersibility. Therefore, since a thin film can be formed by a solution coating method, the substrate from the hole injecting and transporting layer to the organic layer to be laminated such as the light emitting layer can be sequentially formed only by the coating process, and the merit in the manufacturing process is great.
- the hole injection layer is deposited by high-definition mask vapor deposition or the like as in the case of molybdenum oxide which is an inorganic compound
- the hole transport layer or the light-emitting layer is formed by vapor deposition or solution coating.
- the structure of the device material for hole injection transport layer of the present invention will be described in order.
- the organic-transition metal oxide composite used in the device material for a hole injection / transport layer of the present invention is a reaction product of an organic transition metal complex and contains a transition metal oxide.
- the reaction product of the organic transition metal complex includes a reaction product between the organic transition metal complexes, a reaction product of the organic transition metal complex and the organic solvent, or a functional group capable of reacting with the organic transition metal complex and the organometallic complex.
- the reaction product with the organic or inorganic compound which has these, and the reaction product of these combination are mentioned.
- the organic-transition metal oxide complex which is a reaction product of the organic transition metal complex, is used in the process of forming the hole injection / transport layer, for example, in the ink for forming the hole injection / transport layer (coating solution) or layer formation. It may be a reaction product generated by a reaction of an organic transition metal complex performed at the time of heating or after layer formation, at the time of heating, at the time of light irradiation, or at the time of driving an element.
- the organic-transition metal oxide complex may contain transition metal atoms and compounds of various valences, for example, transition metal carbides, sulfides, borides, selenides, halides, and the like depending on processing conditions. .
- the transition metal in the transition metal oxide contained in the organic-transition metal oxide composite is a generic term for metal elements existing between Group 3 to Group 11 in the periodic table.
- Specific examples of the transition metal include molybdenum, tungsten, vanadium, rhenium, nickel, copper, titanium, platinum, and silver.
- the transition metal in the transition metal oxide contained in the organic-transition metal oxide composite may contain at least one metal selected from the group consisting of molybdenum, tungsten, and vanadium. Therefore, it is preferable from the viewpoint of easily forming a charge transfer complex and reducing the driving voltage and improving the device life.
- the metal contained in the organic-transition metal oxide composite may be a single metal or two or more kinds. As an aspect in which two or more kinds of metals are contained, two or more kinds of metals or metal oxides may be contained in combination, or two or more kinds of metals may be contained as an alloy. Further, a different binuclear metal complex may be used.
- the metal contained in the organic-transition metal oxide composite may contain a non-transition metal as long as it contains at least a transition metal. By containing two or more metals, hole injection has other functions such as complementing each other with hole transportability and hole injection property, providing photocatalytic properties, and controlling the refractive index and transmittance of thin films. There is an advantage that a transport layer can be formed.
- the organic transition metal complex used in the present invention is a coordination compound containing a transition metal, and contains a ligand containing an organic compound in addition to the transition metal described above.
- organic molybdenum complexes include complexes having an oxidation number of ⁇ 2 to +6.
- organic tungsten complexes include those having an oxidation number of ⁇ 2 to +6.
- Tungsten complexes tend to be polynuclear and have oxo ligands, and tend to resemble molybdenum complexes, and the coordination number may be 7 or more.
- As the organic vanadium complex there are complexes having an oxidation number of ⁇ 3 to +5.
- the type of the ligand is appropriately selected and is not particularly limited, but a ligand containing an organic part (carbon atom) is used in view of solvent solubility and adhesion to 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. Of these, carbonyl which is easily decomposed at a relatively low temperature is preferable.
- Examples of the bidentate ligand include various carboxylic acids.
- 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 organic transition metal complex. If the complex itself becomes too stable, the reactivity may be poor.
- molybdenum complexes e.g., metal carbonyl [Mo -II (CO) 5] 2-, [(CO) 5 Mo -I Mo -I (CO) 5] 2-, [Mo (CO) 6 ] and the like.
- molybdenum (I) complex having an oxidation number of +1 include non-Werner type complexes containing diphosphane and ⁇ 5 -cyclopentadienide.
- Examples of the molybdenum (II) complex having an oxidation number of +2 include Mo 2 compounds in which molybdenum becomes a binuclear complex and exists in the state of (Mo 2 ) 4+ ions.
- Mo 2 compounds in which molybdenum becomes a binuclear complex and exists in the state of (Mo 2 ) 4+ ions For example, [Mo 2 (RCOO) 4 ] And [Mo 2 X 2 L 2 (RCOO) 4 ].
- R in the RCOO is a hydrocarbon group which may have a substituent, and various carboxylic acids can be used.
- carboxylic acid examples include fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid, halogenated alkyl carboxylic acids such as trifluoromethane carboxylic acid, benzoic acid, naphthalene carboxylic acid, anthracene carboxylic acid, and 2-phenylpropanoic acid.
- hydrocarbon aromatic carboxylic acids such as cinnamic acid and fluorene carboxylic acid, and heterocyclic carboxylic acids such as furan carboxylic acid, thiophene carboxylic acid and pyridine carboxylic acid.
- a carboxylic acid having a carboxyl group in a hole transporting compound (arylamine derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, etc.) as described later may be used.
- arylamine derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, etc. arylamine derivative, carbazole derivative, thiophene derivative, fluorene derivative, distyrylbenzene derivative, etc.
- a structure containing an aromatic ring and / or a heterocyclic ring as described above is preferably used for the carboxylic acid.
- Carboxylic acid has many choices and is suitable for optimizing the interaction with the hole transporting compound to be mixed, optimizing the hole injection transport function, and optimizing the adhesion with the adjacent layer. A child.
- X is halogen or alkoxide, and chlorine, bromine, iodine, methoxide, ethoxide, isopropoxide, sec-butoxide, and tert-butoxide can be used.
- L is a neutral ligand, and triarylphosphine such as trialkylphosphine such as P (n-C 4 H 9 ) 3 or P (CH 3 ) 3 or triphenylphosphine can be used.
- the molybdenum (II) complex having an oxidation number of +2
- other halogen complexes such as [Mo II 2 X 4 L 4 ] and [Mo II X 2 L 4 ] can be used.
- Examples of the molybdenum (III) complex having an oxidation number of +3 include [(RO) 3 Mo ⁇ Mo (OR) 3 ] and [Mo (CN) 7 (H 2 O)] 4 ⁇ .
- R is a linear or branched alkyl group having 1 to 20 carbon atoms.
- 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.
- 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, he
- Examples of the molybdenum (IV) complex having an oxidation number of +4 include [Mo ⁇ N (CH 3 ) 2 ⁇ 4 ], [Mo (CN) 8 ] 4 ⁇ , and MoO 2+ having an oxo ligand. And a complex of Mo 2 O 2 4+ double-crosslinked with O 2 ⁇ .
- Examples of the molybdenum (V) complex having an oxidation number of +5 include, for example, Mo (OCH 2 CH 3 ) 5 , [Mo (CN) 8 ] 3 ⁇ , and 2 in which Mo ⁇ O is bridged with O 2 ⁇ in the trans position.
- As an oxo complex having a nucleus Mo 2 O 3 4+ for example, a xanthogenic acid complex Mo 2 O 3 (S 2 COC 2 H 5 ) 4 , a binuclear structure in which Mo ⁇ O is double-bridged with O 2 ⁇ in the cis position
- Examples of the oxo complex having Mo 2 O 4 2+ include histidine complex [Mo 2 O 4 (L-histidine) 2 ] ⁇ 3H 2 O.
- examples of the molybdenum (VI) complex having an oxidation number of +6 include MoO 2 (acetylacetonate) 2 ].
- MoO 2 acetylacetonate
- Examples of the tungsten complex having an oxidation number of 0 or less include, for example, metal carbonyl [W 2 -II (CO) 5 ] 2 ⁇ , [(CO) 5 W ⁇ I W ⁇ I (CO) 5 ] 2 ⁇ , [W ( CO) 6 ] and the like.
- Examples of the tungsten (I) complex having an oxidation number of +1 include non-Werner type complexes containing diphosphane and ⁇ 5 -cyclopentadienide.
- Examples of the tungsten (II) complex having an oxidation number of +2 include W 2 compounds in which tungsten becomes a binuclear complex and exists in the state of (W 2 ) 4+ ions. For example, [W 2 (RCOO) 4 ] And [W 2 X 2 L 2 (RCOO) 4 ].
- R in the RCOO may be the same as that described for the molybdenum complex.
- Other examples of the tungsten (II) complex having an oxidation number of +2 include halogen complexes such as [W II 2 X 4 L 4 ] and [W II X 2 L 4 ].
- Examples of the tungsten (III) complex having an oxidation number of +3 include [(RO) 3 W ⁇ W (OR) 3 ] and [W (CN) 7 (H 2 O)] 4 ⁇ .
- R is a linear or branched alkyl group having 1 to 20 carbon atoms.
- Examples of the tungsten (IV) complex having an oxidation number of +4 include [W ⁇ N (CH 3 ) 2 ⁇ 4 ], [W (CN) 8 ] 4 ⁇ , and WO 2+ having an oxo ligand. And a complex of W 2 O 2 4+ double-crosslinked with O 2 ⁇ .
- Examples of the tungsten (V) complex having an oxidation number of +5 include [W (CN) 8 ] 3 ⁇ , W (OCH 2 CH 3 ) 5 , and two nuclei in which W ⁇ O is bridged with O 2 ⁇ in the trans position.
- Examples of the oxo complex having 2 O 4 2+ include histidine complex [W 2 O 4 (L-histidine) 2 ] ⁇ 3H 2 O.
- tungsten (VI) complex having an oxidation number of +6 examples include W (OCH 2 CH 3 ) 6 , WO 2 (acetylacetonate) 2 ], and TUNGSTEN (VI) PHENOXIDE.
- W OCH 2 CH 3
- WO 2 acetylacetonate
- TUNGSTEN (VI) PHENOXIDE TUNGSTEN
- Examples of vanadium complexes having an oxidation number of 0 or less include metal carbonyl [V 0 (CO) 6 ], and examples of metal oxide complexes include V III O oxytriisopropoxide.
- Examples of the vanadium (II) complex having an oxidation number of +2 include cyclopentadienyl complex [V II ( ⁇ 5 -C 5 H 5 ) 2 ].
- Examples of the vanadium (III) complex having an oxidation number of +3 include [V III Cl 3 ⁇ N (CH 3 ) 3 ⁇ 2 ], and examples of the metal oxide complex include V III O acetylacetonate.
- Vanadium (IV) complexes with an oxidation number of +4 include [VOCl 2 ⁇ N (CH 3 ) 3 ⁇ 2 ]), [VCl 4 (diars)]), 8 (decahedral [VCl 4 (diars) 2 ] ) And the like.
- the transition metal oxide is necessarily contained in the organic-transition metal oxide complex which is a reaction product of the organic transition metal complex.
- the value of ionization potential is optimized, and changes due to oxidation from unstable oxidation number +0 metal are suppressed in advance, so that the drive voltage is reduced and the device lifetime is reduced. It becomes possible to improve.
- it is preferable that transition metal oxides having different oxidation numbers coexist in the organic-transition metal oxide composite. By including transition metal oxides with different oxidation numbers together, the hole transport and hole injection properties are appropriately controlled by the balance of the oxidation numbers, thereby reducing drive voltage and improving device lifetime. It becomes possible.
- the reaction product of a molybdenum complex or a tungsten complex is a composite having molybdenum oxidation numbers of +5 and +6 or a composite having tungsten oxidation numbers of +5 and +6, respectively. This is preferable from the viewpoint of improving the life.
- the reaction product of the molybdenum complex or the reaction product of the tungsten complex is present in the anion state of a complex of molybdenum oxidation numbers +5 and +6 or tungsten oxidation numbers +5 and +6, respectively. This is preferable from the viewpoint of reducing the device life and improving the device life.
- molybdenum oxide such as MoO 3
- most of the molybdenum is Mo VI
- the composition formula is Mo n O 3n .
- Mo n O 3n-m due to oxygen vacancies at the time of vapor deposition or oxygen defects present on the particle surface caused by physical pulverization at the time of slurry formation, and there may be some Mo V.
- Mo V introduced by MoO 3 is caused by oxygen defects, and therefore is non-uniform and unstable.
- the oxidation number +5 is stable (V 2 O 5 )
- the oxidation number +4 is unstable (V 2 O 4 ).
- the reaction product of the vanadium complex is preferably present in the anion state of the complex having vanadium oxidation numbers of +5 and +4 from the viewpoint of lowering the driving voltage and improving the device lifetime.
- the organic-transition metal oxide complex used in the present invention is preferably at least a reaction product of an organic transition metal complex and an organic solvent. Furthermore, the organic transition metal complex and the organic transition metal complex are subjected to a redox reaction. It is preferably a reaction product with an organic solvent capable of carrying out the reaction, and particularly preferably a reaction product with an organic transition metal complex and an organic solvent having a carbonyl group and / or a hydroxyl group. Since the organic transition metal complex has high reactivity, it is heated or irradiated with light in the process of forming the hole injecting and transporting layer, for example, in the ink for forming the hole injecting and transporting layer or when forming the layer using the ink.
- An oxidation-reduction reaction is performed with the organic solvent contained in the hole injection transport layer forming ink, and at least a part of the transition metal complex becomes a transition metal oxide.
- the organic solvent is an organic solvent having a carbonyl group and / or a hydroxyl group, the reactivity for producing the transition metal oxide is high.
- an organic molybdenum complex or an organotungsten complex is used, an anion state of a complex having molybdenum oxidation numbers of +5 and +6 or a complex having tungsten oxidation numbers of +5 and +6 is formed. Can be stably maintained even in a relatively large amount of +5 molybdenum or tungsten, which is preferable from the viewpoint of lowering the driving voltage and improving the element life.
- the organic solvent used in the present invention is not particularly limited as long as it is an organic solvent capable of appropriately performing an oxidation-reduction reaction with an organic transition metal complex.
- Examples of the organic solvent having a carbonyl group and / or a hydroxyl group that are preferably used include aldehyde, ketone, carboxylic acid, ester, amide, alcohol, phenol, and the like. Those having a temperature of ° 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 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, buty
- a fluorine-containing organic compound is attached to the organic-transition metal oxide composite.
- “attachment” means that the fluorine-containing organic compound is fixed on the surface of the organic-transition metal oxide composite so that it does not peel even when dispersed in an organic solvent. It means being.
- “Adhesion” includes adsorption and coordination, but is preferably a chemical bond such as an ionic bond or a covalent bond.
- the “attachment” may be an embodiment in which the entire surface of the organic-transition metal oxide composite is attached so as to cover the fluorine-containing organic compound, or a part of the surface may contain the fluorine-containing organic compound. It may be an embodiment in which is attached.
- the device material for a hole injecting and transporting layer of the present invention since an organic compound containing at least a fluorine-containing organic compound is attached to the organic-transition metal oxide composite, in particular, it is simply a transition metal as in Patent Document 5. Unlike particles formed by pulverizing oxides, the dispersion stability is extremely high, and a thin film of nm order with high uniformity can be formed. Therefore, the thin film formed with the device material for a hole injecting and transporting layer according to the present invention is not easily short-circuited because of high stability and uniformity over time. Furthermore, it becomes excellent in adhesiveness with an adjacent electrode or an organic layer.
- the type of the fluorine-containing organic compound adhering to the surface is appropriately selected and is not particularly limited.
- the fluorine-containing organic compound include organic compounds in which part or all of hydrogen contained in a linear, branched, or cyclic saturated or unsaturated hydrocarbon which may contain a hetero atom is substituted with fluorine. It may be an organic compound in which part or all of hydrogen contained in an organic compound that may contain a heteroatom conventionally used as a hole injecting and transporting material is substituted with fluorine. Or the compound which introduce
- the fluorine-containing organic compound include a linear, branched, or cyclic alkyl group, a fluorinated alkyl group or a fluorinated aryl group in which part or all of the hydrogen of the aryl group is fluorinated, and combinations thereof. Is mentioned.
- the number of carbon atoms in the fluorinated alkyl group is not particularly limited, but is preferably 2 to 10, and more preferably 4 to 6. Further, the number of carbon atoms of the fluorinated aryl group or the combination of the fluorinated alkyl group such as the fluorinated arylated alkyl group and the fluorinated aryl group is not particularly limited, but is preferably 6 to 12, more preferably 6 to 9.
- the fluorine-containing organic compound preferably contains a fluorinated alkyl group from the viewpoint of good change in wettability due to energy irradiation and excellent patterning.
- the fluorine-containing organic compound include —NH—, —N ⁇ , —S—, —O—, —NH (C ⁇ O) —, —O— (C ⁇ O) —, —O— (SO 2 )-, —O— (C ⁇ O) —O—, —S— (C ⁇ O) —O—, —SiR 2 — (C ⁇ O) —O—, —SiR 2 — It is preferable to include a hetero atom that does not form, since the fluorine organic compound is easily decomposed by energy irradiation, and the sensitivity is improved in the wettability change pattern forming step.
- C n F 2n + 1 C m H 2m ⁇ [m is an integer of 0 to 20, n is an integer of 1 to 20, and m + n is 1 to 30.
- the fluorinated alkyl group represented by the above formula maintains a high oil repellency, and when m is 1 or more, it binds to other elements such as an ether bond rather than directly bonding to C n F 2n + 1.
- the direction through m H 2m is preferred from the viewpoint of increasing the stability of the compound.
- n is preferably an integer of 2 to 10, more preferably an integer of 4 to 6.
- m is preferably an integer of 0 to 10, more preferably an integer of 2 to 8.
- the fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 50 to 100%, more preferably 80 to 100%, and particularly perfluoro having all the hydrogen atoms replaced with fluorine atoms.
- An alkyl group is preferable from the viewpoint of expressing high oil repellency.
- the fluorine-containing organic compound containing an aromatic hydrocarbon and / or a heterocyclic ring is preferable from the viewpoint that the boiling point of the fluorine-containing organic compound can be increased.
- the restriction on the synthesis temperature of the device material for the hole injection transport layer to which the fluorine-containing organic compound of the present invention is attached can be widened, or that the high temperature process temperature can be set high when manufacturing the device. is there.
- aromatic hydrocarbons and / or heterocycles often have charge transport properties, charge mobility in a hole injecting and transporting layer prepared from a fluorine-containing organic compound containing aromatic hydrocarbons and / or heterocycles.
- each layer of an organic device such as an organic EL element usually contains an aromatic hydrocarbon and / or a heterocyclic charge transporting material, so the improvement of the adhesion between the adjacent organic layer and the hole injection transport layer is considered. Then, inclusion of an aromatic hydrocarbon and / or heterocyclic structure is preferable from the viewpoint of contributing to a long driving life.
- fluorinated alkyl group examples include the following structures. CF 3 -, CF 3 CF 2 -, CHF 2 CF 2 -, CF 3 (CF 2) 2 -, CF 3 (CF 2) 3 -, CF 3 (CF 2) 4 -, CF 3 (CF 2) 5 -, CF 3 (CF 2) 6 -, CF 3 (CF 2) 7 -, CF 3 (CF 2) 8 -, CF 3 (CF 2) 9 -, CF 3 (CF 2) 11 -, CF 3 ( CF 2 ) 15 —, CF 3 CH 2 CH 2 —, CF 3 CF 2 CH 2 CH 2 —, CHF 2 CF 2 CH 2 CH 2 —, CF 3 (CF 2 ) 2 CH 2 CH 2 —, CF 3 (CF 2 ) 3 CH 2 CH 2 —, CF 3 (CF 2 ) 4 CH 2 CH 2 —, CF 3 (CF 2 ) 5 CH 2 CH 2 —, CF 3 (CF 2 ) 6 CH 2 —
- fluorine-containing organic compounds containing aromatic hydrocarbons and / or heterocycles include pentafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 3,4,5-trifluorophenyl group, 2 , 4-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, nonafluorobiphenyl group, ⁇ , ⁇ , ⁇ , 2,3,5,6-heptafluoro-p-tolyl group, Heptafluoronaphthyl group, (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, pentafluorophenylmethyl group, 2,3,5,6-tetrafluorophenylmethyl group, 3,4, 5-trifluorophenylmethyl group, 2,4-
- the action of linking with the transition metal and / or transition metal compound on the surface of the organic-transition metal oxide composite It is preferably attached using a linking group that yields That is, the fluorine-containing organic compound is preferably attached to the surface of the organic-transition metal oxide composite by a protective agent containing a linking group at the terminal of the fluorine-containing organic compound.
- the linking group is not particularly limited as long as it has an effect of linking with a transition metal and / or a transition metal compound.
- the connection includes adsorption and coordination, but is preferably a chemical bond such as an ionic bond or a covalent bond.
- the number of linking groups in the protective agent may be any number as long as it is one or more in the molecule. However, in consideration of solubility in a solution, dispersion stability, and oil repellency, it is preferable that there is one linking group in one molecule of the protective agent. When the number of linking groups is one in one molecule, the protective agent binds to the organic-transition metal oxide complex or forms a dimer by a bimolecular reaction to stop the reaction.
- the dimer Since the dimer has poor adhesion to the organic-transition metal oxide composite, it can be easily removed by adding a washing step to the preparation process of the organic-transition metal oxide composite.
- the nanoparticles when two or more linking groups exist in one molecule, the nanoparticles are connected to each other, and the particles may easily aggregate in the ink.
- linking group examples include a hydrophilic group such as a carboxyl group, an amino group, a hydroxyl group, a thiol group, an aldehyde group, a sulfonic acid group, an amide group, a sulfonamide group, a phosphoric acid group, a phosphinic acid group, and a P ⁇ O group, or And ionic liquids such as ammonium salt, imidazolium salt, pyridium salt, sulfonium salt, phosphonium salt, morpholinium salt, piperidinium salt, and the like.
- the linking group is preferably at least one selected from functional groups represented by the following formulas (1a) to (1n).
- Z 1 , Z 2 and Z 3 each independently represent a halogen atom or an alkoxy group.
- Examples of the protective agent suitably used for the device material for a hole injection transport layer according to the present invention and containing a linking group at the terminal of the fluorine-containing organic compound include a protective agent represented by the following general formula (I). It is done.
- Formula (I) YQ- (A′-FQ ′) n- (A-FQ) (In the general formula (I), Y represents the linking group.
- Q represents a linear, branched or cyclic aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group, or A combination of these or a direct bond
- a and A ′ are each independently —NH—, —N ⁇ , —S—, —O—, —NH (C ⁇ O) —, —O— (C ⁇ O) —, —O— (SO 2 ) —, —O— (C ⁇ O) —O—, —S— (C ⁇ O) —O—, —SiR 2 — (C ⁇ O) —O—, —SiR 2 — or a direct bond
- R represents hydrogen or a linear, branched or cyclic aliphatic hydrocarbon group
- FQ and FQ ′ each independently represent the fluorine-containing organic compound.
- n is 0 or an integer of 1 or more.
- a and / or A ′ is —NH—, —N ⁇ , —S—, —O—, —NH (C ⁇ O) —, —O— (C ⁇ O) —, —O— (SO 2 ) —, —O— (C ⁇ O) —O—, —S— (C ⁇ O) —O—, —SiR 2 — (C ⁇ O) —O—, —SiR 2 — Since it is easy to cut
- Q contains an aromatic hydrocarbon group or an aromatic heterocyclic group
- it can contribute to increasing the charge mobility in the hole injecting and transporting layer.
- a and / or A ′ is cleaved by a treatment that decomposes the fluorine-containing organic compound described later, the fluorine-containing organic compound FQ is decomposed and removed, but the aromatic hydrocarbon and / or the heterocyclic ring is removed. Since the portion of Q that is included remains on the surface of the organic-transition metal oxide composite, when Q has a high charge transporting property, it can contribute to higher device efficiency.
- FQ is a monovalent fluorine-containing organic compound group
- FQ ′ is a divalent fluorine-containing organic compound group.
- n is 1 or more, it is easily cleaved at the portion A ′ by energy irradiation, and the fluorine organic compound represented by FQ is easily decomposed. Examples of the case where n is 1 or more include -O- (CH 2 ) p -O- (CH 2 ) 2- (CF 2 ) q -CF 3 .
- n is preferably 5 or less, and more preferably 4 or less from the viewpoint of increasing the decomposition rate.
- Examples of the protecting agent represented by the general formula (I) include, but are not limited to, the following structures.
- N and n ′ are integers of 1 to 5, m and m ′ are 0 or an integer of 1 to 5, and l is an integer of 0 or 1 to 5.
- Y is the formula (1a) to (1n). Any of the functional groups shown.)
- the fluorine-containing organic compound adhering to the surface can be used even if it is a high molecular compound, it is preferable that molecular weight is 1000 or less. As the molecular weight increases, the ratio of the linking group to the organic component in one molecule of the fluorine-containing organic compound decreases, so the probability of binding to nanoparticles decreases, dispersibility deteriorates, and control of particle size uniformity is difficult. Or the particle size may increase. Further, when the molecular weight of the fluorine-containing organic compound attached to the surface is increased, the ratio of the remaining organic component is increased when the device is formed, and there is a risk of adversely affecting characteristics such as higher voltage.
- the molecular weight of the fluorine-containing organic compound adhering to the surface means the molecular weight of the compound itself when it does not have a molecular weight distribution, and in terms of polystyrene measured by gel permeation chromatography (GPC) when it has a molecular weight distribution.
- the value means the weight average molecular weight.
- an organic-transition metal oxide complex which is a reaction product of an organic transition metal complex and an organic compound containing a fluorine-containing organic compound attached to the surface thereof
- the content ratio is appropriately selected and is not particularly limited.
- 10 to 200 parts by weight of fluorine atoms attached to the surface are charged with respect to 100 parts by weight of transition metal atoms.
- the molar ratio of the transition metal atom to the fluorine atom attached to the surface is preferably 5: 1 to 1: 5.
- the molar ratio of transition metal atom to carbon atom is preferably 1: 2 to 1: 200, more preferably 1: 5 to 1:20. These ratios can be determined by, for example, NMR or X-ray photoelectron spectroscopy.
- the amount of the fluorine-containing organic compound adhering to the surface is the liquid repellency of the layer formed using the hole injection / transport layer device material.
- the method for producing a device material for a hole injecting and transporting layer used in the present invention comprises a material having a fluorine-containing organic compound attached to the surface of an organic-transition metal oxide complex, which is a reaction product of the organic transition metal complex described above.
- the method is not particularly limited as long as it can be obtained.
- Examples of the method for producing an organic-transition metal oxide composite having a fluorine-containing organic compound attached to the surface include, for example, an organic transition metal complex and a protective agent having a linking group at the terminal of the fluorine-containing organic compound in the presence of oxygen.
- Examples include a method of reacting in a solvent, preferably an organic solvent having the above carbonyl group and / or hydroxyl group.
- an organic transition metal complex is reacted in the presence of oxygen in an organic solvent, preferably in an organic solvent having the above carbonyl group and / or hydroxyl group, to obtain an organic-transition metal oxide complex.
- An organic-transition metal oxide composite and a protective agent having a linking group at the end of the fluorine-containing organic compound are allowed to act to obtain a material in which the fluorine-containing organic compound is adhered to the surface of the organic-transition metal oxide composite. Also good.
- the hole injection transport layer forming ink contains the hole injection transport layer device material according to the present invention and an organic solvent.
- the hole injection transport layer forming ink according to the second aspect of the present invention comprises an organic-transition metal oxide composite that is a reaction product of an organic transition metal complex, and a transition metal and / or transition metal oxide linked to each other. It contains a fluorine-containing organic compound containing a linking group that produces the action of an organic solvent, and an organic solvent.
- the ink for forming a hole injecting and transporting layer according to the third aspect of the present invention includes an organic transition metal complex, and a fluorine-containing organic compound containing a linking group that causes an action of linking with a transition metal and / or a transition metal oxide, It contains an organic solvent having a carbonyl group and / or a hydroxyl group.
- the hole injecting and transporting layer forming ink of the second and third aspects is a process for forming a hole injecting and transporting layer, for example, in the hole injecting and transporting layer forming ink (coating solution) or at the time of layer formation.
- the organic transition metal complex reaction product which is the device material for a hole injecting and transporting layer according to the present invention, by a reaction performed at the time of heating, light irradiation, element driving, etc.
- a material can be produced in which a fluorine-containing organic compound is attached to the transition metal oxide complex.
- the ink for forming a hole injecting and transporting layer according to the present invention may further contain other compounds as necessary.
- a hole transport compound as described later for example, a hole transport compound as described later, and additives such as a binder resin and a coating property improver that do not trap holes.
- the ink for forming a hole injecting and transporting layer may be prepared by adding, dissolving or dispersing.
- Examples of the organic solvent used in the inks of the first and second embodiments include the device material for a hole injection / transport layer according to the present invention, or an organic-transition metal oxide that is a reaction product of an organic transition metal complex.
- the fluorine-containing organic compound containing a linking group capable of linking to the transition metal and / or transition metal oxide, and other components contained as required are dissolved or dispersed well.
- a fluorine-containing organic compound is attached to the surface of the organic-transition metal oxide composite, a fluorine-based solvent is preferably used.
- trifluoromethylbenzene heptafluoro-n-ethyl butyrate, heptafluoro-n-methyl butyrate, 1,1,3,3-hexafluoro-2-propanol, 1,1,3,3-hexafluoro-2
- Fluorinated all or part of the solvent such as -phenyl-2-propanol, 1H, 1H-trifluoroethanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol be able to.
- the above solvents can be used alone or as a co-solvent in which a plurality of solvents are mixed.
- the organic solvent having a carbonyl group and / or a hydroxyl group used in the third ink the same organic solvent as described in the section of the device material for hole injection / transport layer according to the present invention can be used. .
- the ink of the first aspect may be prepared by mixing the hole injection transport layer device material according to the present invention and an organic solvent.
- an organic transition metal complex and a fluorine-containing organic compound containing a linking group capable of linking with a transition metal and / or transition metal oxide are dissolved or dispersed in an organic solvent having a carbonyl group and / or a hydroxyl group,
- the transition metal in the organic transition metal complex may be oxidized to obtain the hole injection transport layer forming ink according to the present invention. Examples of the oxidation method include heating in the presence of oxygen or light irradiation.
- the organic-transition metal oxide complex in the ink of the second aspect is obtained by dissolving or dispersing an organic transition metal complex in an organic solvent having a carbonyl group and / or a hydroxyl group, It is preferable to obtain the metal by oxidation.
- 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.
- examples of the light irradiation means include a method of exposing to ultraviolet rays. Since the interaction between the organic transition metal complex and the organic-transition metal oxide complex varies depending on the heating temperature or the amount of light irradiation, it is preferable to adjust appropriately.
- the content of the hole injection / transport layer device material according to the present invention in the hole injection / transport layer forming ink according to the present invention can be appropriately adjusted according to the purpose and is not particularly limited.
- the content is preferably about 0.1 to 10.0% by weight.
- a first aspect of a device manufacturing method according to 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.
- a manufacturing method comprising: A hole injection transport layer forming step for forming a hole injection transport layer containing the device material for hole injection transport layer according to the present invention on the substrate on which the first electrode layer is formed in a pattern, After disposing a photocatalyst-containing layer substrate on which a photocatalyst-containing layer containing at least a photocatalyst is formed on the substrate, with a gap that can act as a photocatalyst associated with energy irradiation with respect to the hole injecting and transporting layer, And a wettability change pattern forming step of forming a wettability change pattern having changed wettability on the surface of the hole injecting and transporting layer by irradiating energy in a pattern.
- a second aspect of the device manufacturing method according to the present invention 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. Because A hole injection transport layer forming step of forming a hole injection transport layer containing the device material for hole injection transport layer according to the present invention on a substrate on which an electrode layer is formed in a pattern, And a wettability changing pattern forming step of forming a wettability changing pattern having changed wettability on the surface of the hole injecting and transporting layer by irradiating the pattern with vacuum ultraviolet rays.
- the hole injecting and transporting layer contains a material to which a liquid repellent fluorine-containing organic compound is attached
- the fluorine-containing organic compound is decomposed by the action of a photocatalyst or irradiation with vacuum ultraviolet rays.
- a photocatalyst or irradiation with vacuum ultraviolet rays By removing fluorine, a large difference in wettability can be produced between the irradiated portion and the non-irradiated portion.
- irradiating energy or vacuum ultraviolet rays through the photocatalyst containing layer to the hole injecting and transporting layer where wettability can be changed a wettability change pattern is formed, and the wettability difference of this wettability change pattern is determined.
- a pattern-like device layer necessary for the device can be easily laminated on the hole injecting and transporting layer by a coating method.
- the organic-transition metal oxide composite contained in the hole injection / transport layer device material according to the present invention contained in the hole injection / transport layer is used in the wettability change pattern forming step. Since it has resistance to ultraviolet light, the excellent hole injecting and transporting property is not deteriorated even after the wettability changing pattern forming step, and has an advantage that it is not impaired. Furthermore, through the wettability change pattern forming process such as photocatalyst treatment, the hole injection / transport layer device material according to the present invention has a high ionization potential and the hole injection property is improved.
- the device material for a hole injection transport layer according to the present invention has high heat resistance and light resistance and is not easily deteriorated, and the hole injection property is improved through a wettability change pattern forming step.
- the manufactured device also has an increased lifetime.
- the device material for a hole injecting and transporting layer according to the present invention is resistant to heating at a relatively high temperature (for example, 200 ° C.), the wettability change pattern is not impaired during the heating process.
- the step of laminating a number of layers in a pattern can be performed.
- 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. 1A to 1C are process diagrams showing an example of a device manufacturing method of the present invention.
- a first electrode layer 3 is formed in a pattern on a substrate 2, and the hole injection transport layer device material according to the present invention is formed on the first electrode layer 3.
- the hole injection transport layer 4 to be contained is formed (hole injection transport layer forming step).
- FIG. 1 (B) the substrate 22, the light shielding portion 23 formed in a pattern on the substrate 22, and the photocatalyst is formed on the substrate 22 so as to cover the light shielding portion 23.
- a photocatalyst containing layer substrate 21 having a photocatalyst containing layer 24 to be prepared is prepared.
- the photocatalyst-containing layer substrate 21 is arranged with a gap that can act as a photocatalyst accompanying energy irradiation with respect to the hole injecting and transporting layer 4, and then the hole injecting and transporting layer through the photocatalyst containing layer substrate 21. 4 is irradiated with energy rays 27 in a pattern. As shown in FIG.
- the surface layer of the hole injecting and transporting layer 4 is exposed in the exposed portion of the hole injecting and transporting layer 4 due to the action of the photocatalyst contained in the photocatalyst containing layer 24 by irradiation with the energy beam 27.
- the hole-injecting / transporting layer 4 is decomposed and removed from the fluorine-containing organic compound on the surface of the hole-injecting / transporting layer device material. A lyophilic region 11 is formed.
- the fluorine-containing organic compound present on the surface of the hole injecting and transporting layer device material in the surface layer portion of the hole injecting and transporting layer 24 remains as it is, and the liquid repellent region 12 and (Wetting change pattern forming step) In this way, the device substrate 1 is obtained. Thereafter, on the lyophilic region 11 on the device substrate 1, at least a pattern layer necessary for the device is laminated, and the second electrode layer is laminated, whereby the device can be manufactured.
- FIGS. 2A to 2C are process diagrams showing another example of the device manufacturing method of the present invention.
- the first electrode layer 3 is formed in a pattern on the substrate 2, and a partition (partition 6a) is formed in the opening of the pattern.
- the hole injecting and transporting layer 4 containing the device material for hole injecting and transporting layer according to the present invention is formed on the part (partition wall 6a) (hole injecting and transporting layer forming step).
- substrate 2 is a translucent board
- a photocatalyst containing layer substrate 21 having a base 22 and a photocatalyst containing layer 24 containing a photocatalyst formed on the base 22 is prepared.
- the energy beam 27 is transmitted from the substrate 2 side which is a translucent substrate. Irradiate.
- the partition part (partition wall 6a) since the partition part (partition wall 6a) reflects or absorbs the energy rays, the energy beam 27 is irradiated to the part where the partition part (partition wall 6a) is not formed, and the partition part (partition wall 6a) is formed.
- the energy rays 27 are not irradiated in the places where 2C, at least the surface layer of the hole injection / transport layer 4 is exposed in the exposed portion of the hole injection / transport layer 4 due to the action of the photocatalyst contained in the photocatalyst-containing layer 24.
- the hole-injecting / transporting layer 4 is decomposed and removed from the fluorine-containing organic compound present on the surface of the hole-injecting / transporting layer device material.
- a lyophilic region 11 is formed.
- the fluorine-containing organic compound present on the surface of the hole injecting and transporting layer device material in the surface layer portion of the hole injecting and transporting layer 24 remains as it is, and the liquid repellent region 12 and (Wetting change pattern forming step) In this way, the device substrate 1 is obtained. Thereafter, a pattern-like device layer necessary for the device can be laminated on the lyophilic region 11 on the device substrate 1 by a coating method, and then a second electrode layer is laminated to manufacture the device. Can do.
- the partition that reflects or absorbs the irradiated energy rays functions as a mask. Therefore, a light shielding portion in the photocatalyst-containing substrate or a separate photomask is used. Even if it does not bother to prepare, it is possible to irradiate the hole injecting and transporting layer with energy in a pattern, and the merit in the manufacturing process is great.
- the hole injection / transport layer device material used for the hole injection / transport layer of the present invention has a higher transmittance in the ultraviolet wavelength region than conventional organic compound hole injection / transport materials. Energy irradiation from the back surface of the injecting and transporting layer is also possible.
- FIG. 3A to FIG. 3C are process diagrams showing another example of the device manufacturing method of the present invention.
- the first electrode layer 3 is formed in a pattern on the substrate 2, and a partition (partition 6a) is formed in the opening of the pattern.
- the first electrode layer 3 and the partition The hole injection / transport layer 4 containing the device material for hole injection / transport layer according to the present invention is formed on the (partition wall 6a) (hole injection / transport layer forming step).
- FIG. 3B a photocatalyst containing layer substrate 21 having a base 22 and a photocatalyst containing layer 24 containing a photocatalyst formed on the base 22 is prepared.
- the photocatalyst-containing layer substrate 21 is arranged with a gap that can act as a photocatalyst accompanying energy irradiation with respect to the hole injecting and transporting layer 4, and then the hole injecting and transporting layer through the photocatalyst containing layer substrate 21. 4 is irradiated with an ultraviolet laser beam 28 scanned in a pattern. As shown in FIG. 3C, by irradiation of the ultraviolet laser light 28, at least the hole injection transport layer 4 is exposed in the exposed portion of the hole injection transport layer 4 due to the action of the photocatalyst contained in the photocatalyst containing layer 24.
- the surface of the exposed portion of the hole injection / transport layer 4 is formed with the fluorine decomposition portion 5 of the hole injection / transport layer, in which the fluorine-containing organic compound present on the surface of the hole injection / transport layer device material of the surface layer is decomposed and removed.
- the lyophilic region 11 is formed.
- the fluorine-containing organic compound present on the surface of the hole injecting and transporting layer device material in the surface layer portion of the hole injecting and transporting layer 24 remains as it is, and the liquid repellent region 12 and (Wetting change pattern forming step) In this way, the device substrate 1 is obtained. Thereafter, a pattern-like device layer necessary for the device can be laminated on the lyophilic region 11 on the device substrate 1 by a coating method, and then a second electrode layer is laminated to manufacture the device. Can do.
- FIG. 4A to 4C are process diagrams showing another example of the device manufacturing method of the present invention.
- the first electrode layer 3 is formed in a pattern on the substrate 2, and a partition (partition 6a) is formed in the opening of the pattern.
- the hole injecting and transporting layer 4 containing the device material for hole injecting and transporting layer according to the present invention is formed on the part (partition wall 6a) (hole injecting and transporting layer forming step).
- FIG. 4B a metal mask 30 is disposed on the surface of the hole injection / transport layer 4 and the hole injection / transport layer 4 is irradiated with vacuum ultraviolet light 29 through the metal mask 30. To do.
- FIG. 4 (A) the first electrode layer 3 is formed in a pattern on the substrate 2, and a partition (partition 6a) is formed in the opening of the pattern.
- the hole injecting and transporting layer 4 containing the device material for hole injecting and transporting layer according to the present invention is formed on the part (partition wall 6a) (hole inject
- the surface of the hole injecting and transporting layer device material at least in the surface layer of the hole injecting and transporting layer 4 is exposed to the vacuum ultraviolet light 29 as shown in FIG.
- the fluorine decomposition part 5 of the hole injection transport layer is formed by decomposing and removing the existing fluorine-containing organic compound, and the lyophilic region 11 is formed on the surface of the exposed part of the hole injection transport layer 4.
- the fluorine-containing organic compound present on the surface of the hole injecting and transporting layer device material in the surface layer portion of the hole injecting and transporting layer 24 remains as it is, and the liquid repellent region 12 and (Wetting change pattern forming step) In this way, the device substrate 1 is obtained. Thereafter, a pattern-like device layer necessary for the device can be laminated on the lyophilic region 11 on the device substrate 1 by a coating method, and then a second electrode layer is laminated to manufacture the device. Can do.
- the lyophilic region 11 is formed in at least the surface layer portion of the hole injecting and transporting layer 4 in the portion where the action of the photocatalyst due to the energy irradiation or the portion irradiated with the vacuum ultraviolet light is irradiated.
- the fluorine-containing organic compound present on the surface of the hole injection / transport layer device material in at least the surface layer of the hole injection / transport layer 4 is decomposed and removed by the action of a photocatalyst associated with energy irradiation or vacuum ultraviolet light irradiation.
- the “lyophilic region” means a region where the liquid contact angle is smaller than that of the liquid repellent region, and has good wettability with respect to the layer forming ink formed adjacent to the hole injection transport layer. This is an important area.
- the “liquid repellency region” refers to a region having a liquid contact angle larger than that of the lyophilic region, and is a region having poor wettability with respect to the layer forming ink or the like.
- the contact angle of the liquid in the lyophobic region is preferably 10 ° or more higher than the contact angle of the liquid in the lyophilic region when a liquid having a surface tension of 28.5 mN / m is used, and more preferably 20 ° or more. It is preferably high, and particularly preferably 40 ° or higher.
- the contact angle of a liquid having a surface tension of 28.5 mN / m is preferably 25 ° or more, more preferably 45 ° or more, and further preferably 55 ° or more. Since the liquid repellency region is a portion where liquid repellency is required, if the contact angle of the liquid is too small, the liquid repellency is not sufficient and the layer forming ink or the like adheres to the liquid repellency region. Because there is a possibility.
- the contact angle of a liquid having a surface tension of 28.5 mN / m is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. This is because if the contact angle of the liquid is too high, the layer forming ink or the like may be difficult to spread and the layer formed adjacently may be lost.
- the contact angle of the liquid is measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (dropping droplets from a microsyringe). 5 seconds later) and can be obtained from the result or in the form of a graph.
- a wetting index standard solution manufactured by Junsei Co., Ltd. is used as the liquid having various surface tensions.
- the first hole injection / transport layer forming step in the present invention comprises the step of forming the hole injection / transport layer device material according to the present invention on a substrate on which the first electrode layer is formed in a pattern. It is a step of forming a hole injection transport layer to be contained.
- the device material for the hole injecting and transporting layer according to the present invention can be formed on the entire surface of the substrate on which the first electrode layer is formed in a pattern. If it is, it will not specifically limit.
- a wet process in which the ink for forming a hole injecting and transporting layer according to the first, second, or third aspect of the present invention is prepared and applied using the ink to form a layer is a process advantage. From the point of view, it is preferable.
- a transfer method for transferring a layer formed by applying the ink can also be used. If the first electrode layer is formed in a pattern on the substrate, for example, a hole injection layer is formed on the first electrode layer, and then the hole injection transport layer of the present invention is formed. May be.
- the ink for forming a hole injecting and transporting layer according to the present invention can be prepared in the same manner as described in the section “II. Ink for forming a hole injecting and transporting layer”.
- a hole injecting and transporting layer further containing the other components can be formed.
- the amount of transition metal oxide in the device material for hole injection / transport layer may increase, and the hole injection / transport property may be improved.
- any method can be used as long as the above-described material can be uniformly formed on the entire surface of the substrate, for example, a die coating method, a spin coating method, a dip coating method, a roll coating method.
- a drying treatment may be performed.
- a drying method a general drying method can be used, and for example, a heating method can be mentioned.
- a heating method for example, a method of passing or standing in a device that heats a whole specific space such as an oven, a method of applying hot air, a method of heating directly by far infrared rays, or heating with a hot plate Or the like can be used.
- the content of the transition metal oxide in the hole injection / transport layer device material according to the present invention contained in the layer may increase, and the hole injection / transport property may be improved.
- the hole injecting and transporting layer forming step may include a step of irradiating light in the presence of oxygen in addition to heating in the presence of oxygen.
- 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 substrate may be translucent to transmit light or may not be translucent.
- the substrate when light is extracted from the substrate side or in the process of manufacturing the device of the present invention, energy is irradiated from the substrate side when forming a pattern composed of a lyophilic region and a liquid repellent region.
- the substrate is preferably translucent.
- the light transmissive substrate include quartz and glass.
- metals such as aluminum and its alloys, plastics, woven fabrics, nonwoven fabrics and the like can be used.
- the first electrode layer used in the present invention is formed on the substrate in a pattern.
- the material for forming the first electrode layer is not particularly limited as long as it is a conductive material.
- a material which forms a 1st electrode layer it may have transparency and does not need to have it.
- energy is irradiated from the substrate side when forming a pattern composed of a lyophilic region and a liquid repellent region.
- a 1st electrode layer has transparency.
- the material having conductivity and transparency include In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, and the like.
- IZO In—Zn—O
- ITO In—Sn—O
- ZnO—Al Zn—Sn—O
- the first electrode layer when light is extracted from the opposite side of the substrate, the first electrode layer is not required to be transparent.
- a metal can be used as the conductive material, and specifically, Au, Ta, W, Pt, Ni, Pd, Cr, Al alloy, Ni alloy, Cr alloy, etc. Can do.
- the first electrode layer is formed in a pattern.
- a method for forming the first electrode layer a general electrode forming method can be used, and examples thereof include a sputtering method, an ion plating method, and a vacuum deposition method.
- An example of the patterning method for the first electrode layer is a photolithography method.
- the wettability change pattern forming step in the present invention is a step of forming a wettability change pattern having changed wettability on the surface of the hole injecting and transporting layer.
- the method of irradiating energy in a pattern to form a wettability change pattern on the surface of the hole injection / transport layer is not particularly limited as long as the material contained in the hole injection / transport layer can be decomposed into a pattern.
- a method that can generate active oxygen species such as oxygen radicals by energy irradiation is usually used. This is because the fluorine-containing organic compound adhering to the surface of the material contained in the hole injecting and transporting layer can be decomposed by the strong oxidizing / reducing power of the active oxygen species.
- a photocatalyst-containing layer substrate having a photocatalyst-containing layer containing a photocatalyst is used to form a hole injection transport layer by the action of the photocatalyst accompanying energy irradiation in a pattern.
- a step of forming a pattern comprising a lyophilic region from which fluorine is decomposed and removed, and a liquid repellent region from which fluorine is not decomposed and removed by decomposing and removing fluorine of the contained material; and (2) vacuum By irradiating ultraviolet light in a pattern, the fluorine contained in the hole injecting and transporting layer is decomposed and removed, so that the lyophilic region where fluorine is decomposed and removed, and the repellent where fluorine is not decomposed and removed.
- region is mentioned.
- a method of irradiating an electron beam or plasma through a mask having a patterned opening, a method of blowing oxygen radicals in a vacuum through a mask, or the like can be used.
- the lyophilic region is formed on the surface of the hole injection / transport layer device material contained in the hole injection / transport layer in the portion that has been subjected to the action of the photocatalyst due to energy irradiation or the portion that has been irradiated with vacuum ultraviolet light.
- This is a fluorine decomposition part of the hole injecting and transporting layer in which the attached fluorine-containing organic compound is decomposed and fluorine is removed.
- the lyophilic region does not contain the fluorine-containing organic compound attached to the surface of the device material for the hole injection / transport layer, or is attached to the surface of the material originally contained in the hole injection / transport layer. Compared with the amount of the fluorine-containing organic compound, the lyophilic region contains a small amount of the fluorine-containing organic compound.
- the lyophilic region is the one in which the fluorine-containing organic compound attached to the surface of the device material for hole injection transport layer contained in the hole injection transport layer is decomposed and fluorine is removed,
- the fluorine-containing organic compound attached to the surface of the device material for hole injection transport layer contained in the hole injection transport layer is decomposed and fluorine is removed,
- the formation position of the lyophilic region and the liquid repellent region is not particularly limited as long as the functional layer of the device such as the light emitting layer can be patterned into a desired pattern.
- the lyophilic region is disposed on the pattern of the first electrode layer, and the lyophobic region is the first electrode as shown in FIG. It is preferable to arrange on the opening of the pattern of the layer.
- the partition part (partition 6a) when the partition part (partition 6a) is formed on the board
- the ink of the adjacent layer does not adhere to the liquid repellent region disposed on the top of the partition portion, so that no layer is formed. This is because a layer adjacent to the hole injecting and transporting layer can be patterned with high accuracy.
- the partition wall using a liquid repellent material and the partition wall subjected to lyophobic treatment as in the prior art not only the top part of the partition wall but also the side part has liquid repellency. May be physically peeled off, or a thin portion such as a light emitting layer or a portion where a light emitting layer or the like is not formed may occur.
- the lyophilic region can be disposed on the side portion of the partition portion, the light emitting layer is physically separated from the side portion of the partition portion, or the thickness of the light emitting layer or the like is thin. Generation
- the liquid repellent region may be formed on the top of the partition, and as illustrated in FIG. 5, only the top P1 of the partition (partition 6a) is repelled.
- the liquid region 12 may be disposed, or although not illustrated, the liquid repellent region 12 may be disposed on a part of the top portion P1 and the side portion P2 of the partition portion (partition wall 6a).
- the liquid repellent region may be formed on the entire top of the partition, or may be formed on a part of the top of the partition.
- the liquid repellency is lowered to a position lower than the height assumed when the surface of the layered ink layered on the hole injecting and transporting layer becomes flat.
- the repellent region 12 may be formed, or the liquid repellent region 12 may be formed up to a position higher than the height.
- the pattern shape of the lyophilic region and the liquid repellent region is not particularly limited as long as a layer laminated in a desired pattern on the hole injecting and transporting layer can be patterned.
- the pattern shapes of the lyophilic region and the liquid repellent region are appropriately selected according to the pattern shape of the first electrode layer.
- the lyophilic region is also formed in a stripe shape corresponding to the stripe pattern of the first electrode layer.
- the lyophilic region may be formed in a stripe shape, or may be formed in a lattice shape or a mosaic shape.
- the methods (1) and (2) will be described for the wettability change pattern forming step.
- a method utilizing the action of a photocatalyst accompanying energy irradiation uses a photocatalyst-containing layer substrate in which a photocatalyst-containing layer containing at least a photocatalyst is formed on a substrate, and the photocatalyst-containing layer substrate is used. This is a method of irradiating the hole injection / transport layer with energy in a pattern after being arranged with a gap where the action of the photocatalyst accompanying the irradiation of energy can be achieved.
- the mechanism by which the fluorine-containing organic compound attached to the surface of the device material for the hole injection / transport layer is decomposed by the action of the photocatalyst accompanying the energy irradiation is not necessarily clear.
- the photocatalyst contained in the photocatalyst-containing layer causes an oxidation-reduction reaction by energy irradiation, and the generated active oxygen species such as superoxide radical (• O 2 ⁇ ) and hydroxy radical (• OH)
- the fluorine-containing organic compound becomes a decomposition product, and this decomposition product is volatilized and removed, so that the surface of the device material for the hole injection transport layer contained in the hole injection transport layer is removed.
- the attached fluorine-containing organic compound can be decomposed to form a region from which fluorine has been removed.
- a method for causing the photocatalyst to act on the hole injecting and transporting layer using the photocatalyst-containing layer substrate and the photocatalyst-containing layer substrate will be described.
- the photocatalyst containing layer substrate used in the present invention has a photocatalyst containing layer containing at least a photocatalyst formed on a substrate.
- the photocatalyst-containing layer 24 may be formed on the entire surface of the substrate 22, and as illustrated in FIG.
- the photocatalyst containing layer 24 may be formed on the pattern 22.
- the photocatalyst-containing layer is formed in a pattern
- the photocatalyst-containing layer is arranged with a predetermined gap with respect to the hole injecting and transporting layer, and when irradiating energy, a pattern is used using a photomask or the like. Irradiation is unnecessary, and by irradiating the entire surface, a liquid repellent region in which the material contained in the hole injecting and transporting layer is decomposed can be formed in a pattern.
- the energy irradiation direction may be any direction as long as the energy is irradiated to the portion where the photocatalyst containing layer and the hole injection transport layer face.
- the energy to be irradiated is not limited to parallel light such as parallel light.
- the light-shielding portion may be formed in a pattern on the photocatalyst-containing layer substrate.
- a photocatalyst-containing layer substrate having a patterned light-shielding portion it is not necessary to use a photomask or perform drawing irradiation with a laser beam when irradiating energy. Therefore, in this case, since alignment between the photocatalyst-containing layer substrate and the photomask is unnecessary, it can be a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary. This is advantageous in terms of cost.
- the light shielding portion 23 may be formed in a pattern on the substrate 22, and the photocatalyst containing layer 24 may be formed on the light shielding portion 23.
- a photocatalyst containing layer 24 may be formed on the substrate 22, and the light shielding portion 23 may be formed in a pattern on the photocatalyst containing layer 24.
- the light-shielding portion may be formed in a pattern on the surface on which the photocatalyst-containing layer is not formed.
- the photocatalyst-containing layer and the hole injecting and transporting layer are not spaced as compared with the case of using a photomask. Since the light-shielding portion is disposed in the vicinity of the portion disposed, the influence of energy scattering in the substrate or the like can be reduced. For this reason, it becomes possible to perform pattern irradiation of energy very accurately.
- the photomask can be attached to the surface of the light shielding part to be attachable and detachable. It is suitable for the case where is changed in a small lot.
- the photocatalyst-containing layer substrate can be the same as the photocatalyst-containing layer side substrate described in JP-A No. 2000-249821.
- the photocatalyst-containing layer substrate is arranged with a gap where the photocatalyst action accompanying energy irradiation can reach the hole injecting and transporting layer.
- the gap includes a state where the photocatalyst containing layer and the hole injection transport layer are in contact with each other.
- the distance between the photocatalyst-containing layer and the hole injecting and transporting layer is preferably 200 ⁇ m or less. This is because by disposing the photocatalyst-containing layer and the hole injecting and transporting layer at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed.
- the distance is more preferably in the range of 0.2 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m, considering that the pattern accuracy is very good, the sensitivity of the photocatalyst is high, and the efficiency of decomposition and removal is good. Within the range of ⁇ 10 ⁇ m.
- the gap is preferably in the range of 50 ⁇ m to 150 ⁇ m, and more preferably in the range of 80 ⁇ m to 120 ⁇ m.
- the gap By setting the gap to be in the above range, it is possible to suppress a decrease in pattern accuracy such as blurring or shifting of the pattern, and it is possible to suppress degradation of the efficiency of decomposition and removal due to deterioration of the sensitivity of the photocatalyst. Because it can.
- the setting of the gap in the positioning device between the photocatalyst-containing layer substrate and the hole injecting and transporting layer in the energy irradiation device is in the range of 10 ⁇ m to 200 ⁇ m. In particular, it is preferable to set within the range of 25 ⁇ m to 75 ⁇ m.
- the wavelength of light used for energy irradiation is usually set in a range of 450 nm or less, preferably in a range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above wavelength is preferred as energy for activating the photocatalytic action by the titanium dioxide.
- Examples of light sources that can be used for energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
- a method of irradiating energy in a pattern shape in addition to a method of irradiating a pattern through a photomask using these light sources, a method of irradiating a pattern in a pattern shape using a laser such as an excimer or YAG is used. You can also.
- the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for changing the wettability of the surface of the charge injecting and transporting layer due to the action of the photocatalyst in the photocatalyst containing layer.
- the substrate and the mask are preferably heated within a range of 30 ° C. to 80 ° C.
- the temperature difference between the substrate and the mask is preferably as small as possible from the viewpoint of exposure accuracy, but is preferably within 1 ° C.
- the energy irradiation direction is determined by whether or not a light shielding portion is formed on the photocatalyst-containing layer substrate, or by the light extraction direction of the device. For example, when the light-shielding part is formed on the photocatalyst-containing layer substrate and the base of the photocatalyst-containing layer substrate is transparent, energy irradiation is performed from the photocatalyst-containing layer substrate side. Also, for example, when the photocatalyst-containing layer is formed in a pattern, the energy irradiation direction, as described above, if energy is irradiated to the part facing the photocatalyst-containing layer and the hole injection transport layer, It can be in any direction. Further, for example, when a photomask is used, energy is irradiated from the side where the photomask is disposed. In this case, the side on which the photomask is arranged needs to be transparent.
- the photocatalyst containing layer 24 is formed on the entire surface of the substrate 22, and the pattern may be irradiated by drawing with a laser.
- the photocatalyst containing layer 24 is formed in a pattern on the substrate 22 as illustrated in FIG. 6A, energy is irradiated in a pattern by using a photocatalyst containing layer substrate as a mask.
- the light-shielding part 23 is formed in a pattern as illustrated in FIG. 1B, energy is irradiated in a pattern by using a photocatalyst-containing layer substrate as a mask.
- the characteristics change using the photocatalyst-containing layer side substrate described in JP-A-2000-249821 The method can be the same as the method of exerting the action of the photocatalyst on the layer.
- the method of irradiating vacuum ultraviolet light in a pattern includes a method of using a vacuum ultraviolet light mask as a mask and irradiating vacuum ultraviolet light as energy.
- the material contained in the hole injection transport layer is not necessarily clear.
- the hole injection / transport layer is irradiated with vacuum ultraviolet light
- the molecular bond of the fluorine-containing organic compound contained in the hole injection / transport layer is broken by the action of the vacuum ultraviolet light, or in the presence of oxygen, oxygen Ozone and oxygen atom radicals generated by excitation of fluorine act on the fluorine-containing organic compound, so that the fluorine-containing organic compound becomes a decomposition product, and this decomposition product is volatilized and removed. It is thought that a decomposition part can be formed.
- the wavelength of the vacuum ultraviolet light is not particularly limited as long as it is within a range in which oxygen radicals can be generated by acting with oxygen, but is usually preferably within a range of 100 nm to 250 nm, and more preferably within a range of 150 nm to 200 nm. It is preferable to be within. This is because if the wavelength is longer than the above range, the generation efficiency of oxygen radicals is lowered, and the decomposition and removal efficiency of the material contained in the hole injecting and transporting layer may be lowered. In addition, if the wavelength is shorter than the above range, stable irradiation with vacuum ultraviolet light may be difficult.
- Examples of the light source used for irradiation with vacuum ultraviolet light in the above wavelength range include an excimer lamp, a low-pressure mercury lamp, and various other light sources. Further, the irradiation amount of the vacuum ultraviolet light is not particularly limited as long as the lyophilic layer forming layer can be removed. What is necessary is just to adjust suitably with the wavelength etc. of a vacuum ultraviolet light.
- the vacuum ultraviolet light mask used in the irradiation of vacuum ultraviolet light may be any mask that can transmit vacuum ultraviolet light in a pattern, for example, a metal mask having a patterned opening, a vacuum A mask having a transparent base material that can transmit ultraviolet light and a light shielding part that is formed in a pattern on the transparent base material and that can shield vacuum ultraviolet light can be given.
- a material for the metal mask any material can be used as long as it can block the vacuum ultraviolet light.
- the transparent substrate may be any material that can transmit vacuum ultraviolet light, and for example, a quartz substrate or the like can be used.
- Examples of the light shielding material constituting the light shielding portion include metals such as chromium and chromium oxide.
- vacuum ultraviolet light is dispersed light with no directivity, when irradiating vacuum ultraviolet light through a vacuum ultraviolet light mask, this vacuum ultraviolet light mask is brought as close as possible to the hole injecting and transporting layer. It is preferable to prevent the ultraviolet light from being diffracted between the hole injecting and transporting layer and the vacuum ultraviolet light mask.
- the vacuum ultraviolet light mask is brought as close as possible to the hole injecting and transporting layer, and the vacuum ultraviolet light mask is in contact with the hole injecting and transporting layer.
- the vacuum ultraviolet light mask is brought as close as possible to the hole injection transport layer, and the vacuum ultraviolet light mask is in contact with the hole injection transport layer.
- a vacuum ultraviolet light mask may be arranged, and the vacuum ultraviolet light mask is made as close as possible to the hole injection transport layer, and the vacuum ultraviolet light mask is not in contact with the hole injection transport layer.
- a vacuum ultraviolet light mask may be disposed.
- partitioning parts such as partition walls or insulating layers are formed, and when using a vacuum ultraviolet light mask in which a light shielding part is formed in a pattern on a transparent substrate, the vacuum ultraviolet light mask is properly aligned. It can be fixed so as to be in close contact with the hole injecting and transporting layer.
- the light-shielding region in which the light-shielding part is provided on the substrate A photocatalyst-containing layer substrate having a region other than the light-shielding region and a transmission region in which only the photocatalyst-containing layer is provided on the substrate can be used.
- the liquid repellent region 12 is formed so that the contact angle of the liquid on the surface on the hole injecting and transporting layer side becomes higher from the side part side to the top side of the partition part (partition wall 6a). Can do.
- the hole injection transport layer side is adjusted.
- the liquid repellent region 12 can be formed so that the contact angle of the liquid on the surface increases from the side of the partition (partition 6a) toward the top.
- the former is corrected by adjusting the ratio of the area of the transmission region of the mask to the area of the top of the partition and the distance between the hole injecting and transporting layer and the mask by adjusting the light diffraction phenomenon.
- a gradient occurs in the amount of energy applied to the hole injecting and transporting layer, and as a result, a gradient occurs in the amount by which the material contained in the hole injecting and transporting layer is decomposed.
- the top of the partition is perpendicular to the incidence of light, while the side of the partition has an angle, so the solid angle is small and the apparent light dose is reduced, resulting in A gradient occurs in the amount of the material contained in the hole injecting and transporting layer being decomposed.
- the contact angle of the liquid can be inclined on the surface on the hole injecting and transporting layer side so that the contact angle of the liquid increases from the side portion side to the top side of the partition portion.
- the distance between the hole injecting and transporting layer and the mask gradually increases from the top to the side of the partition.
- the liquid contact angle can be inclined.
- the area of the mask transmission area is equal to the area of the top of the partition. It is preferable to make it larger. This is because it becomes easy to incline the liquid contact angle in the region located near the boundary between the top and the side of the partition.
- Partition formation step In the present invention, if necessary, before the hole injection transport layer formation step, between the patterns of the first electrode layer on the substrate on which the first electrode layer is formed in the pattern, You may have the partition part formation process which forms a partition part.
- a partition part a partition and an insulating layer are mentioned, for example.
- the partition wall 6a in FIGS. 2A, 3A, and 4A As the partition portion, a partition portion that functions as both a partition wall and an insulating layer is integrally formed. Also good.
- the description will be divided into the partition wall and the insulating layer.
- the portion where the partition portion is formed is usually a non-light emitting region.
- the partition wall 6a is patterned on the substrate 2 on which the first electrode layer 3 is formed. It may be formed in a shape. Usually, when the first electrode layer is formed in a pattern, the partition 6 a is formed in the opening of the pattern of the first electrode layer 3.
- the partition wall is provided to coat the layer formed on the hole injecting and transporting layer in a pattern.
- the material for forming the partition is not particularly limited, and may be an organic material or an inorganic material, and generally uses a material used for the partition in a device such as an organic EL element. Can do.
- the organic material include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene-methacrylic acid.
- Acid resin polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether Ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamide Resin, polyamic acid resin, polyether imide resin, phenol resin, urea resin and the like.
- the inorganic material include SiO 2 .
- the height of the partition wall can be about 0.01 ⁇ m to 50 ⁇ m.
- the partition wall width is set such that the width of the partition wall 6a is larger than the width between the patterns of the first electrode layer 3 as illustrated in FIG.
- the width of the partition wall 6a may be wider than the width between the patterns of the first electrode layer 3, as illustrated in FIG. 7B.
- a method for forming the partition wall a general method such as a photolithography method or a printing method can be used as a photolithography method or a printing method.
- the insulating layer 6b is formed in a pattern on the substrate 2 on which the first electrode layer 3 is formed. It may be. Usually, when the first electrode layer is formed in a pattern, the insulating layer 6b is formed in the opening of the pattern of the first electrode layer 3, and covers the end of the pattern of the first electrode layer. Formed. 7A and 7B, the partition wall 6a is also formed on the insulating layer 6b. However, only the insulating layer 6b may be formed and the partition wall 6a may not be formed. The insulating layer is provided to prevent conduction between the patterns of the adjacent first electrode layers and conduction between the first electrode layer and the second electrode layer.
- the insulating layer forming material is not particularly limited as long as it has insulating properties, and may be an organic material or an inorganic material. Generally, in a device such as an organic EL element. The material used for the insulating layer can be used.
- the insulating layer As a method for forming the insulating layer, a general method such as a photolithography method or a printing method can be used.
- the thickness of the insulating layer can be about 10 nm to 50 ⁇ m.
- the second electrode layer which is an essential component of the present invention, may be appropriately formed by a conventionally known process by appropriately adopting a conventionally known material according to each device.
- the second electrode layer is preferably formed of a metal or a metal oxide, usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, or an oxide of indium and / or tin. It can form with metal oxides, such as.
- the electrode is usually formed on the substrate by a method such as sputtering or vacuum deposition, 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 first aspect of a device according to 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,
- the hole injecting and transporting layer contains the device material for hole injecting and transporting layer according to the present invention, and the fluorine-containing organic compound of the device material for hole injecting and transporting layer in the surface layer part of the hole injecting and transporting layer is It is characterized by being decomposed and removed.
- a second aspect of the device according to the present invention is a device having two or more electrodes facing on a substrate and a hole injecting and transporting layer disposed between the two electrodes, A partition is provided between the patterns of the first electrode layer on the substrate on which the first electrode layer is formed in a pattern, and is continuous on the first electrode layer and the partition in the opening of the partition.
- a hole injection transport layer In the hole injecting and transporting layer on the first electrode layer in the opening of the partition part and on the side part of the partition part, at least part of the device material for hole injecting and transporting layer according to the present invention containing fluorine The organic compound is decomposed and removed, and the hole injecting and transporting layer on the top of the insulating layer contains the hole injecting and transporting layer device material according to the present invention. Any of the above-described devices of the present invention can be obtained by the device manufacturing method according to the present invention.
- FIG. 8 is a conceptual cross-sectional view showing the basic layer structure of the first aspect of the device according to the present invention.
- the basic layer structure of the device 10 of the present invention includes two electrodes (3 and 9) facing each other on a substrate 2, and a hole injection / transport layer 4 disposed between the two electrodes (3 and 9).
- the hole injecting and transporting layer 4 contains the hole injecting and transporting layer device material according to the present invention, and the hole injecting and transporting layer device material in the surface layer of the hole injecting and transporting layer contains fluorine. It includes a fluorine decomposition part 5 of the hole injection transport layer from which the organic compound has been decomposed and removed.
- a lyophilic region 11 is formed on the surface layer portion of the hole injection transport layer 4 existing on the first electrode layer 3 and on the side portion of the partition portion 6a, and a liquid repellent region 12 is formed on the top portion of the partition portion 6a.
- a pattern is formed.
- a layer serving as the center of the function of the device hereinafter referred to as a functional layer
- an auxiliary layer of the functional layer hereinafter referred to as an auxiliary layer
- Device layer 7 is formed on the lyophilic region 11 of the hole injecting and transporting layer 4.
- a layer serving as the center of the function of the device hereinafter referred to as a functional layer
- an auxiliary layer of the functional layer hereinafter referred to as an auxiliary layer
- Device layer 7 is formed on the lyophilic region 11 of the hole injecting and transporting layer 4.
- a layer serving as the center of the function of the device hereinafter referred to as a functional layer
- an auxiliary layer of the functional layer hereinafter referred
- the hole injecting and transporting layer 4 contains at least the hole injecting and transporting layer device material according to the present invention, and is a layer responsible for injecting and / or transporting holes from the electrode 3 to the device layer 7.
- the device layer 7 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. When the device layer 7 is composed of multiple layers, it includes a functional layer and an auxiliary layer. For example, in the case of an organic EL element, 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 second electrode layer 9 is provided at least where the hole injection / transport layer 4 and the device layer 7 exist between the opposing electrodes 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. 9 is a conceptual cross-sectional view showing the basic layer structure of the second aspect of the device according to the present invention.
- the basic layer structure of the device of the present invention has a partition 6a between the patterns of the first electrode layer 3 on the substrate 2 on which the first electrode layer 3 is formed in a pattern, and the partition 6a A continuous hole injecting and transporting layer (4 and 5) on the first electrode layer 3 and the partition 6a in the opening of the first electrode layer 3 on the first electrode layer 3 in the opening of the partition 6a
- the hole injecting and transporting layer 4 on the side part of the partition part 6a at least a part of the fluorine-containing organic compound of the device material for hole injecting and transporting layer according to the present invention is decomposed and removed, and hole injecting and transporting is performed.
- the hole injecting and transporting layer 4 on the top of the partition part contains the device material for the hole injecting and transporting layer according to the present invention, in which fluorine is not decomposed. is doing.
- 9 shows the hole injecting and transporting layer according to the present invention in the hole injecting and transporting layer 4 on the first electrode layer 3 in the opening of the partitioning part 6a and on the side part of the partitioning part 6a. The figure shows that all the fluorine-containing organic compounds of the device material for use are decomposed and removed to form the fluorine decomposition part 5 of the hole injection transport layer.
- the fluorine decomposition part 5 of the hole injecting and transporting layer present on the first electrode layer 3 and on the side part of the partition part 6a is formed from the lyophilic area 11 and the liquid repellent area 12 on the top part of the partition part 6a.
- a pattern is formed.
- a device layer 7 is formed on the lyophilic region 11 of the hole injection transport layer 4.
- the second electrode layer 9 has the hole injection transport layer 4 disposed between the two electrodes (3 and 9) on the substrate 2 so that the two electrodes (3 and 9) face each other. Is formed.
- the hole injection / transport layer (4 and 5) continuous on the first electrode layer 3 and the partition 6a in the opening of the partition 6a was provided as a separate layer on the hole injection / transport layer. There is no interface.
- the fluorine decomposition part 5 of the hole injection transport layer is a hole injection as a part in which at least a part of the fluorine-containing organic compound of the device material for hole injection transport layer is decomposed and removed from the same material as the hole injection transport layer 4 It is included in a pattern in the transport layer.
- 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.
- the first electrode layer, the second electrode layer, the hole injecting and transporting layer, and the device material for the hole injecting and transporting layer used for the hole injecting and transporting layer are described in “I. It may be the same as described in “Device material for hole injecting and transporting layer”, “II. Ink for hole injecting and transporting layer”, and “III. Device manufacturing method”. Further, device layers (functional layers and auxiliary layers) included in the device will be described in detail in specific examples of devices to be described later. Here, it supplements further about a positive hole injection transport layer.
- the hole injecting and transporting layer in the device of the present invention contains at least the device material for hole injecting and transporting layer according to the present invention.
- the hole injecting and transporting layer may be composed of only the device material for hole injecting and transporting layer in the present invention, but may further contain other components.
- a compound having a hole transporting property is appropriately used as a hole transporting compound other than the above-described device material for a hole injecting and transporting layer according to the present invention.
- 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 as the hole transporting compound.
- 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.
- a stable coating film that is easily dissolved in an organic solvent and hardly aggregates with a compound. 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
- hole transporting polymer compound for example, polyaniline, polythiophene, polyphenylene vinylene derivative, or the like can be used.
- Conductive polymers such as polyaniline, polythiophene, and polyphenylene vinylene derivatives may be doped with an acid.
- 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 can be given.
- the content of the hole transporting compound is as described above. It is 10 to 10000 parts by weight with respect to 100 parts by weight of the device material for hole injection / transport layer according to the invention, so that the hole injection / transport property is high and the stability of the film is high to achieve a long life. It is preferable from the point.
- 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 such as 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.
- FIG. 10 is a schematic cross-sectional view showing an example of the organic EL element of the present invention.
- the first electrode layer 3 is formed in a pattern on the substrate 2, the partition 6 a is formed in the opening of the pattern of the first electrode layer 3, and the first electrode layer 3 and A hole injecting and transporting layer 4 is formed on the partition wall 6a, and the fluorine-containing organic compound in the device material for the hole injecting and transporting layer in the surface layer portion of the hole injecting and transporting layer 4 is decomposed and removed to form the fluorine removing layer 5
- a light-emitting pattern formed on the surface of the fluorine removal layer 5 is formed, which includes the lyophilic region 11 and the liquid repellent region 12 on the top of the partition wall 6a. It has a layer 32, an electron injecting and transporting layer 33 formed on the light emitting layer 32, and a second electrode layer 34 formed on the electron injecting and transporting layer 33.
- a hole transport layer may be further formed between the lyophilic region 11 of the hole injection transport layer and the light emitting layer 32.
- the first electrode layer 3 functions as an anode
- the second electrode layer 34 functions as a cathode.
- holes are injected from the anode through the hole injection transport layer 4 into the light emitting layer 32, and electrons are injected from the cathode into the light emitting layer.
- 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.
- an electron injecting and transporting layer 33 is provided between the light emitting layer and the electrode 6 (cathode) as necessary.
- each layer of the organic EL element according to the present invention will be described in detail.
- the substrate and the electrode layer those described in the description of the device can be used.
- a hole injection transport layer In addition to the hole injection transport layer containing the device material for hole injection transport layer according to the present invention or a decomposition product thereof, which is an essential component in the device of the present invention, a hole injection transport layer, a hole transport layer, and the like. , And a hole injection layer may be appropriately formed between the light emitting layer and the first electrode layer.
- a hole transporting layer may be further laminated on the hole injecting and transporting layer containing the hole injecting and transporting device device according to the present invention or a decomposition product thereof, and a light emitting layer may be laminated thereon,
- a hole injection / transport layer containing the above-described device material for a hole injection / transport layer according to the present invention or a decomposition product thereof may be further laminated on the hole injection layer, and a light emitting layer may be laminated thereon.
- the hole transport compound used in the hole transport layer is not particularly limited, and the above-described hole injection transport is described above.
- a hole injecting and transporting compound as described in the supplement of the layer can be appropriately selected and used.
- the hole injecting and transporting layer as an essential component of the present invention further contains a hole injecting and transporting compound different from the device material for hole injecting and transporting layer according to the present invention or a decomposition product thereof, adjacent holes For the transport layer, it is possible to use the same compound as the hole transporting compound contained in the hole injecting and transporting layer as an essential component of the present invention.
- the hole transport layer can be formed in the same manner as the light emitting layer described later, using a hole injecting / transporting compound.
- the thickness of the hole transport layer is usually from 0.1 to 1 ⁇ m, preferably from 1 to 500 nm.
- the hole injection material used for the hole injection layer is not particularly limited, and a conventionally known compound is used. be able to. 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 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 is usually 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- HOMO work function
- the light emitting layer 32 is formed on the lyophilic region 11 on the hole injecting and transporting layer between the substrate 2 on which the first electrode layer 3 is formed and the second electrode layer 34. Is done.
- 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 luminescent materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethylzinc complex, porphyrin zinc complex, europium complex, etc., or 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.
- polymer light-emitting materials As 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.
- transduced the spiro group into these can also be used. These materials may be used alone or in combination of two or more.
- 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 polymer type material that is easily dissolved in a non-aqueous solvent such as xylene and forms a layer by a solution coating method can be used.
- 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 by a solution coating method using a light emitting material using a wettability change pattern on the surface of the hole injecting and transporting layer.
- the solution coating method the same method as described in the item of the device manufacturing method can be used.
- the hole transport layer may be formed by a vapor deposition method or a transfer method.
- the vacuum evaporation method the material of the light emitting layer is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁇ 4 Pa by an appropriate vacuum pump, and then the crucible.
- a light emitting layer is formed on the laminate of the substrate, the first electrode layer, the hole injection transport layer, and the hole transport layer placed facing the crucible.
- a light emitting layer formed in advance on a film by a solution coating method or a vapor deposition method is bonded to a hole injecting and transporting layer provided on the first electrode layer, and the light emitting layer is heated to form a hole injecting and transporting layer. It is formed by transferring it upward.
- the thickness of the light emitting layer is usually about 1 to 500 nm, preferably about 20 to 1000 nm.
- the hole injection transport layer is preferably formed by a solution coating method, and the light emitting layer can also be formed by a solution coating method using the wettability change pattern on the surface of the hole injection transport layer. Therefore, in this case, there is an advantage that the process cost can be reduced.
- hole injection is also applied to dye-sensitized solar cells, organic thin film solar cells, organic semiconductors, other organic devices such as organic transistors, quantum dot light emitting devices having a hole injection transport layer, and oxide-based compound solar cells.
- the transport layer is 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.
- a layer made of the material to be measured is formed as a single layer on a cleaned glass substrate with ITO, and a step is made with a cutter knife, and then the height of the step is measured with a probe microscope (SII). -It measured by the tapping mode using Nanotechnology Co., Ltd. product and Nanopics1000.
- ⁇ Measurement of ionization potential> The value of the work function measured using the photoelectron spectrometer AC-1 (manufactured by Riken Keiki Co., Ltd.) was applied as the ionization potential value in the present invention.
- a layer formed of a material to be measured is formed as a single layer on a glass substrate with ITO (manufactured by Sanyo Vacuum Co., Ltd.), and photoelectrons are emitted from the photoelectron spectrometer AC-1. Determined by energy value.
- a light amount of 50 nW was used in increments of 0.05 eV.
- the absorption spectrum is obtained by forming a layer made of the material to be measured as a single layer on a cleaned quartz substrate, and measuring the difference in optical absorption between this thin film-attached substrate and the reference quartz substrate by UV-3100PC (Hitachi). ).
- the transmittance at a wavelength of 254 nm of the thin film (10 nm) formed using the ink for forming a hole injection transport layer obtained in Production Examples 1 to 11 was a high value of 80% or more.
- ⁇ Measurement of liquid contact angle> The contact angle of the liquid was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., fully automatic contact angle meter (DM700)). Xylene (surface tension of 28.5 mN / m) was used as a standard solution, and the contact angle was measured 5 seconds after a 2 microliter droplet was dropped from the microsyringe.
- ⁇ Surface analysis of hole injection transport layer> The valence of the transition metal contained in the organic-transition metal oxide complex and the presence or absence of a fluoroalkyl group were measured by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- An ESCA-3400 model manufactured by Kratos was used for the measurement.
- MgK ⁇ ray was used as the X-ray source used for the measurement.
- the measurement was carried out under the conditions of an acceleration voltage of 10 kV and a filament current of 20 mA without using a monochromator.
- the organic EL device of the present invention is subjected to photocatalytic treatment after forming a hole injecting and transporting layer containing an organic-transition metal oxide composite having a fluorine-containing organic compound attached to the surface on a glass substrate with a transparent anode. After that, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are formed and laminated so as to have a basic layer structure, and then sealed and green-emitting organic EL It produced as an element and evaluated the characteristic and wettability of the organic EL element.
- Example 1 A patterned glass substrate with ITO (manufactured by Sanyo Vacuum Co., ITO film thickness: 150 nm) was subjected to UV ozone treatment by ultrasonic cleaning in the order of neutral detergent and ultrapure water. Next, an organic-transition metal oxide composite thin film is formed by spin coating on the substrate using the hole injection / transport layer forming ink 1 obtained in Production Example 1 as a hole injection / transport layer. did. After forming the coating film, it was dried on a hot plate at 200 ° C. The film thickness after drying was 10 nm. Next, a photomask with a photocatalyst-containing layer was prepared.
- a photomask having a transmission region and a light shielding region formed on a synthetic quartz substrate was prepared.
- a photocatalyst-containing layer-forming coating solution having the following composition is applied by a spin coater, subjected to a heat drying treatment at 150 ° C. for 10 minutes, and cured by a hydrolysis / polycondensation reaction.
- the hole injecting and transporting layer was exposed through the photomask with a photocatalyst containing layer prepared above to form a pattern composed of a lyophilic region and a lyophobic region.
- the distance between the photocatalyst containing layer and the hole injecting and transporting layer of the photocatalyst containing layer is 100 ⁇ m using an ultraviolet exposure apparatus including a high pressure mercury lamp, a photomask with a photocatalyst containing layer, and a position adjusting mechanism of the substrate. After adjusting as described above, exposure was performed for 3 minutes from the back side of the photomask with a photocatalyst-containing layer so that the exposure amount of light at 254 nm was 5 J / cm 2 .
- PVK polyvinyl carbazole
- a hole blocking layer was formed on the light emitting layer by vapor deposition.
- the hole blocking layer uses bis (2-methyl-8-quinolato) (p-phenylphenolate) aluminum complex (BAlq) as a block forming material, and is subjected to vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) by resistance heating method.
- the BAlq vapor deposition film was formed by vapor deposition so that the film thickness was 15 nm.
- An electron transport layer was deposited on the hole blocking layer.
- the electron transport layer was formed by vapor deposition of tris (8-quinolinolato) aluminum complex (Alq3) in a vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) by a resistance heating method so that the film thickness of the Alq3 vapor deposition film was 20 nm.
- An electron injection layer and a cathode were successively deposited on the electron transport layer of the produced glass substrate with a transparent anode / hole injection transport layer / hole transport layer / light emitting layer / hole block layer / electron transport layer.
- a vapor deposition film was formed in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) by resistance heating vapor deposition sequentially for LiF (thickness: 0.5 nm) for the electron injection layer and Al (thickness: 100 nm) for the cathode.
- the cathode After forming the cathode, the anode is sealed with a non-alkali glass and a UV curable epoxy adhesive in a low oxygen, low humidity glove box, and is patterned in a line shape with a width of mm, and orthogonal to the anode.
- the organic EL element of Example 1 provided with the electron injection layer formed in the line shape of width mm and a cathode was produced.
- the organic EL elements produced in the above examples and comparative examples all emitted green light derived from Ir (mppy) 3 .
- Table 3 shows the measurement results.
- 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).
- LT50 lifetime
- Example 2 In Example 1, a hole injection transport layer forming ink 2 was used instead of the hole injection transport layer forming ink 1 as a hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 3 In Example 1, a hole injection / transport layer forming ink 3 was used instead of the hole injection / transport layer forming ink 1 as a hole injection / transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 4 In Example 1, a hole injection transport layer forming ink 4 was used instead of the hole injection transport layer forming ink 1 as a hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and wettability was evaluated.
- Example 5 In Example 1, a hole injection transport layer forming ink 5 was used instead of the hole injection transport layer forming ink 1 as the hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 6 In Example 6, a device was produced and wettability was evaluated in the same manner as in Example 1 except that the hole injection / transport layer was irradiated with only 253 nm ultraviolet light without using a mask with a photocatalyst mask.
- Example 7 In Example 1, a hole injection transport layer forming ink 6 was used instead of the hole injection transport layer forming ink 1 as the hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 8 In Example 1, a hole injection transport layer forming ink 7 was used instead of the hole injection transport layer forming ink 1 as the hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 9 In Example 1, a hole injection transport layer forming ink 1 was used instead of the hole injection transport layer forming ink 1 as a hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 10 In Example 1, a hole injection / transport layer forming ink 9 was used instead of the hole injection / transport layer forming ink 1 as a hole injection / transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 11 In Example 1, a hole injection transport layer forming ink 10 was used instead of the hole injection transport layer forming ink 1 as a hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 12 In Example 1, a hole injection transport layer forming ink 11 was used instead of the hole injection transport layer forming ink 1 as the hole injection transport layer forming ink, except that a thin film having a thickness of 10 nm was formed. A device was produced in the same manner as in Example 1, and the wettability was evaluated.
- Example 1 As a hole injection / transport layer forming ink, a 10 nm thick thin film was formed using the hole injection / transport layer forming comparative ink 1 instead of the hole injection / transport layer forming ink 1. Were fabricated in the same manner as in Example 1 and evaluated for wettability.
- Example 2 In Example 1, instead of the film formed using the hole injection / transport layer forming ink 1 as the hole injection / transport layer, PEDOT / PSS (AI4083 manufactured by Starck) and 4- (3,3,4,) were used. , 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) benzylamine, except that the thin film was formed by spin coating An element was formed in the same manner as in Example 1 and wettability was evaluated. The PEDOT / PSS layer was prepared by diluting a PEDOT / PSS solution with distilled water and dissolving the dried film thickness to 10 nm.
- the thin film was dried by coating using heptadecafluorodecylbenzylamine dissolved in 0.4 wt% of heptafluoro-n-ethyl butyrate.
- the film thickness after drying was not able to be measured and was 5 nm or less.
- Comparative Example 3 In Comparative Example 2, an element was prepared and wettability was evaluated in the same manner as in Comparative Example 2 except that the photocatalyst treatment was not performed on the hole injecting and transporting layer.
- Example 4 In Example 1, instead of the film formed using the hole injection / transport layer forming ink 1 as the hole injection / transport layer, a MoO 3 film (10 nm) deposited in vacuum by a resistance heating method was used. Except for the use, an element was prepared in the same manner as in Example 1, and the wettability was evaluated.
- Example 1 In Example 1, an element was produced in the same manner as in Example 1 except that the photocatalytic treatment was not performed on the hole injecting and transporting layer, and wettability was evaluated.
- Example 2 In Example 2, a device was prepared and wettability was evaluated in the same manner as in Example 2 except that the photocatalytic treatment was not performed on the hole injection transport layer.
- Example 3 In Example 3, a device was prepared and wettability was evaluated in the same manner as in Example 3 except that the photocatalytic treatment was not performed on the hole injecting and transporting layer.
- Example 4 In Example 4, a device was prepared and wettability was evaluated in the same manner as in Example 4 except that the photocatalytic treatment was not performed on the hole injecting and transporting layer.
- Reference Example 5 In Example 5, a device was prepared and wettability was evaluated in the same manner as in Example 5 except that the photocatalytic treatment was not performed on the hole injecting and transporting layer.
- Example 1 Comparing Example 1 and Reference Example 1, in Example 1, the contact angle decreased from 49 ° to 5 ° or less after the photocatalytic treatment, and the ionization potential increased from 5.2 eV to 5.4 eV. Furthermore, in device characteristics, the lifetime is improved from 2.0 hours to 3.0 hours after the photocatalytic treatment.
- Example 1 it is presumed that the fluoroalkyl component was decomposed by the photocatalytic treatment and the surface was modified by the oxidation of the surface of the organic-transition metal oxide composite layer, thereby improving the characteristics. The This result is the same in the comparison between Example 2 and Reference Example 2, the comparison between Example 3 and Reference Example 3, the comparison between Example 4 and Reference Example 4, and the comparison between Example 5 and Reference Example 5.
- Example 5 When Example 5 is compared with Example 1, the initial contact angle is higher when the ink 1 of Example 1 is used, and it is preferable to prepare the ink by the method of making the ink 1 than the ink 5. Further, when Examples were compared, Examples 10 to 12 using inks 9 to 11 were excellent in luminance, current efficiency, and lifetime. It is presumed that the fluorine component having an ether bond is easily decomposed and the residual organic component on the surface of the hole injecting and transporting layer is reduced, thereby improving the adhesion at the thin film interface and improving the device characteristics.
- Example 6 and Comparative Example 1 are compared, the contact angle is reduced from 49 ° to 10 ° by irradiation with vacuum ultraviolet light, and the ionization potential is increased from 5.2 eV to 5.4 eV. Furthermore, in terms of device characteristics, the lifetime is improved from 2.0 hours to 2.6 hours after irradiation with vacuum ultraviolet light. Improved properties by decomposing the fluoroalkyl component by irradiation with vacuum ultraviolet light and oxidizing the surface of the organic-transition metal oxide composite layer with ozone generated by vacuum ultraviolet light. It is speculated that.
- Example 1 has a longer life than Comparative Example 4 using MoO 3 is that the component of oxidation number +5 is appropriately contained in a stable state, as will be described later.
- Example 1 the drive voltage is reduced by 1V. From this result, it is presumed that in Example 1, the organic compound having a fluoroalkyl group was mixed, so that the ionization potential was changed and the hole injection property was improved, so that the device performance was improved.
- Comparative Example 2 and Comparative Example 3 when PEDOT / PSS, which is a general organic hole injection material, is used for the hole injection / transport layer, the lifetime is increased due to light irradiation and photocatalytic treatment. You can see that it is getting shorter. This result is considered that PEDOT / PSS was oxidized or decomposed by light irradiation and photocatalytic treatment, and hole injection property and driving durability were deteriorated.
- Example 1 Using the hole injecting and transporting layer formed in Example 1 and Comparative Example 4, the oxidation number of the transition metal was measured. The oxidation number of the transition metal was measured by X-ray photoelectron spectroscopy (XPS) in the surface analysis of the hole injection transport layer described above. In the said Example 1, the XPS measurement of a photocatalyst process part and a photocatalyst unprocessed part was implemented, and Mo oxidation number was estimated. In the table below, peak intensity of oxidation number +5 is shown when peak separation is performed for peaks of Mo oxidation number +6 and oxidation number +5, and oxidation number +6 is normalized to 100.
- XPS X-ray photoelectron spectroscopy
- Example 1 In the molybdenum spectrum of Example 1, a component having an oxidation number of +5 was detected from both the photocatalyst-treated portion and the photocatalyst-untreated portion. In the photocatalyst-treated film, the ratio of pentavalent is slightly reduced. However, the organic-transition metal oxide composite of the present application was slightly changed to trivalent in spite of strong oxidation treatment. It is very stable. The reason why Example 1 has a longer life than Comparative Example 4 using MoO 3 is suggested to be due to the fact that the component having an oxidation number of +5 is appropriately contained in a stable state.
- Example 1 having a slightly higher oxidation number +5 ratio than Reference Example 1
- the surface of the hole injection transport layer is oxidized in Example 1, and the ionization potential is close to the ITO interface. Is likely to be stepped at 5.2 eV and 5.4 eV at the hole transport layer interface, and it is presumed that the hole-injecting property is improved or stabilized. .
- Example 13 As shown in FIG. 11, an organic-transition metal in which a fluorine-containing organic compound prepared as a hole injection / transport layer 43 in the synthesis example is attached to a surface on a glass substrate 41 on which an ITO transparent electrode (anode) 42 is formed. An oxide composite thin film is formed by spin coating to a thickness of 10 nm, and pattern exposure is performed using a photocatalyst-containing layer substrate (photomask 50 with a photocatalyst-containing layer) in which a light-shielding portion and a photocatalyst-containing layer are formed on a substrate. The wettability of the non-exposed part was examined by contact angle measurement.
- an indium tin oxide (ITO) thin film (thickness: 150 nm) was used as a transparent electrode.
- a glass substrate with ITO manufactured by Sanyo Vacuum Co., Ltd.
- UV ozone treatment by ultrasonic cleaning in the order of neutral detergent and ultrapure water.
- an organic-transition metal oxide composite thin film was applied and formed on the substrate as a hole injection / transport layer by spin coating using the hole injection / transport layer forming ink 1. After forming the coating film, it was dried on a hot plate at 200 ° C.
- the film thickness after drying was 10 nm.
- the contact angle of the hole injecting and transporting layer surface with respect to xylene was 49 °.
- a photomask 50 with a photocatalyst containing layer was prepared.
- a photomask in which a chrome mask 54 was formed so as to provide a transmission region 52 and a light shielding region 53 on a synthetic quartz substrate 51 was prepared.
- a photocatalyst-containing layer-forming coating solution having the following composition is applied by a spin coater, subjected to a heat drying treatment at 150 ° C. for 10 minutes, and cured by a hydrolysis / polycondensation reaction.
- a transmission region 56 where the photocatalyst containing layer 55 is not formed is provided at the end on the synthetic quartz substrate 51.
- the hole injecting and transporting layer was exposed through the photomask with a photocatalyst containing layer prepared above to form a pattern composed of a lyophilic region and a lyophobic region.
- the distance between the photocatalyst containing layer 55 and the hole injecting and transporting layer 43 of the photocatalyst containing layer photomask 50 is determined using an ultraviolet exposure apparatus including a high pressure mercury lamp, a photocatalyst containing layer photomask and a substrate position adjusting mechanism. After adjusting to 100 ⁇ m, exposure was performed for 3 minutes from the rear surface side of the photomask 50 with a photocatalyst containing layer so that the exposure amount of 254 nm light was 5 J / cm 2 .
- the static contact angle of the liquid between the exposed portion and the non-exposed portion on the hole injecting and transporting layer was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).
- a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
- xylene surface tension: 28.5 mN / m
- Example 14 In Example 13, a pattern composed of a lyophilic region and a liquid repellent region was formed in the same manner as in Example 13 except that exposure was performed using vacuum ultraviolet light instead of 253 nm ultraviolet light as an exposure light source. The wettability was evaluated. At this time, a pattern composed of a liquid repellent region and a lyophilic region was formed so that the exposure amount of vacuum ultraviolet light having a wavelength of 172 nm was 5 J / cm 2 from the metal mask side.
- Example 15 In Example 13, a thin film (thickness: 10 nm) was formed using the hole injection / transport layer forming ink 3 instead of the hole injection / transport layer forming ink 1 as the hole injection / transport layer forming ink. Except for the above, a pattern composed of a lyophilic region and a liquid repellent region was formed in the same manner as in Example 13, and the wettability was evaluated.
- Example 16 In Example 13, a thin film (thickness: 10 nm) was formed using the hole injection / transport layer forming ink 4 instead of the hole injection / transport layer forming ink 1 as the hole injection / transport layer forming ink. Except for the above, a pattern composed of a lyophilic region and a liquid repellent region was formed in the same manner as in Example 13, and the wettability was evaluated.
- Example 13 the hole injecting and transporting layer was heated at 200 ° C. for 1 hr. Except for heating, a thin film was formed in the same manner as in Example 13, and wettability was evaluated.
- Reference Example 7 In Reference Example 6, a thin film was formed in the same manner as in Reference Example 6 except that the hole injection / transport layer forming ink 3 was used instead of the hole injection / transport layer forming ink 1, and the wettability was evaluated. .
- Reference Example 6 a thin film was formed in the same manner as in Reference Example 6 except that the hole injection / transport layer forming ink 4 was used instead of the hole injection / transport layer forming ink 1, and the wettability was evaluated. .
- the thin film was dried by coating using heptadecafluorodecylbenzylamine dissolved in 0.4 wt% of heptafluoro-n-ethyl butyrate.
- the film thickness after drying was not able to be measured and was 5 nm or less.
- Example 13 and 15 it can be seen that the material is not decomposed by the light of 254 nm in the region IV where only the exposed portion is exposed, and the presence of the photocatalyst is necessary. XPS measurements of these surfaces showed that fluoroalkyl groups remained as much as untreated films.
- the contact angle of the exposed area in the region IV of Example 14 is 10 °, which is 39 ° lower than that of the unexposed area. Since the liquid-repellent contrast between the unexposed area and the exposed area is 20 ° or more, it can be seen that in the case of vacuum ultraviolet light, the coating can be performed without a photocatalyst.
- Example 17 ⁇ Fabrication of device with light emitting layer patterned> [Example 17] On the ITO substrate on which the insulating layer and the partition wall are formed (a partially enlarged schematic cross-sectional view is shown in FIG. 12A and a partially enlarged schematic plan view seen from above is shown in FIG. 12B). A hole injecting and transporting layer is formed, the hole injecting and transporting layer is exposed with a photomask with a photocatalyst to perform wettability patterning, and the hole transporting layer and the light emitting layer are formed between the partition walls which are lyophilic parts by an inkjet method.
- the light emitting surface of the device was observed.
- the light emitting layer was painted in two colors, green and blue.
- an ITO substrate on which a grid-like insulating layer and a line-shaped partition wall as shown in FIGS. 12A and 12B are formed is ultrasonically cleaned in the order of neutral detergent and ultrapure water. Finally, UV ozone treatment was performed. Next, an organic-transition metal oxide composite thin film was formed on the substrate as a hole injection / transport layer by spin coating. As the hole injection transport layer forming ink, the hole injection transport layer forming ink 1 was used. After forming the coating film, it was dried on a hot plate at 200 ° C. The film thickness after drying was 10 nm. When the contact angle was measured at a flat portion having no partition wall structure, the contact angle on the surface of the hole injecting and transporting layer with respect to xylene was 49 °.
- the opening is adjusted so as to be positioned on the linear partition, and the substrate is adjusted.
- the film was exposed to and subjected to wettability patterning with high liquid repellency and contrast.
- the distance between the photocatalyst containing layer and the hole injecting and transporting layer of the photocatalyst containing layer is 100 ⁇ m using an ultraviolet exposure apparatus including a high pressure mercury lamp, a photomask with a photocatalyst containing layer, and a position adjusting mechanism of the substrate.
- the hole transport layer was formed by applying a coating liquid for forming a hole transport layer having the following composition to the lyophilic region formed between the partition walls by an inkjet method. After forming the coating film, it was dried in nitrogen at 200 ° C. for 60 minutes. The amount of ink applied was adjusted so that the film thickness after drying was 30 nm.
- (Coating fluid for hole transport layer formation) Poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec-butylphenyl)) diphenylamine)] (TFB) 1.8 wt.
- a coating solution for forming a green light emitting layer having the following composition was applied every other line by an ink jet method, followed by The blue light emitting layer forming coating solution was applied to the lines where the green light emitting layer forming coating solution was not applied by the inkjet method to form a light emitting layer in which green and blue were arranged every other line.
- After forming the coating film it was dried in nitrogen at 100 ° C. for 30 minutes. The amount of ink applied was adjusted so that the film thickness after drying was 40 nm.
- a hole blocking layer was uniformly deposited on the light emitting layer.
- bis (2-methyl-8-quinolato) (p-phenylphenolate) aluminum complex (BAlq) is used as a block forming material in a vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) by a resistance heating method. Vapor deposition was performed so that the thickness of the BAlq vapor deposition film was 15 nm. An electron transport layer was deposited on the hole blocking layer.
- the electron transport layer was formed by vapor deposition of tris (8-quinolinolato) aluminum complex (Alq3) in a vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) by a resistance heating method so that the film thickness of the Alq3 vapor deposition film was 20 nm.
- An electron injection layer and a cathode were successively deposited on the electron transport layer of the produced glass substrate with a transparent anode / hole injection transport layer / hole transport layer / light emitting layer / hole block layer / electron transport layer.
- a vapor deposition film was formed in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa) by resistance heating vapor deposition sequentially for LiF (thickness: 0.5 nm) for the electron injection layer and Al (thickness: 100 nm) for the cathode. After forming the cathode, it was sealed using a non-alkali glass and a UV curable epoxy adhesive in a low oxygen, low humidity glove box.
- the light emitting layer was applied, the light emitting layer was observed with a fluorescence microscope, and it was confirmed that the green and blue colors could be neatly mixed without being mixed. Furthermore, when the light emitting surface of the manufactured device was observed with a microscope, it was confirmed that a device that emitted blue and green light every other line could be manufactured. It was confirmed that the light emission within each pixel was uniform, the light emission variation between the pixels was small, and the colors could be painted with very high accuracy. In this embodiment, two colors of green and blue are separately applied. However, according to the method of this embodiment, in principle, it can be easily expanded to three colors and four colors. It can be easily applied to production.
- Example 17 was the same as Example 17 except that exposure was performed using vacuum ultraviolet light instead of 253 nm ultraviolet light as an exposure light source, and a photomask without a photocatalyst was used instead of a photomask with a photocatalyst.
- an organic EL device of Example 18 was produced.
- a pattern composed of a liquid repellent region and a lyophilic region was formed so that the exposure amount of vacuum ultraviolet light having a wavelength of 172 nm was 5 J / cm 2 from the photomask side.
- the light emitting surface of the manufactured device was observed with a microscope, it was confirmed that a device emitting blue and green every other line was manufactured.
- Example 19 In Example 17, the organic EL of Example 19 was used in the same manner as in Example 17 except that an ITO substrate having only an insulating layer and no barrier ribs was used instead of the ITO substrate having the insulating layer and barrier ribs formed thereon. An element was produced. After applying the light-emitting layer, the light-emitting layer was observed with a fluorescence microscope. Even though there was no partition wall structure, the ink was not broken and green and blue were not mixed with each other. It could be confirmed. Furthermore, when the light emitting surface of the manufactured device was observed with a microscope, it was confirmed that a device that emitted blue and green light every other line could be manufactured.
- Example 20 In Example 17, the photocatalyst with photocatalyst was not provided with a chrome pattern, and a photomask having no chrome pattern was used, and exposure at 254 nm was performed from the ITO substrate side, not from the back side of the photomask with a photocatalyst containing layer.
- An organic EL device of Example 20 was produced in the same manner as in Example 17 except that the exposure was performed for 9 minutes so as to be 2 .
- the light emitting surface of the manufactured device was observed with a microscope, it was confirmed that a device emitting blue and green every other line was manufactured. It was confirmed that the light emission within each pixel was uniform, the light emission variation between the pixels was small, and the pixels could be painted with very high accuracy.
- the hole injection / transport layer device material obtained in Synthesis Example 1 has a high transmittance at 254 nm, and further, as shown in the previous example, the device characteristics are not deteriorated by UV irradiation at 254 nm. It is advantageous for exposure from the back side.
- Example 17 instead of using the hole injection transport layer forming ink 1, PEDOT / PSS (AI4083 manufactured by Starck) and 4- (3,3,4,4,5,5,6,6,7, 7,8,8,9,9,10,10,10-heptadecafluorodecyl) benzylamine, and the organic layer of Comparative Example 6 was the same as Example 17 except that a multilayer thin film was formed by spin coating. An EL element was produced.
- the PEDOT / PSS layer was prepared by diluting a PEDOT / PSS solution with distilled water and dissolving the dried film thickness to 10 nm.
- the thin film was dried by applying and forming a solution obtained by dissolving 0.4 wt% of heptadecafluorodecylbenzylamine in ethyl heptafluoro-n-butyrate.
- the film thickness after drying was not able to be measured and was 5 nm or less.
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Abstract
Description
これら電子注入層、電子輸送層、正孔輸送層、正孔注入層などの発光層以外の層には、電荷を発光層へ注入・輸送しやすくする効果、あるいはブロックすることにより電子電流と正孔電流のバランスを保持する効果や、光エネルギー励起子の拡散を抑制するなどの効果があるといわれている。
特許文献1~4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、化合物半導体である金属酸化物が用いられている。例えば五酸化バナジウムや三酸化モリブデンなどの金属酸化物を用いて蒸着法で薄膜を形成したり、或いはモリブデン酸化物とアミン系の低分子化合物との共蒸着により混合膜を形成している。
非特許文献1においては、5酸化バナジウムの塗膜形成の試みとして、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。しかしながら、非特許文献1では、加水分解-重縮合反応により固化するため、バナジウムが凝集し易く、膜質制御が困難で、良好な膜が得られない。また、オキソバナジウム(V)トリ-i-プロポキシドオキシドだけでは塗膜にならないため、正孔輸送性高分子と混合しているので、非特許文献1の塗膜は有機成分濃度が必然的に高く、素子の寿命の有効成分と考えられるバナジウムの濃度が不十分となる。このように非特許文献1では、寿命特性や素子特性に更なる改善が必要であった。
特許文献5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。
同時に、溶液塗布法により正孔注入輸送層を形成可能で製造プロセスが容易でありながら、正孔注入輸送性に優れ、デバイスの長寿命を達成可能な正孔注入輸送材料が望まれていた。
また、本発明の更なる目的は、上記正孔注入輸送層用デバイス材料を用いて親液性領域及び撥液性領域からなるパターンを形成することにより、正孔注入輸送層上に積層される層をパターニング可能で、且つ、長寿命を達成可能なデバイス及びその製造方法を提供することにある。
すなわち、本発明の正孔注入輸送層用デバイス材料は、有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体の表面に、フッ素含有有機化合物が付着していることを特徴とする。
更に、本発明の正孔注入輸送層形成用インクは、有機遷移金属錯体と、遷移金属及び/又は遷移金属酸化物と連結する作用を生ずる連結基を含むフッ素含有有機化合物と、カルボニル基及び/又は水酸基を有する有機溶媒を含有するものであってもよい。
パターン状に第一電極層が形成された基板上に、上記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する正孔注入輸送層形成工程と、
基体上に少なくとも光触媒を含有する光触媒含有層が形成されている光触媒含有層基板を、前記正孔注入輸送層に対して、エネルギー照射に伴う光触媒の作用が及び得る間隙をおいて配置した後、パターン状にエネルギー照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成する濡れ性変化パターン形成工程とを有することを特徴とする。
パターン状に電極層が形成された基板上に、上記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する正孔注入輸送層形成工程と、
パターン状に真空紫外線を照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成する濡れ性変化パターン形成工程とを有することを特徴とする。
前記正孔注入輸送層が、上記本発明に係る正孔注入輸送層用デバイス材料を含有し、前記正孔注入輸送層の表層部の前記正孔注入輸送層用デバイス材料のフッ素含有有機化合物が分解除去されていることを特徴とする。
パターン状に第一電極層が形成された基板上の前記第一電極層のパターン間に、仕切部を有し、前記仕切部の開口部内の前記第一電極層上及び前記仕切部上に連続した正孔注入輸送層を有し、
前記仕切部の開口部内の前記第一電極層上及び前記仕切部の側部上の正孔注入輸送層においては、上記本発明に係る正孔注入輸送層用デバイス材料の少なくとも一部のフッ素含有有機化合物が分解除去されており、且つ、前記絶縁層の頂部上の正孔注入輸送層は上記本発明に係る正孔注入輸送層用デバイス材料を含有していることを特徴とする。
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、正孔注入輸送層の良好な濡れ性変化パターンを利用でき、優れた正孔注入輸送層を得ることができるので、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。
本発明に係るデバイスは、製造プロセスが容易でありながら、正孔注入輸送性に優れ、長寿命を達成可能である。
本発明の正孔注入輸送層用デバイス材料は、有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体に、フッ素含有有機化合物が付着していることを特徴とする。
また、有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体は、含まれる遷移金属酸化物の反応性が高く、電荷移動錯体を形成しやすいと考えられる。そのため、本発明の正孔注入輸送層用デバイス材料は、低電圧駆動、高電力効率、長寿命なデバイスを実現可能な正孔注入輸送層を形成することが可能である。
以下、本発明の正孔注入輸送層用デバイス材料の構成を順に説明する。
本発明の正孔注入輸送層用デバイス材料に用いられる有機-遷移金属酸化物複合体は、有機遷移金属錯体の反応生成物であって、遷移金属酸化物を含むものである。有機遷移金属錯体の反応生成物としては、有機遷移金属錯体同士の反応生成物や、有機遷移金属錯体と有機溶媒の反応生成物や、有機遷移金属錯体と当該有機金属錯体と反応可能な官能基を有する有機又は無機化合物との反応生成物、及びこれらの組み合わせの反応生成物が挙げられる。
有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体は、正孔注入輸送層を形成する過程、例えば、正孔注入輸送層形成用インク(塗布溶液)中、或いは、層形成時又は層形成後において、加熱時、光照射時、素子駆動時等に行われる、有機遷移金属錯体の反応によって生成される反応生成物であってもよい。
有機-遷移金属酸化物複合体中には、処理条件によって様々な価数の遷移金属原子や化合物、例えば遷移金属の炭化物、硫化物、ホウ化物、セレン化物、ハロゲン化物等を含んでいても良い。
なお、前記有機-遷移金属酸化物複合体に含まれる金属は、少なくとも遷移金属が含まれれば、非遷移金属が含まれていても良い。
2種以上の金属を含むことにより、正孔輸送性や正孔注入性を互いに補い合ったり、光触媒性を付与したり、薄膜の屈折率や透過率を制御するなど他の機能を併せ持つ正孔注入輸送層を形成できるというメリットがある。
例えば、有機モリブデン錯体としては、酸化数-2から+6までの錯体がある。また、有機タングステン錯体としても、酸化数-2から+6までの錯体がある。タングステン錯体は、多核になりやすくオキソ配位子がつきやすいなど、モリブデン錯体に似た傾向を示し、配位数が7以上になることもある。また、有機バナジウム錯体としては、酸化数-3から+5までの錯体がある。
配位子の種類は適宜選択され、特に限定されないが、溶剤溶解性や隣接する有機層との密着性から有機部分(炭素原子)を含むものを用いる。また、配位子は、比較的低温(例えば200℃以下)で錯体から分解するものであることが好ましい。
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。
また、酸化数が+1のモリブデン(I)錯体としては、ジホスファンやη5-シクロペンタジエニドを含む非ウェルナー型錯体が挙げられ、具体的には、MoI(η6-C6H6) 2]+,[MoCl(N2)(diphos)2](diphosは、2座配位子(C6H5)2PCH2CH2P(C6H5)2)が挙げられる。
酸化数が+2のモリブデン(II)錯体としては、その他、[MoII 2X4L4] 、[MoIIX2L4] などのハロゲン錯体を用いることができ、例えば、[MoIIBr4(P(n-C4H9)3)4] や[MoIII2(diars)2](diarsは、ジアルシン(CH3)2As-C6H4-As(CH3)2)などが挙げられる。
また、酸化数が+4のモリブデン(IV)錯体としては、例えば、[Mo{N(CH3)2}4]、[Mo(CN)8]4-、それにオキソ配位子をもつMoO2+の錯体や、O2-で2重架橋したMo2O2 4+の錯体が挙げられる。
また、酸化数が+6のモリブデン(VI)錯体としては、例えば、MoO2(acetylacetonate)2]が挙げられる。なお、2核以上の錯体の場合には、混合原子価錯体もある。
また、酸化数が+1のタングステン(I)錯体としては、ジホスファンやη5-シクロペンタジエニドを含む非ウェルナー型錯体が挙げられ、具体的には、WI(η6-C6H6) 2]+,[ WCl(N2)(diphos)2](diphosは、2座配位子(C6H5)2PCH2CH2P(C6H5)2)が挙げられる。
また、酸化数が+4のタングステン(IV)錯体としては、例えば、[W{N(CH3)2}4]、[W(CN)8]4-、それにオキソ配位子をもつWO2+の錯体や、O2-で2重架橋したW2O2 4+の錯体が挙げられる。
また、酸化数が+6のタングステン(VI)錯体としては、例えば、W(OCH2CH3)6、WO2(acetylacetonate)2]、TUNGSTEN (VI) PHENOXIDEが挙げられる。なお、2核以上の錯体の場合には、混合原子価錯体もある。
酸化数が+2のバナジウム(II)錯体としては、シクロペンタジエニル錯体[VII(η5-C5H5)2] 等が挙げられる。
酸化数が+4のバナジウム(IV)錯体としては、[VOCl2{N(CH3)3}2])、 [VCl4(diars)]),8(10面体の[VCl4(diars)2])等が挙げられる。
モリブデンの酸化数が+5と+6の複合体又はタングステンの酸化数が+5と+6の複合体である場合に、酸化数が+6のモリブデン又はタングステン100モルに対して、酸化数が+5のモリブデン又はタングステンが10モル以上であることが、駆動電圧の低下や素子寿命を向上させる点から好ましい。一方、通常のMoO3のなどのモリブデン酸化物の場合は、モリブデンのほとんどがMoVIであり、組成式だとMonO3nとなる。しかし蒸着時の酸素欠損やスラリー形成時の物理的な粉砕により生じた粒子表面などに存在する酸素欠陥などによりMonO3n-mになり、MoVも多少存在するかもしれない。しかし、MoO3で導入されるMoVは酸素欠陥により生じるので、不均一であり不安定である。
バナジウムの場合には酸化数+5が安定(V2O5)、酸化数+4が不安定(V2O4)である。バナジウム錯体の反応生成物はそれぞれ、バナジウムの酸化数が+5と+4の複合体のアニオン状態で存在することが、駆動電圧の低下や素子寿命を向上させる点から好ましい。
例えば、有機モリブデン錯体や有機タングステン錯体を用いた場合、モリブデンの酸化数が+5と+6の複合体又はタングステンの酸化数が+5と+6の複合体のアニオン状態が形成され、本来不安定な酸化数が+5のモリブデン又はタングステンが比較的多い状態でも安定に保持され得るため、駆動電圧の低下や素子寿命を向上させる点から好ましい。
好適に用いられる上記カルボニル基及び/又は水酸基を有する有機溶媒としては、アルデヒド系、ケトン系、カルボン酸系、エステル系、アミド系、アルコール系、フェノール系などが挙げられ、沸点が50℃~250℃であるものが好適に用いられる。上記カルボニル基及び/又は水酸基を有する有機溶媒は、具体的には例えば、アセトン、メチルエチルケトン、2-ペンタノン、3-ペンタノン、2-ヘキサノン、2-ヘプタノン、4-ヘプタノン、メチルイソプロピルケトン、ジイソブチルケトン、アセトニルアセトン、イソホロン、シクロヘキサノン等のケトン系溶媒;アセトアルデヒド、プロピオンアルデヒド、フルフラール、ベンズアルデヒド等のアルデヒド系溶媒;酢酸、プロピオン酸、酪酸、吉草酸等のカルボン酸系溶媒;酢酸エチル、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル、酢酸n-アミル、安息香酸エチル、安息香酸ブチル等のエステル系溶媒;N-メチルホルムアミド、N,N-ジメチルホルムアミド、N-エチルアセトアミド等のアミド系溶媒;例えば、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、グリセリン、エチレングリコール、プロピレングリコール、1,2-ブチレングリコール、シクロヘキサノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル等のアルコール系溶媒;フェノール、クレゾール、キシレノール、エチルフェノール、トリメチルフェノール、イソプロピルフェノール、t-ブチルフェノール等のフェノール系溶媒等が挙げられる。
本発明の正孔注入輸送層用デバイス材料は、前記有機-遷移金属酸化物複合体に、フッ素含有有機化合物が付着している。
本発明の正孔注入輸送層用デバイス材料において「付着」とは、有機溶剤中に分散しても、剥離しない程度に、フッ素含有有機化合物が有機-遷移金属酸化物複合体表面に固定していることをいう。「付着」には、吸着や配位も含まれるが、イオン結合、共有結合等の化学結合であることが好ましい。「付着」の態様は、有機-遷移金属酸化物複合体の表面の全体をフッ素含有有機化合物が被覆するように付着している態様であっても良いし、表面の一部にフッ素含有有機化合物が付着している態様であっても良い。
前記フッ素含有有機化合物としては、フッ素化アルキル基を含有することが、エネルギー照射による濡れ性の変化が良好で、優れたパターニングが得られる点から好ましい。
また、フッ素含有有機化合物としては、-NH-、-N=、-S-、-O-、-NH(C=O)-、-O-(C=O)-、-O-(SO2)-、-O-(C=O)-O-、-S-(C=O)-O-、-SiR2-(C=O)-O-、-SiR2-のような、複素環を形成していないヘテロ原子を含むことが、エネルギー照射によってフッ素有機化合物が分解されやすいため、濡れ性変化パターン形成工程で感度が向上する点から好ましい。
前記フッ素化アルキル基のフッ素化率(アルキル基中のフッ素原子の割合)は、好ましくは50~100%、さらに好ましくは80~100%であり、特に水素原子をすべてフッ素原子で置換したパーフルオロアルキル基が、高い撥油性を発現させる点から好ましい。
また、芳香族炭化水素及び/又は複素環は電荷輸送性を有することが多いため、芳香族炭化水素及び/又は複素環を含むフッ素含有有機化合物により作製した正孔注入輸送層中の電荷移動度を高く維持できるので、低電圧化をはじめとする高効率化に対して利点がある。後述するフッ素含有有機化合物を分解するような処理により、膜の表層部のフッ素含有有機化合物は除去されるが、膜の内部には芳香族炭化水素及び/又は複素環を含むフッ素含有有機化合物が残るため、電荷輸送性が高い方が高効率化に寄与し得る。
また、例えば有機EL素子等の有機デバイスの各層には通常芳香族炭化水素及び/又は複素環電荷輸送性材料が含まれるため、隣接する有機層と正孔注入輸送層の密着性の向上を考慮すると、芳香族炭化水素及び/又は複素環の構造を含むことが長駆動寿命化に寄与する点から好ましい。
CF3-、CF3CF2-、CHF2CF2-、CF3(CF2)2-、CF3(CF2)3-、CF3(CF2)4-、CF3(CF2)5-、CF3(CF2)6-、CF3(CF2)7-、CF3(CF2)8-、CF3(CF2)9-、CF3(CF2)11-、CF3(CF2)15-、CF3CH2CH2-、CF3CF2CH2CH2-、CHF2CF2CH2CH2-、CF3(CF2)2CH2CH2-、CF3(CF2)3CH2CH2-、CF3(CF2)4CH2CH2-、CF3(CF2)5CH2CH2-、CF3(CF2)6CH2CH2-、CF3(CF2)7CH2CH2-、CF3(CF2)8CH2CH2-、CF3(CF2)9CH2CH2-、CF3(CF2)11CH2CH2-、CF3(CF2)15CH2CH2-、CF3(CF2)5O(CF3)CF-、CF3(CF2)2O(CF3)CFCF2O(CF3)CF-、CF3(CF2)2O(CF3)CFCF2O(CF3)CFCF2O(CF3)CFCF2O(CF3)CF-、CF3(CF2)5O(CF3)CF-。以上は、直鎖構造を例示したが、イソプロピル基など分岐構造であっても良い。
芳香族炭化水素及び/又は複素環を含むフッ素含有有機化合物の例としては、ペンタフルオロフェニル基、2,3,5,6-テトラフルオロフェニル基、3,4,5-トリフルオロフェニル基、2,4-ジフルオロフェニル基、3,4-ジフルオロフェニル基、3,5-ジフルオロフェニル基、ノナフルオロビフェニル基、α,α,α,2,3,5,6-ヘプタフルオロ-p-トリル基、ヘプタフルオロナフチル基、(トリフルオロメチル)フェニル基、3,5-ビス(トリフルオロメチル)フェニル基、ペンタフルオロフェニルメチル基、2,3,5,6-テトラフルオロフェニルメチル基、3,4,5-トリフルオロフェニルメチル基、2,4-ジフルオロフェニルメチル基、3,4-ジフルオロフェニルメチル基、3,5-ジフルオロフェニルメチル基、ノナフルオロビフェニルメチル基、α,α,α,2,3,5,6-ヘプタフルオロ-p-トリルメチル基、ヘプタフルオロナフチルメチル基、(トリフルオロメチル)フェニルメチル基、3,5-ビス(トリフルオロメチル)フェニルメチル基、4,4’,4”-トリフルオロトリチル基等が挙げられる。
一般式(I)
Y-Q-(A’-FQ’)n-(A-FQ)
(一般式(I)において、Yは前記連結基を表す。Qは、直鎖、分岐又は環状の脂肪族炭化水素基、芳香族炭化水素基、脂肪族複素環基、芳香族複素環基又はこれらの組み合わせ、或いは直接結合を表す。A及びA’はそれぞれ独立に、-NH-、-N=、-S-、-O-、-NH(C=O)-、-O-(C=O)-、-O-(SO2)-、-O-(C=O)-O-、-S-(C=O)-O-、-SiR2-(C=O)-O-、-SiR2-、又は直接結合を表し、当該Rは水素又は直鎖、分岐又は環状の脂肪族炭化水素基を表す。FQ及びFQ’はそれぞれ独立に、前記フッ素含有有機化合物を表す。また、nは0又は1以上の整数である。)
nが1以上の場合はエネルギー照射によってA’の部分で切断されやすく、FQで表わされるフッ素有機化合物が分解されやすくなる。nが1以上の場合としては、例えば、-O-(CH2)p-O-(CH2)2-(CF2)q- CF3などが挙げられる。
nは5以下であることが好ましく、更に4以下であることが分解速度が速くなる点から好ましい。
なお、表面に付着したフッ素含有有機化合物の分子量は、分子量分布を有しない場合には、化合物そのものの分子量を意味し、分子量分布を有する場合にはゲル浸透クロマトグラフィー(GPC)により測定したポリスチレン換算値である重量平均分子量を意味する。
例えば、表面張力28.5mN/mの液体の接触角が25°以上となるように、より好ましくは45°以上、さらに好ましくは55°以上となるように選択することが挙げられる。
本発明に係る第一の態様の正孔注入輸送層形成用インクは、前記本発明に係る正孔注入輸送層用デバイス材料と、有機溶媒とを含有することを特徴とする。
本発明に係る第二の態様の正孔注入輸送層形成用インクは、有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体と、遷移金属及び/又は遷移金属酸化物と連結する作用を生ずる連結基を含むフッ素含有有機化合物と、有機溶媒を含有することを特徴とする。
本発明に係る第三の態様の正孔注入輸送層形成用インクは、有機遷移金属錯体と、遷移金属及び/又は遷移金属酸化物と連結する作用を生ずる連結基を含むフッ素含有有機化合物と、カルボニル基及び/又は水酸基を有する有機溶媒を含有することを特徴とする。
また本発明では、有機-遷移金属酸化物複合体の表面にフッ素含有有機化合物が付着しているため、フッ素系の溶媒が好適に用いられる。例えば、トリフルオロメチルベンゼン、ヘプタフルオロ-n-酪酸エチル、ヘプタフルオロ-n-酪酸メチル、1,1,3,3-ヘキサフルオロ-2-プロパノール、1,1,3,3-ヘキサフルオロ-2-フェニル-2-プロパノール、1H,1H-トリフルオロエタノール、1H,1H,3H-テトラフルオロプロパノール、1H,1H,5H-オクタフルオロペンタノールなど前記溶媒の全部あるいは一部をフッ素化したものを用いることができる。以上の溶媒は単独で用いても、複数を混ぜ合わせた共溶媒にして用いて用いることもできる。
前記第二の態様のインク中の有機-遷移金属酸化物複合体は、有機遷移金属錯体と
を、カルボニル基及び/又は水酸基を有する有機溶媒に溶解乃至分散させ、前記有機遷移金属錯体中の遷移金属を酸化して得ることが好ましい。
酸化する方法として光照射する場合には、光照射手段としては、紫外線を露光する方法等が挙げられる。
加熱温度、又は光照射量により、有機遷移金属錯体や有機-遷移金属酸化物複合体の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。
本発明に係るデバイスの製造方法の第一の態様は、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、
パターン状に第一電極層が形成された基板上に、前記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する正孔注入輸送層形成工程と、
基体上に少なくとも光触媒を含有する光触媒含有層が形成されている光触媒含有層基板を、前記正孔注入輸送層に対して、エネルギー照射に伴う光触媒の作用が及び得る間隙をおいて配置した後、パターン状にエネルギー照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成する濡れ性変化パターン形成工程とを有することを特徴とする。
パターン状に電極層が形成された基板上に、前記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する正孔注入輸送層形成工程と、
パターン状に真空紫外線を照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成する濡れ性変化パターン形成工程とを有することを特徴とする。
また、本発明に係る正孔注入輸送層用デバイス材料は、比較的高温(例えば200℃)の加熱にも耐性があるため、加熱プロセス時に濡れ性変化パターンが損なわれず、正孔注入輸送層上に何層もパターン状に積層する工程を行うことができる。
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(A)~図1(C)は、本発明のデバイスの製造方法の一例を示す工程図である。まず、図1(A)に示すように、基板2上に第一電極層3をパターン状に形成し、この第一電極層3上に上記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層4を形成する(正孔注入輸送層形成工程)。次に、図1(B)に示すように、基体22と、この基体22上にパターン状に形成された遮光部23と、遮光部23を覆うように基体22上に形成され、光触媒を含有する光触媒含有層24とを有する光触媒含有層基板21を準備する。次いで、光触媒含有層基板21を、正孔注入輸送層4に対して、エネルギー照射に伴う光触媒の作用が及び得る間隙をおいて配置した後、光触媒含有層基板21を介して正孔注入輸送層4に対してパターン状にエネルギー線27を照射する。エネルギー線27の照射により、図1(C)に示すように、光触媒含有層24に含有される光触媒の作用から、正孔注入輸送層4の露光部では、正孔注入輸送層4の少なくとも表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物が分解除去された、正孔注入輸送層のフッ素分解部5が形成され、正孔注入輸送層4の露光部の表面に親液性領域11が形成される。一方、正孔注入輸送層4の未露光部では、正孔注入輸送層24の表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物がそのまま残り、撥液性領域12となる(濡れ性変化パターン形成工程)。このようにして、デバイス用基板1が得られる。その後、デバイス用基板1上の親液性領域11上に、少なくともデバイスに必要なパターン状の層を積層し、第二電極層を積層し、デバイスを製造することができる。
まず、図2(A)に示すように、基板2上に第一電極層3をパターン状に形成し、パターンの開口部に仕切り部(隔壁6a)を形成し、第一電極層3および仕切り部(隔壁6a)の上に上記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層4を形成する(正孔注入輸送層形成工程)。ここで、基板2が透光性基板であって、前記仕切部(隔壁6a)が濡れ性変化パターン形成工程にて照射されるエネルギー線を反射または吸収する仕切部である。次に、図2(B)に示すように、基体22と、この基体22上に形成された光触媒を含有する光触媒含有層24とを有する光触媒含有層基板21を準備する。次いで、光触媒含有層基板21を、正孔注入輸送層4に対して、エネルギー照射に伴う光触媒の作用が及び得る間隙をおいて配置した後、透光性基板である基板2側からエネルギー線27を照射する。この態様の場合、仕切部(隔壁6a)がエネルギー線を反射または吸収するので、仕切部(隔壁6a)が形成されていない箇所はエネルギー線27が照射され、仕切部(隔壁6a)が形成されている箇所はエネルギー線27が照射されない。エネルギー線27の照射により、図2(C)に示すように、光触媒含有層24に含有される光触媒の作用から、正孔注入輸送層4の露光部では、正孔注入輸送層4の少なくとも表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物が分解除去された、正孔注入輸送層のフッ素分解部5が形成され、正孔注入輸送層4の露光部の表面に親液性領域11が形成される。一方、正孔注入輸送層4の未露光部では、正孔注入輸送層24の表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物がそのまま残り、撥液性領域12となる(濡れ性変化パターン形成工程)。このようにして、デバイス用基板1が得られる。その後、デバイス用基板1上の親液性領域11上に、デバイスに必要なパターン状のデバイス層を塗布法により積層することが可能で、その後第二電極層を積層し、デバイスを製造することができる。
まず図3(A)に示すように、基板2上に第一電極層3をパターン状に形成し、パターンの開口部に仕切り部(隔壁6a)を形成し、第一電極層3および仕切り部(隔壁6a)の上に上記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層4を形成する(正孔注入輸送層形成工程)。次に、図3(B)に示すように、基体22と、この基体22上に形成された光触媒を含有する光触媒含有層24とを有する光触媒含有層基板21を準備する。次いで、光触媒含有層基板21を、正孔注入輸送層4に対して、エネルギー照射に伴う光触媒の作用が及び得る間隙をおいて配置した後、光触媒含有層基板21を介して正孔注入輸送層4に対して紫外レーザー光28をパターン状にスキャンして照射する。紫外レーザー光28の照射により、図3(C)に示すように、光触媒含有層24に含有される光触媒の作用から、正孔注入輸送層4の露光部では、正孔注入輸送層4の少なくとも表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物が分解除去された、正孔注入輸送層のフッ素分解部5が形成され、正孔注入輸送層4の露光部の表面に親液性領域11が形成される。一方、正孔注入輸送層4の未露光部では、正孔注入輸送層24の表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物がそのまま残り、撥液性領域12となる(濡れ性変化パターン形成工程)。このようにして、デバイス用基板1が得られる。その後、デバイス用基板1上の親液性領域11上に、デバイスに必要なパターン状のデバイス層を塗布法により積層することが可能で、その後第二電極層を積層し、デバイスを製造することができる。
まず、図4(A)に示すように、基板2上に第一電極層3をパターン状に形成し、パターンの開口部に仕切り部(隔壁6a)を形成し、第一電極層3および仕切り部(隔壁6a)の上に上記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層4を形成する(正孔注入輸送層形成工程)。次に、図4(B)に示すように、メタルマスク30を正孔注入輸送層4の表面に配置し、メタルマスク30を介して正孔注入輸送層4に対して真空紫外光29を照射する。真空紫外光29の照射により、図4(C)に示すように、正孔注入輸送層4の露光部では、正孔注入輸送層4の少なくとも表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物が分解除去された、正孔注入輸送層のフッ素分解部5が形成され、正孔注入輸送層4の露光部の表面に親液性領域11が形成される。一方、正孔注入輸送層4の未露光部では、正孔注入輸送層24の表層部の正孔注入輸送層デバイス材料の表面に存在するフッ素含有有機化合物がそのまま残り、撥液性領域12となる(濡れ性変化パターン形成工程)。このようにして、デバイス用基板1が得られる。その後、デバイス用基板1上の親液性領域11上に、デバイスに必要なパターン状のデバイス層を塗布法により積層することが可能で、その後第二電極層を積層し、デバイスを製造することができる。
本発明における第1正孔注入輸送層形成工程は、パターン状に第一電極層が形成された基板上に、前記本発明に係る正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する工程である。
正孔注入輸送層の形成方法としては、パターン状に第一電極層が形成された基板上の全面に、前記本発明に係る正孔注入輸送層用デバイス材料を成膜することが可能な方法であれば特に限定されるものではない。例えば、前記本発明に係る、第一、第二、又は第三の態様の正孔注入輸送層形成用インクを調製し、当該インクを用いて塗布して層を形成するウェットプロセスがプロセス優位性の点から好ましい。また、当該インクを用いて塗布して形成された層を転写する転写法も用いることができる。なお、パターン状に第一電極層が形成された基板上であれば、当該第一電極層上に例えば別途正孔注入層が形成された上に、本発明の正孔注入輸送層が形成されてもよい。
また、塗布する前に当該正孔注入輸送層形成用インクを酸素存在下で加熱する工程を有していても良い。この場合、正孔注入輸送層用デバイス材料中の遷移金属酸化物量が増加し、正孔注入輸送性が向上する場合がある。
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。
基板は、光を透過する透光性であってもよく、透光性でなくてもよい。例えば、本発明のデバイスにおいて、基板側から光を取り出す場合や、本発明のデバイスを作製する過程において、親液性領域および撥液性領域からなるパターンを形成する際に基板側からエネルギーを照射する場合には、基板は透光性であることが好ましい。透光性基板としては、例えば、石英、ガラス等を挙げることができる。透光性が必要とされない場合の基板としては、アルミニウムおよびその合金等の金属、プラスチック、織物、不織布等を用いることができる。
本発明に用いられる第一電極層は、パターン状に基板上に形成されているものである。
第一電極層を形成する材料としては、導電性を有する材料であれば特に限定されるものではない。
また、第一電極層を形成する材料としては、透明性を有していてもよく、有さなくてもよい。例えば、本発明のデバイスにおいて、基板側から光を取り出す場合や、本発明のデバイスを作製する過程において、親液性領域および撥液性領域からなるパターンを形成する際に基板側からエネルギーを照射する場合には、第一電極層は透明性を有することが好ましい。導電性および透明性を有する材料としては、In-Zn-O(IZO)、In-Sn-O(ITO)、ZnO-Al、Zn-Sn-O等を好ましいものとして例示することができる。一方、例えば、本発明のデバイスにおいて、基板の反対側から光を取り出す場合には、第一電極層に透明性は要求されない。この場合、導電性を有する材料として、金属を用いることができ、具体的には、Au、Ta、W、Pt、Ni、Pd、Cr、あるいは、Al合金、Ni合金、Cr合金等を挙げることができる。
本発明における濡れ性変化パターン形成工程は、前記正孔注入輸送層表面に濡れ性(wetting)の変化した濡れ性変化パターンを形成する工程である。
正孔注入輸送層表面に濡れ性変化パターンを形成するための、パターン状にエネルギー照射する方法としては、正孔注入輸送層に含有される材料をパターン状に分解できる方法であれば特に限定されるものではないが、通常、エネルギー照射によって、酸素ラジカルなどの活性酸素種を発生させることができる方法が用いられる。この活性酸素種の強力な酸化・還元力により、正孔注入輸送層に含有される材料の表面に付着しているフッ素含有有機化合物を分解することができるからである。
親液性領域は、正孔注入輸送層用デバイス材料の表面に付着されたフッ素含有有機化合物が含有されていない、または、正孔注入輸送層にもともと含有されていた材料の表面に付着されたフッ素含有有機化合物の量と比較して、親液性領域はフッ素含有有機化合物が少ない量含有されている。
さらに、従来のような撥液性材料を用いた隔壁や撥液化処理された隔壁では、隔壁の頂部だけでなく側部も撥液性を有するものとなるため、仕切部の側部から発光層が物理的に剥離したり、発光層等の厚みの薄い箇所や発光層等が形成されない箇所が発生したりするという不具合があった。これに対し、本発明においては、仕切部の側部上には親液性領域が配置され得るので、仕切り部の側部から発光層が物理的に剥離したり、発光層等の厚みの薄い箇所や発光層等が形成されない箇所が発生したりするのを抑制することができる。
以下、濡れ性変化パターン形成工程について、上記(1)、(2)の方法をそれぞれ説明する。
エネルギー照射に伴う光触媒の作用を利用する方法は、基体上に少なくとも光触媒を含有する光触媒含有層が形成されている光触媒含有層基板を用い、上記光触媒含有層基板を、上記正孔注入輸送層に対して、エネルギーの照射に伴う光触媒の作用がおよび得る間隙をおいて配置した後、パターン状にエネルギーを照射する方法である。
以下、光触媒含有層基板および光触媒含有層基板を用いて正孔注入輸送層に光触媒の作用を及ぼす方法について説明する。
本発明に用いられる光触媒含有層基板は、基体上に少なくとも光触媒を含有する光触媒含有層が形成されているものである。
光触媒含有層の形成位置としては、図2(B)に例示するように、基体22上の全面に光触媒含有層24が形成されていてもよく、図6(A)に例示するように、基体22上に光触媒含有層24がパターン状に形成されていてもよい。
光触媒含有層がパターン状に形成されている場合には、光触媒含有層を正孔注入輸送層に対して所定の間隙をおいて配置し、エネルギーを照射する際に、フォトマスク等を用いてパターン照射する必要がなく、全面に照射することにより、正孔注入輸送層に含有される材料が分解された撥液性領域をパターン状に形成することができる。また、この場合、エネルギーの照射方向としては、光触媒含有層と正孔注入輸送層とが面する部分にエネルギーが照射されれば、いかなる方向であってもよい。さらには、照射されるエネルギーも、平行光等の平行なものに限定されない。
本発明においては、光触媒含有層基板を、正孔注入輸送層に対して、エネルギー照射に伴う光触媒の作用がおよび得る間隙をおいて配置する。なお、間隙とは、光触媒含有層および正孔注入輸送層が接触している状態も含むものとする。
上記間隔は、パターン精度が極めて良好であり、光触媒の感度も高く、分解除去の効率が良好である点を考慮すると、0.2μm~20μmの範囲内であることがより好ましく、さらに好ましくは1μm~10μmの範囲内である。
なお、上述のような間隙をおいた配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
エネルギー照射に用いる光の波長は、通常、450nm以下の範囲で設定され、好ましくは380nm以下の範囲で設定される。これは、上述したように、光触媒含有層に用いられる好ましい光触媒が二酸化チタンであり、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上記の波長の光が好ましいからである。
また、パターン状にエネルギーを照射する方法としては、これらの光源を用い、フォトマスクを介してパターン照射する方法の他、エキシマ、YAG等のレーザーを用いてパターン状に描画照射する方法を用いることもできる。
この際、光触媒含有層を加熱しながらエネルギー照射することが好ましい。感度を上昇させことができ、効率的に濡れ性を変化させることができるからである。具体的には、基板およびマスクを30℃~80℃の範囲内で加熱することが好ましい。基板とマスクの温度差は、露光精度の観点からできるだけ小さい方が良いが、1℃以内であることが好ましい。
基体22上の全面に光触媒含有層24が形成されている場合には、フォトマスクを介してパターン状にエネルギーを照射するか、或いは、図2(B)に例示するように、マスクとして、エネルギー線を反射または吸収する仕切部を有する透光性基板側(正孔注入輸送層の背面側)から照射してパターン状にエネルギーを照射する。また、図3(B)に例示するように基体22上の全面に光触媒含有層24が形成されている場合であって、レーザーを用いてパターン状に描画照射しても良い。また、図6(A)に例示するように基体22上に光触媒含有層24がパターン状に形成されている場合には、マスクとして光触媒含有層基板を用いることによりパターン状にエネルギーを照射する。さらに、図1(B)に例示するように遮光部23がパターン状に形成されている場合には、マスクとして光触媒含有層基板を用いることによりパターン状にエネルギーを照射する。
パターン状に真空紫外光を照射する方法は、マスクとして真空紫外光用マスクを用い、エネルギーとして真空紫外光を照射する方法が挙げられる。
また、真空紫外光の照射量としては、上記親液性層形成用層を除去できる範囲内であれば特に限定されるものではなく、正孔注入輸送層に含有される材料の種類や、上記真空紫外光の波長等によって適宜調整すればよい。
メタルマスクの材料としては、上記真空紫外光を遮光することができるものであればよく、例えば、特開2007-178783号公報等に記載されたものを用いることができる。
一方、透明基材としては、真空紫外光を透過することができるものであればよく、例えば、石英基板等を用いることができる。また、遮光部を構成する遮光材料としては、クロム、酸化クロム等の金属が挙げられる。
一方、隔壁や絶縁層等の仕切部が形成されている場合には、真空紫外光用マスクを正孔注入輸送層にできるだけ接近させ、かつ、真空紫外光用マスクが正孔注入輸送層に接触するように、真空紫外光用マスクを配置してもよく、また真空紫外光用マスクを正孔注入輸送層にできるだけ接近させ、かつ、真空紫外光用マスクが正孔注入輸送層に接触しないように、真空紫外光用マスクを配置してもよい。隔壁や絶縁層等の仕切部が形成されている場合であって、透明基材上に遮光部がパターン状に形成された真空紫外光用マスクを用いる場合には、真空紫外光用マスクを正孔注入輸送層に密着するように固定することができる。
仕切部の頂部上に位置する正孔注入輸送層の部分にエネルギーを照射する場合であって、マスクとして透過領域および遮光領域を有するマスクを用いる場合には、仕切部の頂部の面積に対するマスクの透過領域の面積の比率、および、正孔注入輸送層およびマスク間の距離の少なくともいずれか一方を調整して、正孔注入輸送層側の表面での液体の接触角が仕切部の側部側から頂部側に向かって高くなるように、撥液性領域を形成してもよい。
また、隔壁のように膜厚が比較的厚い仕切部の場合、仕切部の頂部側から側部側に向かって、正孔注入輸送層とマスクとの距離が徐々に広くなることから、この正孔注入輸送層とマスクとの距離に応じて、液体の接触角に傾斜をもたせることもできる。
本発明においては、必要に応じて、前記正孔注入輸送層形成工程前に、前記パターン状に第一電極層が形成された基板上の前記第一電極層のパターン間に、仕切部を形成する仕切部形成工程を有していても良い。
仕切部としては、例えば、隔壁および絶縁層が挙げられる。図2(A)、図3(A)、図4(A)の隔壁6aとして例示するように、仕切部としては、隔壁及び絶縁層の両方の機能を果たすものが一体となって形成されても良い。以下、隔壁および絶縁層に分けて説明する。
本発明に係るデバイスにおいて、この仕切部が形成された部分は、通常、非発光領域となる。
本発明においては、図2(A)、図3(A)、図4(A)に例示するように、第一電極層3が形成された基板2上に、隔壁6aがパターン状に形成されていてもよい。通常、第一電極層がパターン状に形成されている場合には、隔壁6aは第一電極層3のパターンの開口部に形成される。
隔壁は、正孔注入輸送層上に形成される層をパターン状に塗り分けるために設けられるものである。
有機材料としては、例えば、エチレン-酢酸ビニル共重合体、エチレン-塩化ビニル共重合体、エチレン-ビニル共重合体、ポリスチレン、アクリロニトリル-スチレン共重合体、ABS樹脂、ポリメタクリル酸樹脂、エチレン-メタクリル酸樹脂、ポリ塩化ビニル樹脂、塩素化塩化ビニル、ポリビニルアルコール、セルロースアセテートプロピオネート、セルロースアセテートブチレート、ナイロン6、ナイロン66、ナイロン12、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリビニルアセタール、ポリエーテルエーテルケトン、ポリエーテルサルフォン、ポリフェニレンサルファイド、ポリアリレート、ポリビニルブチラール、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリアミック酸樹脂、ポリエーテルイミド樹脂、フェノール樹脂、ユリア樹脂等が挙げられる。
無機材料としては、例えば、SiO2などを挙げることができる。
また、絶縁層上に別途、隔壁が形成されている場合、隔壁の幅としては、図7(A)に例示するように、隔壁6aの幅が第一電極層3のパターン間の幅よりも狭くてもよく、図7(B)に例示するように、隔壁6aの幅が第一電極層3のパターン間の幅よりも広くてもよい。
また、隔壁の形成方法としては、フォトリソグラフィー法、印刷法等の一般的な方法を
用いることができる。
本発明においては、図7(A)及び図7(B)に例示するように、第一電極層3が形成された基板2上に、絶縁層6bがパターン状に形成されていてもよい。通常、第一電極層がパターン状に形成されている場合には、絶縁層6bは第一電極層3のパターンの開口部に形成され、かつ、第一電極層のパターンの端部を覆うように形成される。図7(A)及び図7(B)においては、絶縁層6b上に隔壁6aも形成されているが、絶縁層6bのみが形成され、隔壁6aが形成されていない態様であっても良い。
絶縁層は、隣接する第一電極層のパターン間での導通や、第一電極層および第2電極層
間での導通を防ぐために設けられるものである。
を用いることができる。
絶縁層の膜厚としては、10nm~50μm程度とすることができる。
デバイスの製造方法における、その他の工程については、各デバイスに応じて、従来公知の工程を適宜用いることができる。
本発明の必須成分である第二電極層としても、各デバイスに応じて、従来公知の材料を適宜採用して、従来公知の工程により適宜形成すれば良い。本発明のデバイスにおいて、第二電極層は、金属又は金属酸化物で形成されることが好ましく、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。
本発明に係るデバイスの第一の態様は、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、前記本発明に係る正孔注入輸送層用デバイス材料を含有し、前記正孔注入輸送層の表層部の前記正孔注入輸送層用デバイス材料のフッ素含有有機化合物が分解除去されていることを特徴とする。
パターン状に第一電極層が形成された基板上の前記第一電極層のパターン間に、仕切部を有し、前記仕切部の開口部内の前記第一電極層上及び前記仕切部上に連続した正孔注入輸送層を有し、
前記仕切部の開口部内の前記第一電極層上及び前記仕切部の側部上の正孔注入輸送層においては、前記本発明に係る正孔注入輸送層用デバイス材料の少なくとも一部のフッ素含有有機化合物が分解除去されており、且つ、前記絶縁層の頂部上の正孔注入輸送層は前記本発明に係る正孔注入輸送層用デバイス材料を含有していることを特徴とする。
上記本発明のデバイスはいずれの態様も、前記本発明に係るデバイスの製造方法によって得ることができるものである。
図8は、本発明に係るデバイスの第一の態様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10の基本的な層構成は、基板2上に対向する2つの電極(3及び9)と、その2つの電極(3及び9)間に配置された正孔注入輸送層4を含み、当該正孔注入輸送層4が、前記本発明に係る正孔注入輸送層用デバイス材料を含有し、前記正孔注入輸送層の表層部の前記正孔注入輸送層用デバイス材料のフッ素含有有機化合物が分解除去されている、正孔注入輸送層のフッ素分解部5を含む。そして前記第一電極層3上及び仕切り部6aの側部上に存在する正孔注入輸送層4の表層部に親液性領域11、及び仕切部6aの頂部上に撥液性領域12からなるパターンが形成されている。上記正孔注入輸送層4の親液性領域11上に、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。)を含むデバイス層7が形成されている。
基板2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。
デバイス層7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。デバイス層7が多層からなる場合は、機能層や、補助層を含んでいる。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。
第二電極層9は、対向する電極1との間に正孔注入輸送層4とデバイス層7が存在する箇所に少なくとも設けられる。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。
そして前記第一電極層3上及び仕切部6aの側部上に存在する正孔注入輸送層のフッ素分解部5が親液性領域11、及び仕切部6aの頂部上に撥液性領域12からなるパターンが形成されている。上記正孔注入輸送層4の親液性領域11上に、デバイス層7が形成されている。更に、第二電極層9が、基板2上に2つの電極(3及び9)が対向し、その2つの電極(3及び9)間に配置された正孔注入輸送層4を有するように、形成されている。
なお、前記仕切部6aの開口部内の前記第一電極層3上及び前記仕切部6a上に連続した正孔注入輸送層(4及び5)は、正孔注入輸送層に別層として設けられた界面がない。正孔注入輸送層のフッ素分解部5は、正孔注入輸送層4と同じ材料から正孔注入輸送層用デバイス材料の少なくとも一部のフッ素含有有機化合物が分解除去された部分として、正孔注入輸送層にパターン状に含まれるものである。
本発明のデバイスにおいて、第一電極層、第二電極層、正孔注入輸送層、及び、当該正孔注入輸送層に用いられる正孔注入輸送層用デバイス材料については、上記の「I.正孔注入輸送層用デバイス材料」、「II.正孔注入輸送層用インク」、「III.デバイスの製造方法」において記載したのと同様であっても良い。更にデバイスに含まれるデバイス層(機能層や補助層)については、後述するデバイスの具体例において、詳細に述べる。
ここでは、正孔注入輸送層について、さらに補足する。
本発明のデバイスにおける正孔注入輸送層は、少なくとも上記本発明に係る正孔注入輸送層用デバイス材料を含有するものである。当該正孔注入輸送層は、上記本発明に正孔注入輸送層用デバイス材料のみからなるものであっても良いが、更に他の成分を含有していても良い。
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、ポリアニリン、ポリチオフェン、ポリフェニレンビニレン誘導体等を用いることができる。ポリアニリン、ポリチオフェン、ポリフェニレンビニレン誘導体等の導電性高分子は、酸によりドーピングされていてもよい。更に、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。
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10を用いて順に説明する。
図10は、本発明の有機EL素子の一例を示す概略断面図である。図10に例示する有機EL素子31は、基板2上に第1電極層3がパターン状に形成され、第1電極層3のパターンの開口部に隔壁6aが形成され、第1電極層3および隔壁6aの上に正孔注入輸送層4が形成され、この正孔注入輸送層4の表層部の前記正孔注入輸送層用デバイス材料のフッ素含有有機化合物が分解除去されてフッ素除去層5が形成されており、フッ素除去層5の表面に親液性領域11、および隔壁6aの頂上部に撥液性領域12からなるパターンが形成され、さらに、親液性領域11上に形成された発光層32と、発光層32上に形成された電子注入輸送層33と、電子注入輸送層33上に形成された第2電極層34とを有している。
上記図10においては、第一電極層3は陽極、第二電極層34は陰極として機能する。上記有機EL素子は、陽極と陰極の間に電場を印加されると、正孔が陽極から正孔注入輸送層4を経て発光層32に注入され、且つ電子が陰極から発光層に注入されることにより、発光層5の内部で注入された正孔と電子が再結合し、素子の外部に発光する機能を有する。
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、必要に応じて電子注入輸送層33が設けられる。
なお、基板、電極層については、上記デバイスの説明において挙げたものを用いることができる。
本発明のデバイスにおいて必須成分である、上記本発明に係る正孔注入輸送層用デバイス材料又はその分解物を含有する正孔注入輸送層以外にも、更に正孔注入輸送層、正孔輸送層、及び正孔注入層が、発光層と第一電極層の間に適宜形成されても良い。上記本発明に係る正孔注入輸送層用デバイス材料又はその分解物を含有する正孔注入輸送層の上に更に正孔輸送層を積層し、その上に発光層を積層してもよいし、正孔注入層の上に更に上記本発明に係る正孔注入輸送層用デバイス材料又はその分解物を含有する正孔注入輸送層を積層し、その上に発光層を積層してもよい。
正孔輸送層は、正孔注入輸送性化合物を用いて、後述の発光層と同様方法で形成することができる。正孔輸送層の膜厚は、通常0.1~1μm、好ましくは1~500nmである。
正孔注入層は、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。
発光層32は、図10に示すように、第一電極層3が形成された基板2と第二電極層34との間の、上記正孔注入輸送層上の親液性領域11上に形成される。
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。
発光層の膜厚は、通常、1~500nm、好ましくは20~1000nm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り、正孔注入輸送層表面の濡れ性変化パターンを利用して、発光層も溶液塗布法で形成することができるので、この場合、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。
本発明について、以下に有機EL素子の実施例を挙げて、さらに具体的に説明する。なお、本発明は以下の実施例の記載に限定されるものではない。
[合成例1:フッ素含有有機化合物F-1の合成]
ジクロロメタン溶媒中で、N,N'-ジシクロヘキシルカルボジイミド(東京化成社製)を用いて、2,2,3,3,4,4,5,5,6,6,7,7,7-トリデカフルオロヘプタン酸(アルドリッチ社製)と1,4-ジアミノブタン(東京化成社製)との縮合反応を行い、フッ素含有有機化合物F-1を合成した。得られた化合物F-1の分子量が質量分析により434であること、及び1H NMRより、下記構造式の化合物が合成されていることを確認した。
クロロホルム中、トリエチルアミン存在下で、1H,1H,2H,2H-トリデカフルオロ-n-オクチルヨージド(東京化成社製)と2-アミノエタンチオール(東京化成社製)との縮合反応を行い、フッ素含有有機化合物F-2を合成した。得られた化合物F-2の分子量が質量分析により423であること、及び1H NMRより、下記構造式の化合物が合成されていることを確認した。
水素化アルミニウムリチウムを用いて、合成例1で得られたフッ素含有有機化合物F-1を還元することにより、フッ素含有有機化合物F-3を得た。得られた化合物F-3の分子量が質量分析により420であること、及び1H NMRより、下記構造式の化合物が合成されていることを確認した。
2,3,3,3-テトラフルオロ-2-(1,1,2,2,3,3,3-ヘプタフルオロプロポキシ)プロパン酸ナトリウム(アルドリッチ社製)をジクロロメタン溶媒中、ピリジン共存下でシアヌル酸フルオライド(アルドリッチ社製)を反応させることにより酸フッ化物に変換した。ジクロロメタン溶媒中で、当該酸フッ化物と1,4-ジアミノブタンとの縮合反応を行うことにより、フッ素含有有機化合物F-4を合成した。得られた化合物F-4の分子量が質量分析により400であること、及び1H NMRより、下記構造式の化合物が合成されていることを確認した。
モリブデンヘキサカルボニルをシクロヘキサノンに0.4wt%溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻して作製した溶液と、4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ヘプタデカフルオロデシル)ベンジルアミンをシクロヘキサノンに0.4wt%溶解させた後に室温に戻して作製した溶液を、重量比で1:1に混合して大気中で攪拌した後にフィルターでろ過して正孔注入輸送層形成用インク1を作製した。
モリブデンヘキサカルボニルをシクロヘキサノンに0.4wt%溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻して作製した溶液と、4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-ヘプタデカフルオロウンデシルアミンをシクロヘキサノンに0.2wt%溶解させた後に室温に戻して作製した溶液を、重量比で1:1に混合して大気中で攪拌した後にフィルターでろ過して正孔注入輸送層形成用インク2を作製した。
タングステンヘキサカルボニルをシクロヘキサノンに0.4wt%溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻して作製した溶液と、4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ヘプタデカフルオロデシル)ベンジルアミンをシクロヘキサノンに0.4wt%溶解させた後に室温に戻して作製した溶液を、重量比で1:1に混合して大気中で攪拌した後にフィルターでろ過して正孔注入輸送層形成用インク3を作製した。
バナジウム(III)アセチルアセトナートをシクロヘキサノンに0.4wt%溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻して作製した溶液と、4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ヘプタデカフルオロデシル)ベンジルアミンをシクロヘキサノンに0.2wt%溶解させた後に室温に戻して作製した溶液を、重量比で1:1に混合して大気中で攪拌した後にフィルターでろ過して正孔注入輸送層形成用インク4を作製した。
モリブデンヘキサカルボニル0.008gと4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ヘプタデカフルオロデシル)ベンジルアミン0.004gをシクロヘキサノン2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク5を作製した。
モリブデンヘキサカルボニル0.008gと、0.004gの合成例1で得られたフッ素含有有機化合物F-1をシクロヘキサノン2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク6を作製した。
モリブデンヘキサカルボニル0.008gと、0.004gの合成例2で得られたフッ素含有有機化合物F-2をシクロヘキサノン2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク7を作製した。
モリブデンヘキサカルボニル0.008gと、0.004gの合成例3で得られたフッ素含有有機化合物F-3をシクロヘキサノン2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク8を作製した。
モリブデンヘキサカルボニル0.008gと、0.004gの合成例4で得られたフッ素含有有機化合物F-4をシクロヘキサノン2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク9を作製した。
モリブデンヘキサカルボニル0.008gと、0.004gの合成例4で得られたフッ素含有有機化合物F-4をイソプロピルアルコール2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク10を作製した。
モリブデンヘキサカルボニル0.008gと、0.004gの合成例4で得られたフッ素含有有機化合物F-4を安息香酸エチル2.0gに溶解させ、大気中100℃で10分加熱して溶解させた後に室温に戻してフィルターでろ過して正孔注入輸送層形成用インク11を作製した。
モリブデンヘキサカルボニルをシクロヘキサノンに0.4wt%溶解させ、大気中100℃で10分加熱して正孔注入輸送層形成用比較インク1を作製した。
膜厚は、洗浄済みのITOつきガラス基板上に、測定しようとする材料で形成した層を単層として形成し、カッターナイフで段差を作製してから、段差の高さをプローブ顕微鏡(エスアイアイ・ナノテクノロジー(株)製、Nanopics1000)を用い、タッピングモードで測定した。
本発明でのイオン化ポテンシャルの値は、光電子分光装置AC-1(理研計器製)を用いて測定した仕事関数の値を適用した。測定は、洗浄済みのITO付きガラス基板(三容真空社製)上に、測定しようとする材料で形成した層を単層として形成し、前記の光電子分光装置AC-1で光電子が放出されるエネルギー値で決定した。測定条件としては、50nWの光量で0.05eV刻みで行った。
吸収スペクトルは、洗浄済みの石英基板上に、測定しようとする材料で形成した層を単層として形成し、この薄膜付基板とリファレンスの石英基板との光学吸収の差を、UV-3100PC(日立製)を用いて測定した。
製造例1~11で得られた正孔注入輸送層形成用インクを用いて形成された薄膜(10nm)の254nmの波長での透過率はいずれも80%以上と高い値であった。
液体の接触角は接触角測定器(協和界面科学(株)製、全自動接触角計(DM700))を用いて測定した。標準溶液としてキシレン(表面張力28.5mN/m)を用い、マイクロシリンジから2マイクロリットルの液滴を滴下してから5秒後の接触角を測定した。
X線光電子分光法(XPS)にて有機-遷移金属酸化物複合体に含まれる遷移金属の価数とフルオロアルキル基の有無を測定した。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。
本発明の有機EL素子は、透明陽極付ガラス基板の上に、表面にフッ素含有有機化合物が付着している有機-遷移金属酸化物複合体を含む正孔注入輸送層を形成した後に光触媒処理を施し、その後に正孔輸送層、発光層、正孔ブロック層、電子輸送層、電子注入層、陰極の基本層構成を有するように製膜して積層し、封止して緑発光の有機EL素子として作製し、その有機EL素子の特性、及び濡れ性を評価した。
パターン形成されたITO付ガラス基板(三容真空社製、ITO膜厚:150nm)を、中性洗剤、超純水の順番に超音波洗浄し、UVオゾン処理を施した。
次に、上記基板の上に正孔注入輸送層として、製造例1で得られた正孔注入輸送層形成用インク1を用いて有機-遷移金属酸化物複合体薄膜をスピンコート法により塗布形成した。塗膜形成後はホットプレート上200℃で乾燥させた。乾燥後の膜厚は10nmであった。
次に、光触媒含有層付きフォトマスクを調製した。合成石英基板上に透過領域と遮光領域を形成したフォトマスクを用意した。このフォトマスク上に、下記組成の光触媒含有層形成用塗工液をスピンコーターにより塗布し、150℃で10分間の加熱乾燥処理を施し、加水分解・重縮合反応を進行させて硬化させ、光触媒がオルガノシロキサン中に強固に固定された、膜厚100nmの透明な光触媒含有層を形成した。
・二酸化チタン(石原産業(株)製、ST-K01) 2重量部
・オルガノアルコキシシラン(東芝シリコーン(株)製、TSL8113) 0.4重量部
・イソプロピルアルコール 3重量部
次に処理された正孔注入輸送層の上に、正孔輸送層として、ポリビニルカルバゾール(PVK)(分子量70万)薄膜をスピンコート法により塗布形成した。塗工液は、PVKを1,2-ジクロロエタンに溶解させて調製した。塗膜形成後はホットプレート上150℃で乾燥させた。乾燥後の膜厚は20nmであった。
次に、上記正孔輸送層の上に、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(9-カルバゾリル-2,2’ジメチルビフェニル(CDBP)をホストとして含有する発光層薄膜をスピンコート法により塗布形成した。塗工液は、ホストであるCDBPとドーパントであるIr(mppy)3の重量比が20:1で含有した状態で、乾燥後の合計膜厚が40nmになるように、トルエンに溶解させて調製した。塗膜形成後はホットプレート上100℃で乾燥させた。
上記発光層の上に、正孔ブロック層を蒸着形成した。正孔ブロック層はブロック形成材料にビス(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)を用い、抵抗加熱法により真空中(圧力:1×10-4Pa)でBAlq蒸着膜の膜厚が15nmになるように蒸着形成した。
作製した透明陽極付きガラス基板/正孔注入輸送層/正孔輸送層/発光層/正孔ブロック層/電子輸送層の電子輸送層上に、さらに、電子注入層及び陰極を順次蒸着形成した。電子注入層は、LiF(厚み:0.5nm)を、陰極は、Al(厚み:100nm)を順次抵抗加熱蒸着法により真空中(圧力:1×10-4Pa)で蒸着膜を形成した。
陰極形成後、低酸素、低湿度状態の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、幅mmのライン状にパターニングされた陽極と、この陽極に直交するように幅mmのライン状に形成された電子注入層、陰極を備える実施例1の有機EL素子を作製した。
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。
更に、上述のように、正孔注入輸送層に対して、光触媒処理前後の濡れ性と、イオン化ポテンシャルの評価を行った。これらの結果も合わせて表1に示す。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク2を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク3を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク4を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク5を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例6において、正孔注入輸送層に光触媒マスクつきマスクを介さずに253nmの紫外光のみを照射した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク6を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク7を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク8を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク9を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク10を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク11を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用比較インク1を用いて膜厚10nmの薄膜を形成した以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層として、正孔注入輸送層形成用インク1を用いて形成された膜の代わりに、PEDOT/PSS(スタルク社製AI4083)と4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-ヘプタデカフルオロデシル)ベンジルアミンをスピンコート法で積層薄膜を形成した以外は、実施例1と同様に素子を形成し、濡れ性の評価を行った。PEDOT/PSS層はPEDOT/PSS溶液を蒸留水で薄めて、乾燥後の膜厚が10nmになるように溶解させて作製した。次にヘプタデカフルオロデシルベンジルアミンを、ヘプタフルオロ-n-酪酸エチルに0.4wt%溶解させた溶液を用いて、塗布形成して薄膜を乾燥させた。乾燥後の膜厚は計測不能で5nm以下であった。
比較例2において、正孔注入輸送層に光触媒処理を施さなかった以外は、比較例2と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層として、正孔注入輸送層形成用インク1を用いて形成された膜の代わりに、抵抗加熱法により真空中で蒸着形成されたMoO3膜(10nm)を用いた以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
実施例1において、正孔注入輸送層に光触媒処理を施さなかった以外は、実施例1と同様に素子を作製し、濡れ性の評価を行った。
[参考例2]
実施例2において、正孔注入輸送層に光触媒処理を施さなかった以外は、実施例2と同様に素子を作製し、濡れ性の評価を行った。
[参考例3]
実施例3において、正孔注入輸送層に光触媒処理を施さなかった以外は、実施例3と同様に素子を作製し、濡れ性の評価を行った。
[参考例4]
実施例4において、正孔注入輸送層に光触媒処理を施さなかった以外は、実施例4と同様に素子を作製し、濡れ性の評価を行った。
[参考例5]
実施例5において、正孔注入輸送層に光触媒処理を施さなかった以外は、実施例5と同様に素子を作製し、濡れ性の評価を行った。
実施例1と参考例1を比較すると、実施例1は光触媒処理後に接触角は49°から5°以下に低下し、イオン化ポテンシャルは5.2eVから5.4eVに上昇している。さらに素子特性では光触媒処理後に寿命が2.0時間から3.0時間に向上している。実施例1では、光触媒処理によってフルオロアルキル成分が分解されたことと、有機-遷移金属酸化物複合体層の表面が酸化されたことにより表面が改質されて、特性が改善したものと推測される。この結果は、実施例2と参考例2の比較、および実施例3と参考例3の比較、および実施例4と参考例4の比較、および実施例5と参考例5の比較においても同様に光触媒処理をしても特性が同等で劣化していない、あるいは光触媒処理で改善されたと示される結果が得られている。
実施例5と実施例1を比較すると、実施例1のインク1を用いた方が初期の接触角が高く、インク5よりもインク1の作り方でインクを作製することが好ましい。
また、実施例同士を比較すると、インク9~11を用いた実施例10~12が、輝度、電流効率及び寿命のいずれも優れていた。これは、エーテル結合を持つフッ素成分が分解しやすく、正孔注入輸送層表面の残留有機成分が少なくなることにより、薄膜界面の密着性が向上し、素子特性が向上したのではないかと推定される。
実施例6と比較例1を比較すると、真空紫外光照射により接触角は49°から10°に低下し、イオン化ポテンシャルは5.2eVから5.4eVに上昇している。さらに素子特性では真空紫外光照射後に寿命が2.0時間から2.6時間に向上している。真空紫外光照射によりフルオロアルキル成分が分解されたことと、有機-遷移金属酸化物複合体層の表面が真空紫外光で発生したオゾンにより酸化されたことにより表面が改質されて、特性が改善したものと推測される。
実施例1がMoO3を用いた比較例4よりも長寿命である理由は、後述するように、酸化数+5の成分が安定な状態で適度に含有されていることが要因であると示唆される。
実施例1と比較例1を比較すると、実施例1では駆動電圧が1V減少している。この結果は、実施例1ではフルオロアルキル基の付いた有機物が混合されていることによりイオン化ポテンシャルが変化し、正孔注入性が向上したために素子性能が高くなったものと推測される。
比較例2と比較例3とを比較すると、正孔注入輸送層に一般的な有機系正孔注入材料であるPEDOT/PSSを用いた場合には光照射および、光触媒処理により高電圧化し寿命が短くなっていることがわかる。この結果は光照射および光触媒処理によって、PEDOT/PSSが酸化あるいは分解されて、正孔注入性や駆動耐性が劣化したものと考えられる。
上記実施例1と比較例4で形成された正孔注入輸送層を用いて、遷移金属の酸化数を測定した。当該遷移金属の酸化数は、上記した正孔注入輸送層の表面分析における、X線光電子分光法(XPS)により、測定を行った。
上記実施例1において、光触媒処理部と光触媒未処理部のXPS測定を実施し、Mo酸化数を見積もった。下表においては、Moの酸化数+6と酸化数+5のピークに対して、ピーク分離を行い、酸化数+6を100と規格化した場合の酸化数+5のピーク強度を示した。
実施例1のモリブデンのスペクトルにおいては、光触媒処理部および光触媒未処理部の両方から酸化数+5の成分が検出された。光触媒処理された膜では若干5価の割合が減っているが、強力な酸化処理にも関わらず、少ししか3価に変質していなかったのは、本願の有機-遷移金属酸化物複合体が非常に安定であることを示している。実施例1がMoO3を用いた比較例4よりも長寿命である理由は、酸化数+5の成分が安定な状態で適度に含有されていることが要因であると示唆される。また酸化数+5の割合が多い参考例1よりも若干少ない実施例1の方の特性が高い要因として、実施例1では正孔注入輸送層の表面が酸化されて、イオン化ポテンシャルが、ITO界面近くで5.2eV、正孔輸送層界面で5.4eVと階段状になっている可能性が高く、それによって正孔注入性が良くなったり安定化されたりしているのではないかと推察される。
[実施例13]
図11に示すように、ITO透明電極(陽極)42が形成されたガラス基板41の上に、正孔注入輸送層43として合成例で作製したフッ素含有有機化合物が表面に付着した有機-遷移金属酸化物複合体薄膜をスピンコート法で10nm形成し、基体上に遮光部と光触媒含有層とが形成された光触媒含有層基板(光触媒含有層付きフォトマスク50)を用いてパターン露光し、露光部と非露光部の濡れ性を接触角測定により調べた。
次に、上記基板の上に正孔注入輸送層として、有機-遷移金属酸化物複合体薄膜を正孔注入輸送層形成用インク1を用いてスピンコート法により塗布形成した。塗膜形成後はホットプレート上200℃で乾燥させた。乾燥後の膜厚は10nmであった。キシレンに対する正孔注入輸送層表面の接触角は49°であった。
・二酸化チタン(石原産業(株)製、ST-K01) 2重量部
・オルガノアルコキシシラン(東芝シリコーン(株)製、TSL8113) 0.4重量部
・イソプロピルアルコール 3重量部
続いて、正孔注入輸送層上の露光部と非露光部との液体の静的接触角を接触角計(協和界面科学社製)により測定した。液体にはキシレン(表面張力:28.5mN/m)を使用した。
実施例13において、露光用光源として253nmの紫外光の代わりに、真空紫外光を用いて露光した以外は、実施例13と同様に親液性領域および撥液性領域からなるパターンを形成し、濡れ性の評価を行った。この際、メタルマスク側から波長172nmの真空紫外光を、光の露光量が5J/cm2になるように、撥液性領域および親液性領域からなるパターンを形成した。
実施例13において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク3を用いて薄膜(膜厚:10nm)を形成した以外は、実施例13と同様に親液性領域および撥液性領域からなるパターンを形成し、濡れ性の評価を行った。
実施例13において、正孔注入輸送層形成用インクとして、正孔注入輸送層形成用インク1の代わりに、正孔注入輸送層形成用インク4を用いて薄膜(膜厚:10nm)を形成した以外は、実施例13と同様に親液性領域および撥液性領域からなるパターンを形成し、濡れ性の評価を行った。
実施例13において、光触媒処理をせずに、正孔注入輸送層をホットプレートで200℃1hr.加熱した以外は、実施例13と同様に薄膜を形成し、濡れ性の評価を行った。
参考例6において、正孔注入輸送層形成用インク1の代わりに正孔注入輸送層形成用インク3を用いた以外は、参考例6と同様に薄膜を形成し、濡れ性の評価を行った。
参考例6において、正孔注入輸送層形成用インク1の代わりに正孔注入輸送層形成用インク4を用いた以外は、参考例6と同様に薄膜を形成し、濡れ性の評価を行った。
参考例6において、正孔注入輸送層形成用インク1の代わりに、PEDOT/PSS(スタルク社製AI4083)と4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-ヘプタデカフルオロデシル)ベンジルアミンをスピンコート法で積層薄膜を形成した以外は、参考例6と同様に素子を形成し、濡れ性の評価を行った。PEDOT/PSS層はPEDOT/PSS溶液を蒸留水で薄めて、乾燥後の膜厚が10nmになるように溶解させて作製した。次にヘプタデカフルオロデシルベンジルアミンを、ヘプタフルオロ-n-酪酸エチルに0.4wt%溶解させた溶液を用いて、塗布形成して薄膜を乾燥させた。乾燥後の膜厚は計測不能で5nm以下であった。
[評価]
実施例13~16について、光照射前の正孔注入輸送層の表面である領域I、図11に示す、光が照射され、光触媒が作用した領域II、未露光部で光触媒が作用しなかった領域III、及び、光が照射されたが、光触媒は作用しなかった領域IVにおける液体の接触角を下記表3に示す。
参考例6~8において、本発明に係る正孔注入輸送層用デバイス材料は加熱によってそれぞれ10°程度接触角が低下していることが観察されたが、未露光部と比較してコントラストは20°以上あるため、塗り分けが可能であることがわかる。従って、正孔輸送層の乾燥や熱硬化プロセスで高温の加熱が必要な場合も撥油性が維持できることがわかる。一方、比較例5では加熱により撥液性が完全に損なわれており、加熱により塗り分けが不可能になることがわかる。
[実施例17]
絶縁層と隔壁が形成されたITO基板(図12(A)に一部拡大概略断面図及び図12(B)に上から見た一部拡大概略平面図が示されている)上に、正孔注入輸送層を形成し、正孔注入輸送層に対して光触媒つきフォトマスクで露光して濡れ性パターニングを施し、親液性部である隔壁間に正孔輸送層と発光層をインクジェット法で塗布形成し、正孔ブロック層、電子輸送層、電子注入層、陰極の基本層構成を有するように製膜して積層し、封止して緑発光の有機EL素子として作製し、その有機EL素子の発光面を観察した。発光層は緑と青の2色で塗り分けた。
次に、上記基板の上に正孔注入輸送層として、有機-遷移金属酸化物複合体薄膜をスピンコート法により塗布形成した。正孔注入輸送層形成用インクとしては、正孔注入輸送層形成用インク1を用いた。塗膜形成後はホットプレート上200℃で乾燥させた。乾燥後の膜厚は10nmであった。隔壁構造の無い平坦部で接触角を測ったところ、キシレンに対する正孔注入輸送層表面の接触角は49°であった。
(正孔輸送層形成用塗工液)
・ポリ[(9,9-ジオクチルフルオレニル-2,7-ジイル)-co-(4,4’-(N-(4-sec-ブチルフェニル))ジフェニルアミン)](TFB) 1.8重量部
・メチルアニソール 98.2重量部
次に、隔壁の間に形成された正孔輸送層の上に下記組成の緑発光層形成用塗工液を1ライン置きにインクジェット法により塗布し、続いて緑発光層形成用塗工液を塗布しなかったラインに青発光層形成用塗工液をインクジェット法により塗布して、1ライン置きに緑と青が配列した発光層を形成した。塗膜形成後、窒素中100℃で30分乾燥させた。乾燥後の膜厚が40nmになるようにインクの塗出量を調整した。
(緑発光層形成用塗工液)
・2-メチル-9、10-ビス(ナフタレン-2-イル)アントラセン(MADN) 1.8重量部
・9,10-ビス[N,N-ジ-(p-トリル)-アミノ]アントラセン(TTPA) 0.02重量部
・安息香酸エチル 98重量部
(青発光層形成用塗工液)
・2-メチル-9、10-ビス(ナフタレン-2-イル)アントラセン(MADN) 1.8重量部
・1-tert-ブチル-ペリレン(TBP) 0.02重量部
・安息香酸エチル 98重量部
上記正孔ブロック層の上に、電子輸送層を蒸着形成した。電子輸送層は、トリス(8-キノリノラト)アルミニウム錯体(Alq3)を抵抗加熱法により真空中(圧力:1×10-4Pa)でAlq3蒸着膜の膜厚が20nmになるように蒸着形成した。
作製した透明陽極付きガラス基板/正孔注入輸送層/正孔輸送層/発光層/正孔ブロック層/電子輸送層の電子輸送層上に、さらに、電子注入層及び陰極を順次蒸着形成した。電子注入層は、LiF(厚み:0.5nm)を、陰極は、Al(厚み:100nm)を順次抵抗加熱蒸着法により真空中(圧力:1×10-4Pa)で蒸着膜を形成した。
陰極形成後、低酸素、低湿度状態の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た。
本実施例では緑と青の2色を塗り分けたが、本実施例の方法に従えば、原理的には3色、4色にも容易に拡張することができ、RGBの塗り分けパネルの作製にも容易に適用可能である。
実施例17において、露光用光源として253nmの紫外光の代わりに、真空紫外光を用いて露光し、光触媒付きのフォトマスクの代わりに光触媒なしのフォトマスクを使用した以外は、実施例17と同様にして実施例18の有機EL素子を作製した。この際、フォトマスク側から波長172nmの真空紫外光を、光の露光量が5J/cm2になるように、撥液性領域および親液性領域からなるパターンを形成した。
作製したデバイスの発光面を顕微鏡で観察したところ、青と緑が1ライン置きに発光するデバイスが作製できていることを確認された。各ピクセルのピクセル内の発光は一様で、ピクセル間の発光ばらつきは小さく、非常に精度高く塗り分けできていることが確認された。
本実施例では緑と青の2色を塗り分けたが、本実施例の方法に従えば、原理的には3色、4色にも容易に拡張することができ、RGBの塗り分けパネルの作製にも容易に適用可能である。
実施例17において、絶縁層と隔壁が形成されたITO基板の代わりに、絶縁層のみで隔壁が形成されていないITO基板を用いた以外は、実施例17と同様にして実施例19の有機EL素子を作製した。
発光層を塗布した後に、蛍光顕微鏡により発光層の観察を行ったところ、隔壁構造が無いにもかかわらず、インキが決壊することなく緑と青が混色することなくきれいに塗り分けできていることが確認できた。さらに、作製したデバイスの発光面を顕微鏡で観察したところ、青と緑が1ライン置きに発光するデバイスが作製できていることを確認された。各ピクセルのピクセル内の発光は一様で、ピクセル間の発光ばらつきは小さく、非常に精度高く塗り分けできていることが確認された。
本実施例では緑と青の2色を塗り分けたが、本実施例の方法に従えば、原理的には3色、4色にも容易に拡張することができ、RGBの塗り分けパネルの作製にも容易に適用可能である。
実施例17において、光触媒付きフォトマスクがクロムパターン付きではなく、クロムパターンがまったく無いフォトマスクを用い、254nmの露光を光触媒含有層付きフォトマスクの裏面側からではなく、ITO基板側から15J/cm2となるように9分間露光した以外は、実施例17と同様にして実施例20の有機EL素子を作製した。
作製したデバイスの発光面を顕微鏡で観察したところ、青と緑が1ライン置きに発光するデバイスが作製できていることを確認された。各ピクセルのピクセル内の発光は一様で、ピクセル間の発光ばらつきは小さく、非常に精度高く塗り分けできていることが確認された。
合成例1で得られた正孔注入輸送層用デバイス材料は254nmでの透過率が高く、更に、先の実施例で示したように254nmのUV照射で素子特性が劣化することは無いので、背面からの露光に有利であることを示している。
実施例17において、正孔注入輸送層形成用インク1を用いる代わりに、PEDOT/PSS(スタルク社製AI4083)と4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-ヘプタデカフルオロデシル)ベンジルアミンを用いて、スピンコート法で積層薄膜を形成した以外は、実施例17と同様に比較例6の有機EL素子を作製した。PEDOT/PSS層はPEDOT/PSS溶液を蒸留水で薄めて、乾燥後の膜厚が10nmになるように溶解させて作製した。次にヘプタデカフルオロデシルベンジルアミンを、ヘプタフルオロ-n-酪酸エチルに0.4wt%溶解させた溶液を用いて、塗布形成して薄膜を乾燥させた。乾燥後の膜厚は計測不能で5nm以下であった。
作製したデバイスの発光面を顕微鏡で観察したところ、青と緑のインキの混色がひどく、ピクセル間の発光ばらつきはひどく悪く、撥油性層がまったく機能していないことが確認された。
2 基板
3 第一電極層
4 正孔注入輸送層
5 正孔注入輸送層のフッ素分解部
6a 仕切部(隔壁)
6b 仕切部(絶縁層)
11 親液性領域
12 撥液性領域
21 光触媒含有層基板
22 基体
23 遮光部
24 光触媒含有層
27 エネルギー線
28 レーザー
29 真空紫外光
30 メタルマスク
31 有機EL素子
32 発光層
33 電子注入輸送層
34 第二電極層
41 ガラス基板
42 ITO透明電極(陽極)
43 正孔注入輸送層
50 光触媒含有層付きフォトマスク
51 合成石英基板
52 透過領域
53 遮光領域
54 クロムマスク
55 光触媒含有層
56 光触媒含有層を形成しない透過領域
60 絶縁層と隔壁が形成されたITO基板
61 ガラス基板
62 ITO透明電極(陽極)
63 仕切部(絶縁層)
64 仕切部(隔壁)
Claims (20)
- 有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体に、フッ素含有有機化合物が付着していることを特徴とする、正孔注入輸送層用デバイス材料。
- 前記有機-遷移金属酸化物複合体に含まれる、遷移金属酸化物中の遷移金属として、モリブデン、タングステン、及びバナジウムよりなる群から選択される少なくとも1種の金属を含むことを特徴とする、請求項1に記載の正孔注入輸送層用デバイス材料。
- 前記有機-遷移金属酸化物複合体は、前記有機遷移金属錯体と、有機溶媒との反応生成物であることを特徴とする、請求項1又は2に記載の正孔注入輸送層用デバイス材料。
- 前記有機-遷移金属酸化物複合体は、遷移金属は同じで酸化数の異なる遷移金属酸化物が2種以上含まれることを特徴とする、請求項1乃至3のいずれかに記載の正孔注入輸送層用デバイス材料。
- 前記フッ素含有有機化合物が、フッ素化アルキル基を含有することを特徴とする、請求項1乃至4のいずれかに記載の正孔注入輸送層用デバイス材料。
- 前記請求項1乃至5のいずれかに記載の正孔注入輸送層用デバイス材料と、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。
- 有機遷移金属錯体と、遷移金属及び/又は遷移金属酸化物と連結する作用を生ずる連結基を含むフッ素含有有機化合物とを、カルボニル基及び/又は水酸基を有する有機溶媒に溶解乃至分散させ、前記有機遷移金属錯体中の遷移金属を酸化して製造されたことを特徴とする、請求項6に記載の正孔注入輸送層形成用インク。
- 有機遷移金属錯体の反応生成物である有機-遷移金属酸化物複合体と、遷移金属及び/又は遷移金属酸化物と連結する作用を生ずる連結基を含むフッ素含有有機化合物と、有機溶媒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。
- 有機遷移金属錯体と、遷移金属及び/又は遷移金属酸化物と連結する作用を生ずる連結基を含むフッ素含有有機化合物と、カルボニル基及び/又は水酸基を有する有機溶媒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。
- 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、
パターン状に第一電極層が形成された基板上に、前記請求項1乃至5のいずれかに記載の正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する正孔注入輸送層形成工程と、
基体上に少なくとも光触媒を含有する光触媒処理層が形成されている光触媒処理層基板を、前記正孔注入輸送層に対して、エネルギー照射に伴う光触媒の作用が及び得る間隙をおいて配置した後、パターン状にエネルギー照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成する濡れ性変化パターン形成工程とを有することを特徴とする、デバイスの製造方法。 - 前記正孔注入輸送層形成工程前に、前記パターン状に第一電極層が形成された基板上の前記第一電極層のパターン間に、仕切部を形成する仕切部形成工程を有することを特徴とする、請求項10に記載のデバイスの製造方法。
- 前記第一電極層が形成された基板が透光性基板であって、前記仕切部が濡れ性変化パターン形成工程にて照射されるエネルギー線を反射または吸収する仕切部であって、前記濡れ性変化パターン形成工程において、前記透光性基板側からエネルギー照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成することを特徴とする、請求項10又は11に記載のデバイスの製造方法。
- 前記濡れ性変化パターン形成工程において、パターン状にエネルギー照射する方法が、マスクを用いてエネルギー照射する方法であることを特徴とする、請求項10乃至12のいずれかに記載のデバイスの製造方法。
- 前記濡れ性変化パターン形成工程において、パターン状にエネルギー照射する方法が、紫外レーザーをパターン状にスキャンしてエネルギー照射する方法であることを特徴とする、請求項10乃至13のいずれかに記載のデバイスの製造方法。
- 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、
パターン状に第一電極層が形成された基板上に、前記請求項1乃至5のいずれかに記載の正孔注入輸送層用デバイス材料を含有する正孔注入輸送層を形成する正孔注入輸送層形成工程と、
パターン状に真空紫外線を照射することにより、前記正孔注入輸送層表面に濡れ性の変化した濡れ性変化パターンを形成する濡れ性変化パターン形成工程とを有することを特徴とする、デバイスの製造方法。 - 前記正孔注入輸送層形成工程において、前記請求項6乃至9のいずれかに記載の正孔注入輸送層形成用インクを塗布する工程を含むことを特徴とする、請求項10乃至15のいずれかに記載のデバイスの製造方法。
- 前記正孔注入輸送層形成工程において、酸素存在下で加熱又は光照射する工程を含むことを特徴とする、請求項16に記載のデバイスの製造方法。
- 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、前記請求項1乃至5のいずれかに記載の正孔注入輸送層用デバイス材料を含有し、前記正孔注入輸送層の表層部の前記正孔注入輸送層用デバイス材料のフッ素含有有機化合物が分解除去されていることを特徴とする、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であって、
パターン状に第一電極層が形成された基板上の前記第一電極層のパターン間に、仕切部を有し、前記仕切部の開口部内の前記第一電極層上及び前記仕切部上に連続した正孔注入輸送層を有し、
前記仕切部の開口部内の前記第一電極層上及び前記仕切部の側部上の正孔注入輸送層においては、前記請求項1乃至5のいずれかに記載の正孔注入輸送層用デバイス材料の少なくとも一部のフッ素含有有機化合物が分解除去されており、且つ、前記仕切部の頂部上の正孔注入輸送層は前記請求項1乃至5のいずれかに記載の正孔注入輸送層用デバイス材料を含有していることを特徴とする、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、請求項18又は19に記載のデバイス。
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CN201080029866.5A CN102473849B (zh) | 2009-07-31 | 2010-07-29 | 空穴注入传输层用器件材料、空穴注入传输层形成用油墨、具有空穴注入传输层的器件及其制造方法 |
US13/387,244 US9105859B2 (en) | 2009-07-31 | 2010-07-29 | Device material for hole injection transport layer, ink for forming hole injection transport layer, device comprising hole injection transport layer, and method for producing the device |
KR1020157020047A KR20150092346A (ko) | 2009-07-31 | 2010-07-29 | 정공 주입 수송층용 디바이스 재료, 정공 주입 수송층 형성용 잉크 및 정공 주입 수송층을 갖는 디바이스 |
KR1020127002574A KR101570899B1 (ko) | 2009-07-31 | 2010-07-29 | 정공 주입 수송층을 갖는 디바이스의 제조 방법 |
EP10804507A EP2461389A1 (en) | 2009-07-31 | 2010-07-29 | Device material for hole injection/transport layer, ink for forming hole injection/transport layer, device having hole injection/transport layer, and method for manufacturing same |
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KR (2) | KR20150092346A (ja) |
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JP2011049547A (ja) | 2011-03-10 |
KR20120061812A (ko) | 2012-06-13 |
US20120119201A1 (en) | 2012-05-17 |
CN102473849A (zh) | 2012-05-23 |
KR20150092346A (ko) | 2015-08-12 |
KR101570899B1 (ko) | 2015-11-20 |
EP2461389A1 (en) | 2012-06-06 |
JP5560996B2 (ja) | 2014-07-30 |
CN102473849B (zh) | 2014-11-05 |
US9105859B2 (en) | 2015-08-11 |
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