WO2012176335A1 - 有機発光素子および有機発光素子の製造方法 - Google Patents
有機発光素子および有機発光素子の製造方法 Download PDFInfo
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- WO2012176335A1 WO2012176335A1 PCT/JP2011/064568 JP2011064568W WO2012176335A1 WO 2012176335 A1 WO2012176335 A1 WO 2012176335A1 JP 2011064568 W JP2011064568 W JP 2011064568W WO 2012176335 A1 WO2012176335 A1 WO 2012176335A1
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- dielectric layer
- light emitting
- layer
- organic light
- electrode layer
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- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 238000004402 ultra-violet photoelectron spectroscopy Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
- H10K59/80515—Anodes characterised by their shape
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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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
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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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/813—Anodes characterised by their shape
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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
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/875—Arrangements for extracting light from the devices
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- 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
Definitions
- the present invention relates to, for example, an organic light emitting element used for a display device or a lighting device.
- organic light-emitting elements that are expected to be applied to display devices, lighting devices, etc. are provided with a pair of electrodes consisting of an anode and a cathode on a light-emitting layer in which a light-emitting material is formed in layers, and a voltage is applied. Holes and electrons are injected from the anode and the cathode, respectively, and light is emitted using energy generated by recombination of the injected electrons and holes in the light emitting layer.
- Patent Document 1 includes a dielectric layer inserted between a hole injection electrode layer and an electron injection electrode layer, and passes through at least one of the dielectric layer and the electrode layer.
- a cavity light emitting device has been proposed in which a light emitting coating material is applied to the inner surface of a cavity that extends and includes a hole injection electrode region, an electron injection electrode region, and a dielectric region.
- Patent Document 2 discloses an organic light emitting device in which a low refractive index region made of a material having a refractive index lower than that of the substrate is provided in the light emitting region.
- Patent Document 3 discloses a hole injection electrode layer, an electron injection electrode layer, a dielectric layer inserted between the hole injection electrode layer and the electron injection electrode layer, and at least one of the dielectric layer and the electrode layer.
- An electroluminescent device is disclosed that is in electrical contact with the electrode region and the electron injection electrode region.
- Patent Document 4 discloses an organic LED element in which an anode, which is a transparent electrode, an organic layer, and a cathode are laminated in this order on a transparent substrate on which a dielectric film is formed.
- Patent Document 5 discloses an organic electroluminescence element having a diffraction grating on a surface layer of a substrate and having an organic EL layer including a light emitting layer between an anode and a cathode provided thereon via an intermediate layer. It is disclosed.
- Patent Document 6 discloses an optical component in which a microlens array, a base material, a structure layer, a planarization layer, and a first gas barrier layer are sequentially laminated, and the first gas barrier layer is less than 50 dyn / cm (JIS An optical component that is a transparent inorganic oxide layer having a wetting index of K 6768) is disclosed.
- Patent Document 7 includes a substrate and a circuit portion formed on the substrate, and a pixel region corresponding to each driving TFT is formed on the circuit portion.
- the anode buffer layer included in the organic EL element is formed by irradiating a polysiloxane derivative film obtained by plasma polymerization of a precursor (monomer) with ultraviolet rays.
- An active matrix display device is disclosed which is formed by changing the derivative to SiO 2 .
- etching may be performed to pattern the substrate side electrode and the dielectric layer. At this time, since the etching conditions of the dielectric layer and the electrode are generally different, the process tends to be complicated. In general, etching of an electrode layer is more severe than etching of a dielectric layer, so that a resist used as a mask needs to be thick.
- an electrode layer made of indium tin oxide (hereinafter also referred to as “ITO”) is positioned below the low refractive index region. Since the light transmittance of ITO is smaller than the light transmittance in the low refractive index region, the light that has entered the electrode layer from the low refractive index region is greatly attenuated.
- An object of the present invention is to provide an organic light emitting device and the like having high light emission efficiency by suppressing the light emitted from the light emitting portion from being confined inside the light emitting device.
- the present inventors have provided an organic light emitting device in which a dielectric layer is sandwiched between a pair of electrodes, and a light emitting portion is provided in a through portion formed through the electrode and the dielectric layer. It has been found that by forming a dielectric layer in the penetrating portion, more light can be extracted from the inside of the light emitting layer and the inside of the electrode layer, and the present invention has been completed. That is, the present invention is summarized below.
- the organic light-emitting device of the present invention is formed on the first electrode layer formed on the substrate, the first dielectric layer formed on the first electrode layer, and the first dielectric layer.
- a light emitting portion formed in contact with the side surface of the first electrode layer, the upper surface of the second dielectric layer, and the second electrode layer in the penetrating portion.
- the thickness of the second dielectric layer with respect to the upper surface of the substrate is smaller than the thickness of the first electrode layer.
- the penetrating portion preferably has a circular shape or a polygonal shape having a maximum width of 10 ⁇ m or less on the upper surface of the first dielectric layer, or is formed in a plurality of parallel strips having a width of 10 ⁇ m or less.
- the penetrating portion has a circular shape or a polygonal shape, it is preferable that 10 3 to 10 8 penetrating portions are formed in an arbitrary 1 mm square surface on the first dielectric layer. In the case where the penetrating portions are band-shaped, the interval between the penetrating portions is preferably 10 ⁇ m or less.
- the second dielectric layer is preferably formed of a material that is transparent to visible light of 400 nm to 750 nm. Furthermore, it is preferable that the refractive index of the first dielectric layer and the second dielectric layer are both smaller than the refractive index of the first electrode layer, and the refractive index of the first dielectric layer is The refractive index is preferably smaller than the refractive index. And it is preferable that the thickness of the first dielectric layer is smaller than the thickness of the second dielectric layer. Further, the penetrating portion may be composed of a penetrating upper portion formed penetrating at least the first electrode layer and the first dielectric layer and a perforated portion formed in the substrate.
- the manufacturing method of the organic light emitting element of the present invention includes a first step of forming a first electrode layer on a substrate, a second step of forming a plurality of through holes penetrating the first electrode layer, Forming a first dielectric layer on the electrode layer and forming a second dielectric layer in contact with the upper surface of the substrate exposed in the through hole and the side surface of the first electrode layer, thereby forming the through hole
- a thinning step for reducing the thickness of the first dielectric layer between the third step and the fourth step, and the first step between the third step and the fourth step. It is preferable to further include a step of exposing a part of the first electrode layer covered with the dielectric layer and / or the second dielectric layer. In the second step, a perforated portion can be further formed in the substrate at the bottom of the through hole.
- the method for manufacturing an organic light emitting device includes a first step of forming a first electrode layer on a substrate, a second step of forming a first dielectric layer on the first electrode layer, and at least A third step of forming a plurality of penetrating portions penetrating the first electrode layer and the first dielectric layer; and contacting the upper surface of the substrate exposed in the penetrating portion and the side surface of the first electrode layer in the penetrating portion.
- a fourth step of forming a second dielectric layer a fifth step of forming a light emitting portion in contact with the side surface of the first electrode layer exposed in the through portion and the upper surface of the second dielectric layer, And a sixth step of forming a second electrode layer in contact with the light-emitting portion and covering the dielectric layer and the light-emitting portion.
- the method may further include a step of exposing a part of the first electrode layer covered with the first dielectric layer and / or the second dielectric layer between the fourth step and the fifth step.
- a perforated part can be further formed in the substrate at the bottom of the penetrating part.
- an organic light emitting device having high light extraction efficiency and high light emission efficiency can be provided.
- (A)-(c) is the fragmentary sectional view which illustrated and illustrated the other form of the light emission part in the organic light emitting element to which this Embodiment is applied. It is the fragmentary sectional view explaining the 5th example of the organic light emitting element to which this Embodiment is applied. It is the fragmentary sectional view explaining the 6th example of the organic light emitting element to which this Embodiment is applied.
- FIG. 1 is a partial cross-sectional view illustrating a first example of an organic light emitting device to which the present embodiment is applied.
- the organic light emitting device 10 shown in FIG. 1 includes a substrate 11 and an anode layer 12 as a first electrode layer that is formed on the substrate 11 and injects holes when the substrate 11 side is the lower side.
- a structure is adopted in which a cathode layer 14 as a second electrode layer for injecting electrons and a first dielectric layer 13 formed between the anode layer 12 and the cathode layer 14 are laminated.
- a through-hole 16 formed through the anode layer 12 and the first dielectric layer 13 is provided, and the upper surface of the substrate 11 in the through-hole 16 is formed on the upper surface of the substrate 11 and the side surface of the anode layer 12.
- a second dielectric layer 19 is formed in contact therewith.
- the penetrating portion 16 includes a light emitting portion 17 formed on the second dielectric layer 19 so as to be in contact with the anode layer 12 and made of a light emitting material that emits light when a voltage is applied.
- the light emitting material forming the light emitting portion 17 is also developed from the penetrating portion 16 to the upper surface of the first dielectric layer 13 to form the extended portion 17a.
- the light emitting material forming the light emitting portion 17 is continuously extended from the through portion 16 between the first dielectric layer 13 and the cathode layer 14. Further, the cathode layer 14 is formed so as to be further laminated on the light emitting material, and is formed as a continuous film similarly to the light emitting portion 17.
- the substrate 11 serves as a support for forming the anode layer 12, the first dielectric layer 13, the cathode layer 14, the light emitting part 17, and the second dielectric layer 19.
- a material that satisfies the mechanical strength required for the organic light emitting device 10 is used for the substrate 11.
- the substrate 11 As a material for the substrate 11, when light is to be extracted from the substrate 11 side of the organic light emitting element 10, it is necessary to be transparent to visible light. Specifically, glass such as sapphire glass, soda glass, and quartz glass; transparent resin such as acrylic resin, methacrylic resin, polycarbonate resin, polyester resin, nylon resin, and silicone resin; transparent metal oxide such as aluminum nitride and alumina Etc. In addition, when using the resin film etc. which consist of the said transparent resin as the board
- gas permeability with respect to gas such as water and oxygen
- the material of the substrate 11 is not limited to a material that is transparent to visible light, and an opaque material can also be used.
- niobium (Nb) alone or an alloy thereof, or a material made of stainless steel, an oxide such as SiO 2 or Al 2 O 3 , or a semiconductor such as n-Si can be used.
- the thickness of the substrate 11 is preferably 0.1 mm to 10 mm, more preferably 0.25 mm to 2 mm, although it depends on the required mechanical strength.
- the anode layer 12 applies a voltage between the cathode layer 14 and injects holes from the anode layer 12 into the light emitting portion 17.
- the material used for the anode layer 12 needs to have electrical conductivity.
- the work function is large, and the work function is preferably 4.5 eV or more.
- the electrical resistance does not change significantly with respect to the alkaline aqueous solution.
- Metal oxides, metals, and alloys can be used as materials that satisfy these conditions.
- the metal oxide include ITO (indium tin oxide) and IZO (indium zinc oxide).
- the metal include copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta), niobium (Nb), and the like.
- An alloy such as stainless steel containing these metals can also be used.
- the anode layer 12 can be formed with a thickness of 2 nm to 2 ⁇ m, for example.
- the work function can be measured by, for example, ultraviolet photoelectron spectroscopy.
- the first dielectric layer 13 is for making the light emitted from the light emitting portion 17 refracted so as to easily enter the substrate 11.
- the refractive index of the first dielectric layer 13 is smaller than the refractive index of the light emitting unit 17. Therefore, as shown in FIG. 2A (a diagram illustrating the path of light emitted from the light emitting unit 17), the light L1 emitted from the light emitting unit 17 is more incident when entering the first dielectric layer 13. The light is refracted at an angle close to the normal direction of the substrate 11. That is, in FIG. 2-1, ⁇ 1 > ⁇ 2 .
- the light L1 reaching the anode layer 12 and the substrate 11 is reflected at the interface between the first dielectric layer 13 and the anode layer 12 and the anode layer 12. Total reflection is less likely to occur at the interface between the substrate 11 and the substrate 11. Therefore, it becomes easier to enter the anode layer 12 and the substrate 11.
- the refractive index of the first dielectric layer 13 is smaller than the refractive index of the anode layer 12, the light L 1 is also close to the normal direction of the substrate 11 at the interface between the first dielectric layer 13 and the anode layer 12. The light is refracted at an angle and is more likely to enter the substrate 11. That is, by providing the first dielectric layer 13, more light emitted from the light emitting unit 17 can be extracted from the substrate 11 side, and the light extraction efficiency is improved.
- the first dielectric layer 13 separates the anode layer 12 and the cathode layer 14 at a predetermined interval in order to cause the light emitting portion 17 to emit light by applying a voltage to the light emitting portion 17 by the anode layer 12 and the cathode layer 14. And has an insulating function. Therefore, the first dielectric layer 13 needs to be a high resistivity material, and the electrical resistivity is required to be 10 8 ⁇ cm or more, preferably 10 12 ⁇ cm or more.
- Specific materials include metal nitrides such as silicon nitride, boron nitride, and aluminum nitride; metal oxides such as silicon oxide (silicon dioxide) and aluminum oxide, sodium fluoride, lithium fluoride, magnesium fluoride, and fluoride.
- Metal fluorides such as calcium and barium fluoride can be mentioned, but other polymer compounds such as polyimide, polyvinylidene fluoride, and parylene, and coating type silicone such as poly (phenylsilsesquioxane) can also be used. It is.
- the thickness of the first dielectric layer 13 is preferably as thick as possible in order to reproducibly manufacture the organic light emitting device 10 that is less likely to cause a short circuit and current leakage.
- the thickness of the first dielectric layer 13 As the thickness of the first dielectric layer 13 is increased, it becomes easier to eliminate or suppress the influence of defects in the first dielectric layer 13 that cause a short circuit and current leakage.
- the cause of the occurrence of such a short circuit / current leakage is a protrusion on the surface of the anode layer 12 forming the first dielectric layer 13 or the first dielectric layer generated in the manufacturing process of the first dielectric layer 13. 13 pinholes.
- the thickness of the first dielectric layer 13 does not exceed 1 ⁇ m in order to suppress the total thickness of the organic light emitting element 10. Further, the narrower the distance between the anode layer 12 and the cathode layer 14, the lower the voltage required for light emission.
- the first dielectric layer 13 is preferably thinner. However, if it is too thin, the dielectric strength may not be sufficient with respect to the voltage for driving the organic light emitting element 10.
- the dielectric strength is obtained when a voltage 2V higher than the voltage at the time of driving the organic light emitting element 10 is applied.
- the current density of the current flowing through the dielectric layer is preferably at 0.1 mA / cm 2 or less, and more preferably 0.01 mA / cm 2 or less.
- the upper limit of the thickness of the first dielectric layer 13 that satisfies this is preferably 750 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. Further, the lower limit is preferably 15 nm or more, more preferably 30 nm or more, and further preferably 50 nm or more.
- the cathode layer 14 applies a voltage between the anode layer 12 and injects electrons into the light emitting portion 17.
- the cathode layer 14 is formed as a continuous film in the form of being laminated on the light emitting part 17 containing the light emitting material in the through part 16 and the light emitting material developed on the first dielectric layer 13. ing.
- the material used for the cathode layer 14 is not particularly limited as long as it has electrical conductivity like the anode layer 12, but a material having a small work function and being chemically stable is preferable. . Specifically, materials such as Al, MgAg alloy, Al and alkali metal alloys such as AlLi and AlCa can be exemplified.
- the thickness of the cathode layer 14 is preferably 10 nm to 1 ⁇ m, more preferably 50 nm to 500 nm. In the case of the organic light emitting device 10 of the present embodiment, the light emitted from the light emitting unit 17 is taken out from the substrate 11 side. Therefore, the cathode layer 14 may be made of an opaque material.
- the cathode layer 14 is a continuous film and covers the light emitting portion 17 as in the present embodiment, when it is desired to extract light not only from the substrate 11 side but also from the cathode layer 14 side, the cathode layer 14 is It is necessary to form the transparent material such as ITO.
- a cathode buffer layer may be provided adjacent to the cathode layer 14 for the purpose of increasing the electron injection efficiency by lowering the electron injection barrier from the cathode layer 14 to the light emitting portion 17.
- the work function of the material used for the cathode buffer layer is preferably lower than the material of the cathode layer 14, and a metal material or the like is suitably used.
- alkali metals Na, K, Rb, Cs
- alkaline earth metals Sr, Ba, Ca, Mg
- rare earth metals Pr, Sm, Eu, Yb
- fluorides or chlorides of these metals A simple substance selected from oxides or a mixture of two or more can be used.
- the thickness of the cathode buffer layer is preferably from 0.05 nm to 50 nm, more preferably from 0.1 nm to 20 nm, and even more preferably from 0.5 nm to 10 nm.
- the penetrating portion 16 is for forming the light emitting portion 17 therein and extracting light from the light emitting portion 17, and in the present embodiment, the anode layer 12 that is the first electrode layer and the first layer It is formed so as to penetrate through the dielectric layer 13.
- the light emitted from the light emitting portion 17 by providing the through portion 16 in this manner propagates through the through portion 16 and can be extracted in both directions on the substrate 11 side and the cathode layer 14 side.
- the penetrating portion 16 is formed so as to penetrate the anode layer 12 and the first dielectric layer 13, the anode layer 12 that is the first electrode layer and the cathode layer 14 that is the second electrode layer. Even when is formed of an opaque material, light can be extracted from the substrate 11 side.
- the shape of the penetrating portion 16 is not particularly limited, but is preferably a cylindrical column shape or a polygonal column shape such as a quadrangular column from the viewpoint of easy shape control. That is, in this case, the shape of the penetrating portion 16 is a circular shape or a polygonal shape on the upper surface of the first dielectric layer 13. In these shapes, the shape in the upper surface of the first dielectric layer 13 may change in the thickness direction of the first dielectric layer 13 and the anode layer 12, or the size of the shape may change. Good. That is, for example, the shape may be a cone shape, a pyramid shape, a truncated cone shape, a truncated pyramid shape, or the like.
- the penetrating portion 16 By appropriately selecting the shape of the penetrating portion 16, it is possible to control the light distribution and the like when taking out the light emitted from the light emitting portion 17 to the outside.
- the organic light emitting device 10 when the penetrating portion 16 shines strongly, if the interval between the penetrating portions 16 is reduced, the number of the penetrating portions 16 per unit area increases accordingly, and thus the emission intensity is increased. be able to.
- the light emitting unit 17 easily emits light in the vicinity of the anode layer 12 and the cathode layer 14.
- the central portion of the penetrating portion 16 tends to be a non-light emitting portion, and if the area of the non-light emitting portion is large, it is difficult for the organic light emitting element 10 to emit light with high luminance. Therefore, if the width of the penetrating portion 16 is reduced, the non-light emitting portion at the central portion of the penetrating portion 16 is reduced, so that the emission intensity can be easily increased. More specifically, the width (W) of the penetrating portion 16 is preferably 10 ⁇ m or less, more preferably 2 ⁇ m or less, and even more preferably 1 ⁇ m or less. Moreover, from a viewpoint that manufacture is easy, 0.1 micrometer or more is preferable and 0.5 micrometer or more is more preferable.
- the “width of the through portion 16” refers to the maximum width of the shape of the through portion 16 on the surface of the first dielectric layer 13, that is, the diameter of the minimum circle including the shape.
- the arrangement of the through portions 16 on the upper surface of the first dielectric layer 13 may be a regular arrangement such as a tetragonal lattice shape or a hexagonal lattice shape, or may be an irregular arrangement. It is preferable that 10 3 to 10 8 are formed in an arbitrary 1 mm square plane on the dielectric layer 13. About this arrangement
- the shape of the penetrating portion 16 may be a plurality of parallel strips.
- the upper limit of the width of the penetrating portion 16 is preferably 10 ⁇ m or less, more preferably 2 ⁇ m or less, still more preferably 1 ⁇ m or less, and the lower limit is preferably 0.1 ⁇ m or more for the same reason as above. More preferably, it is 0.5 ⁇ m or more.
- the interval between the plurality of strip-shaped through portions 16 is preferably 10 ⁇ m or less, more preferably 2 ⁇ m or less, and even more preferably 1 ⁇ m or less, but 0.1 ⁇ m from the viewpoint of easy manufacture. The above is preferable, and 0.5 ⁇ m or more is more preferable.
- the light emitting portion 17 is a light emitting material that emits light by applying a voltage and supplying a current, and is formed in contact with the side surface of the anode layer 12 in the through portion 16 and the cathode layer 14. In the light emitting unit 17, the holes injected from the anode layer 12 and the electrons injected from the cathode layer 14 are recombined to emit light.
- the material of the light emitting unit 17 either an organic material or an inorganic material can be used.
- an organic material any of known low molecular compounds and high molecular compounds can be used.
- a material excellent in applicability is preferable. That is, in the structure of the organic light emitting device 10 in the present embodiment, in order for the light emitting portion 17 to emit light stably in the through portion 16, the light emitting portion 17 is uniformly formed on the inner surface of the through portion 16 and the film thickness is uniform. It is preferable that the coverage is improved.
- the light emitting part 17 is formed without using a material having excellent coating properties, the light emitting part 17 is not uniformly in contact with the entire penetrating part 16 or the film thickness in the penetrating part 16 is not uniform. Cheap. For this reason, variations in the luminance of the light emitted from the penetrating portion 16 are likely to occur. Moreover, in order to form the light emission part 17 uniformly in the penetration part 16, it is preferable to carry out by the coating method. That is, in the coating method, since it is easy to embed a light emitting material solution containing a light emitting material in the penetrating portion 16, it is possible to form a film with improved coverage even on a surface having unevenness.
- materials having a weight average molecular weight of 1,000 to 2,000,000 are preferably used mainly for the purpose of improving coating properties.
- coating property improvement additives such as a leveling agent and a defoaming agent, can also be added, and binder resin with few charge trap ability can also be added.
- examples of the material having excellent coatability include, for example, an arylamine compound having a predetermined structure and a molecular weight of 1500 to 6000 as disclosed in JP-A-2007-86639, and JP-A 2000-034476.
- examples thereof include the predetermined polymeric fluorescent substances.
- a light-emitting polymer compound is preferable in terms of simplifying the manufacturing process of the organic light-emitting element 10, and a phosphorescent compound is preferable in terms of high light emission efficiency. Therefore, a phosphorescent polymer compound is particularly preferable.
- the addition amount of the low molecular light emitting material is preferably 30 wt% or less.
- the light-emitting polymer compound can be classified into a conjugated light-emitting polymer compound and a non-conjugated light-emitting polymer compound, and among them, the non-conjugated light-emitting polymer compound is preferable.
- the light-emitting material used in this embodiment is particularly preferably a phosphorescent non-conjugated polymer compound (a light-emitting material that is both a phosphorescent polymer and a non-conjugated light-emitting polymer compound).
- the light emitting portion 17 in the organic light emitting device 10 of the present invention is preferably a phosphorescent polymer (phosphorescent) having a phosphorescent unit emitting phosphorescence and a carrier transporting unit transporting carriers in one molecule.
- a light emitting organic material The phosphorescent polymer can be obtained by copolymerizing a phosphorescent compound having a polymerizable substituent and a carrier transporting compound having a polymerizable substituent.
- the phosphorescent compound is a metal complex containing a metal element selected from iridium (Ir), platinum (Pt), and gold (Au), and among them, an iridium complex is preferable.
- a carrier transporting compound having a polymerizable substituent is a compound in which one or more hydrogen atoms in an organic compound having one or both of a hole transporting property and an electron transporting property are substituted with a polymerizable substituent. Can be mentioned.
- the polymerization method of the phosphorescent compound having a polymerizable substituent and the carrier transporting compound having a polymerizable substituent may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred.
- the molecular weight of the polymer is preferably 1,000 to 2,000,000 in terms of weight average molecular weight, and more preferably 5,000 to 1,000,000.
- the molecular weight in this Embodiment is a polystyrene conversion molecular weight measured using GPC (gel permeation chromatography) method.
- the phosphorescent polymer may be a copolymer of one phosphorescent compound and one carrier transporting compound, one phosphorescent compound and two or more carrier transporting compounds, or two.
- the above phosphorescent compound may be copolymerized with a carrier transporting compound.
- the arrangement of the monomer in the phosphorescent polymer may be any of random copolymer, block copolymer, and alternating copolymer, the number of repeating units of the phosphorescent compound structure is m, and the repeating unit of the carrier transporting compound structure
- the number is n (m, n is an integer of 1 or more)
- the ratio of the number of repeating units of the phosphorescent compound structure to the total number of repeating units, that is, the value of m / (m + n) is 0.001 to 0.00. 5 is preferable, and 0.001 to 0.2 is more preferable.
- the light emitting portion 17 of the organic light emitting device 10 in the present embodiment preferably includes the phosphorescent compound described above, but includes a hole transporting compound or an electron transporting compound for the purpose of supplementing the carrier transportability of the light emitting portion 17. It may be.
- TPD N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′diamine
- ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
- m-MTDATA 4,4 ′, 4 ′′ -tris (3-methylphenylphenylamino
- low molecular triphenylamine derivatives such as triphenylamine.
- polyvinylcarbazole a triphenylamine derivative obtained by introducing a polymerizable functional group into a polymer; a polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575; polyparaphenylene vinylene, And polydialkylfluorene.
- the electron transporting compound include low molecular weight materials such as quinolinol derivative metal complexes such as Alq3 (aluminum triskinolinolate), oxadiazole derivatives, triazole derivatives, imidazole derivatives, triazine derivatives, and triarylborane derivatives.
- a polymer obtained by introducing a polymerizable functional group into the above low molecular electron transporting compound for example, a known electron transporting compound such as poly PBD disclosed in JP-A-10-1665 is exemplified. .
- the light emitting portion 17 can be formed even when a light emitting low molecular weight compound is used as the light emitting material used for the light emitting portion 17 instead of the light emitting polymer compound described above.
- the above-described light-emitting polymer compound can be added as a light-emitting material, and a hole-transporting compound or an electron-transporting compound can also be added.
- the hole transporting compound in this case include, for example, TPD, ⁇ -NPD, m-MTDATA, phthalocyanine complex, DTDPFL, spiro-TPD, TPAC, PDA described in JP-A-2006-76901. Etc.
- electron transport compound examples include BPhen, BCP, OXD-7, TAZ and the like described in JP-A-2006-76901.
- the light emitting unit 17 may have a single-layer structure including only one light emitting layer formed of a light emitting material between the anode layer 12 and the cathode layer 14, but a layer other than the light emitting layer or a plurality of light emitting layers A laminated structure including When a layer other than the light emitting layer is included, examples of the layer formed between the light emitting layer and the anode layer 12 include a hole injection layer, a hole transport layer, and an electron block layer. Examples of the layer formed therebetween include an electron transport layer and a hole blocking layer.
- Each of these layers is formed by using the above-described known hole transporting compound or electron transporting compound, resistance heating vapor deposition method, electron beam vapor deposition method, sputtering method, spin coating method, dip coating method, ink jet method, printing method, spray coating.
- the film can be formed by a method such as a method or a dispenser method.
- the second dielectric layer 19 is provided to allow more light to enter the substrate 11 by providing the second dielectric layer 19.
- the refractive index of the second dielectric layer 19 is preferably smaller than the refractive index of the light emitting unit 17.
- the second dielectric layer 19 is made of a material transparent to visible light of 400 nm to 750 nm.
- the light transmittance in the wavelength range of light to be extracted is higher than the light transmittance of the light emitting unit 17 compared with the same optical path length.
- the light extraction efficiency is improved as compared with the case where the second dielectric layer 19 is not provided. That is, when the second dielectric layer 19 is not provided and this portion is filled with the light emitting material, the light transmittance of the light emitting material is lower than the light transmittance of the second dielectric layer 19, and thus the light emitting portion 17. The light emitted from is more likely to attenuate.
- the second dielectric layer 19 when the second dielectric layer 19 is provided, the light L2 emitted from the light emitting portion 17 and passing through the second dielectric layer 19 is not attenuated so much as shown in FIG. It reaches the substrate 11. As a result, more light emitted from the light emitting unit 17 can be extracted from the substrate 11 side, and the light extraction efficiency is improved.
- the anode layer 12 does not exist in the portion of the through portion 16 of the present embodiment. Therefore, in this portion, the light that has entered the anode layer 12 is not greatly attenuated by the small transmittance of the anode layer 12. Therefore, also from this point of view, the organic light emitting device 10 of the present embodiment is advantageous from the viewpoint of light extraction efficiency.
- the refractive index of the second dielectric layer 19 is preferably smaller than the refractive index of the anode layer 12. That is, if the refractive index of the first dielectric layer 13 and the second dielectric layer 19 are both smaller than the refractive index of the anode layer 12, the light extraction efficiency in the organic light emitting element 10 is particularly high.
- the second dielectric layer 19 is formed in such a thickness that the side surface of the anode layer 12 is exposed in the through portion 16. That is, the second dielectric layer 19 is formed such that the upper surface of the second dielectric layer 19 is preferably 1 nm or more, more preferably 10 nm or more lower than the upper surface of the anode layer 12. However, the second dielectric layer 19 is preferably formed with a thickness of 1 nm or more, more preferably 10 nm or more, based on the upper surface of the substrate 11 as much as possible within the range of the film thickness.
- the second dielectric layer 19 and the first dielectric layer 13 may be formed of different materials, or may be formed of the same material. However, when the same material is used, the second dielectric layer 19 and the first dielectric layer 13 can be formed in one manufacturing process, as will be described later with reference to FIG. Therefore, the organic light emitting device 10 can be manufactured more easily. Since the first dielectric layer 13 and the second dielectric layer 19 are both insulative, for example, the second dielectric layer 19 is formed to be thinner than the anode layer 12, It is necessary that the side surface of the light emitting unit 17 is in contact with the side surface 12 a of the anode layer 12. As a result, the anode layer 12 and the light emitting unit 17 are electrically connected, and a current can flow from the anode layer 12 to the light emitting unit 17.
- the light emitting portion 17 is formed not only on the inside of the through portion 16 but also on the upper surface of the first dielectric layer 13, but is not limited thereto. .
- FIGS. 3A to 3C are partial cross-sectional views illustrating other forms of the light emitting unit 17 in the organic light emitting device to which the present embodiment is applied. These are the second to fourth examples of the organic light emitting device to which the present embodiment is applied.
- the organic light emitting element 10a shown in FIG. 3A shows a case where the light emitting portion 17 is formed inside the through portion 16 but not formed on the upper surface of the first dielectric layer 13. Yes.
- the organic light emitting device 10b shown in FIG. 3B the light emitting portion 17 is not formed on the upper surface of the first dielectric layer 13, and the penetrating portion 16 is entirely formed. Yes.
- the cathode layer 14 can be formed in a planar shape.
- the penetrating portion 16 also penetrates the cathode layer 14, and the light emitting portion 17 extends along the inside of the penetrating portion 16 on the second dielectric layer 19.
- the light-emitting part 17 fills only a part of the penetrating part 16. Since the through portion 16 is also formed on the cathode layer 14, even when the cathode layer 14 is formed of an opaque material, light can be extracted not only from the substrate 11 side but also from the cathode layer 14 side. Become. Also in such organic light emitting devices 10a, 10b, and 10c, the light extraction efficiency is improved by providing the first dielectric layer 13 and the second dielectric layer 19.
- FIG. 4 is a partial cross-sectional view illustrating a fifth example of the organic light emitting device to which the present embodiment is applied.
- the organic light emitting device 10d shown in FIG. 4 has a positional relationship among the substrate 11, the anode layer 12, the first dielectric layer 13, the cathode layer 14, the penetrating portion 16, the light emitting portion 17, and the second dielectric layer 19. This is the same as the organic light emitting device 10 shown in FIG. However, the first dielectric layer 13 is fabricated so that the thickness is smaller than the thickness of the second dielectric layer 19. By doing in this way, the level
- FIG. 5 is a partial cross-sectional view illustrating a sixth example of the organic light emitting device to which the present embodiment is applied.
- the organic light emitting device 10e shown in FIG. 5 the positional relationship among the substrate 11, the anode layer 12, the first dielectric layer 13, the cathode layer 14, the penetrating portion 16, the light emitting portion 17, and the second dielectric layer 19 is This is the same as the organic light emitting device 10 shown in FIG. However, the difference is that the cross-sectional shape of the first dielectric layer 13 is tapered at the end in contact with the penetrating portion 16.
- the organic light emitting element 10 e is different from the organic light emitting element 10 in that the light emitting portion 17 is further in contact with the upper surface 12 b of the anode layer 12. By doing so, a sufficient amount of current can be supplied from the anode layer 12 even if the volume of the light emitting unit 17 is increased. Even if the end of the first dielectric layer 13 is as in the present embodiment, the light emitted from the light emitting unit 17 is more incident on the first dielectric layer 13 when entering the first dielectric layer 13. Refracts at an angle close to the normal direction.
- FIG. 6 is a partial cross-sectional view illustrating a seventh example of the organic light emitting device to which the present embodiment is applied.
- the organic light emitting device 10f shown in FIG. 6 has a positional relationship among the substrate 11, the anode layer 12, the first dielectric layer 13, the cathode layer 14, the penetrating portion 16, the light emitting portion 17, and the second dielectric layer 19. This is the same as the organic light emitting device 10 shown in FIG.
- the penetrating portion 16 includes a penetrating upper portion 16 a formed through the anode layer 12 and the first dielectric layer 13 and a perforated portion 16 b formed in the substrate 11.
- the thickness of the second dielectric layer 19 can be increased by the depth of the perforated part 16b. That is, the thickness of the second dielectric layer 19 can be adjusted by adjusting the depth of the perforated portion 16b.
- the perforated part 16b can be formed with a depth of 1 nm to 1000 nm from the upper surface of the substrate 11.
- the present invention is not limited to this, and a structure in which the anode layer 12 and the cathode layer 14 are interchanged may be used. That is, when the substrate 11 side is the lower side, the cathode layer 14 may be formed on the lower side, and the anode layer 12 may be formed on the upper side with the first dielectric layer 13 interposed therebetween.
- FIG. 7A to 7G are diagrams illustrating a method for manufacturing the organic light emitting device 10 to which the exemplary embodiment is applied.
- the anode layer 12 as the first electrode layer is formed on the substrate 11 (FIG. 7A).
- a glass substrate is used as the substrate 11.
- ITO was used as a material for forming the anode layer 12.
- a resistance heating vapor deposition method an electron beam vapor deposition method, a sputtering method, an ion plating method, a CVD method, or the like can be used.
- a coating film forming method that is, a method in which the target material is dissolved in a solvent and applied to the substrate 11 and dried
- a spin coating method a dip coating method, an ink jet method, a printing method, a spray method is used. It is also possible to form a film using a method such as a method or a dispenser method.
- the through hole 16c is formed so as to penetrate the anode layer 12.
- a method using lithography can be used. In order to do this, first, a resist solution is applied onto the anode layer 12, and the excess resist solution is removed by spin coating or the like to form a resist layer 71 (FIG. 7B).
- the exposed portion of the anode layer 12 is removed by etching using the remaining resist layer 71 as a mask (FIG. 7D).
- etching either dry etching or wet etching can be used.
- the shape of the through hole 16c can be controlled by combining isotropic etching and anisotropic etching.
- dry etching reactive ion etching (RIE) or inductively coupled plasma etching can be used.
- RIE reactive ion etching
- wet etching a method of immersing in dilute hydrochloric acid or dilute sulfuric acid can be used. By this etching, the surface of the substrate 11 is exposed corresponding to the pattern.
- the remaining resist layer 71 is removed with a resist removing solution or the like, and the first dielectric layer 13 and the second dielectric layer 19 are formed (FIG. 7E).
- silicon dioxide (SiO 2 ) is used as a material for forming the first dielectric layer 13.
- the resistance heating vapor deposition method, the electron beam vapor deposition method, the sputtering method, the ion plating method, the CVD method, the coating method, and the like can be used as in the formation of the anode layer 12. Then, by using these methods, the first dielectric layer 13 and the second dielectric layer 19 can be formed together.
- the first dielectric layer 13 is formed on the anode layer 12 so as to form the through portion 16, and the second dielectric layer 19 is formed at the bottom of the through portion 16.
- the first dielectric layer 13 and the second dielectric layer 19 can be formed separately, the first dielectric layer 13 and the second dielectric made of the same material as in the present embodiment. By forming the layer 19 at a time, the manufacture of the organic light emitting device 10 becomes easier.
- the first dielectric layer 13 and the second dielectric layer 19 are separately formed, for example, the anode layer 12 is formed on the substrate 11 and the first dielectric layer 13 is further formed on the anode layer 12. Form.
- the through portion 16 penetrating the anode layer 12 and the first dielectric layer 13 may be formed, and then the second dielectric layer 19 may be formed in the through portion 16.
- the anode layer 12, the first dielectric layer 13, the penetrating portion 16, and the second dielectric layer 19 can be formed by the same method as described above.
- a light emitting portion 17 containing a light emitting material is formed on the first dielectric layer 13 and the second dielectric layer 19 (FIG. 7F).
- the coating method described above in the description of the light emitting portion 17 is used. Specifically, first, a light emitting material solution (coating liquid) in which a light emitting material constituting the light emitting unit 17 is dispersed in a predetermined solvent such as an organic solvent or water is applied. When applying, various methods such as spin coating, spray coating, dip coating, ink jet, slit coating, dispenser, and printing can be used.
- the luminescent material solution is dried by heating or evacuating, and the luminescent material adheres to the inner surface of the penetrating portion 16 to form the light emitting portion 17.
- the light emitting portion 17 is formed in a form developed on the first dielectric layer 13. According to this embodiment, it is not necessary to remove the coating liquid applied to the part other than the through part 16 after the application, and therefore organic light emission is performed as compared with the case where the light emitting part 17 is formed only inside the through part 16.
- the device 10 can be manufactured more easily.
- the cathode layer 14 as the second electrode layer is formed on the light emitting portion 17 (FIG. 7G).
- the cathode layer 14 can be formed by a method similar to the method for forming the anode layer 12.
- the organic light emitting device 10 can be manufactured through the above steps.
- the step of forming the through hole 16c is provided after the step of forming the anode layer 12. Therefore, compared to the case where the first dielectric layer 13 is formed after the step of forming the anode layer 12 and then the penetration layer 16 is formed by etching the anode layer 12 and the first dielectric layer 13.
- the material forming the first dielectric layer 13 can be patterned in the process of forming the through portion 16. Although it is limited, it is not limited by the manufacturing method of the present embodiment.
- the first dielectric layer 13 is limited to those whose physical properties do not change in the process of forming the through portion 16. However, the manufacturing method of the present embodiment is not limited.
- anisotropic etching may be performed after the step of forming the dielectric layer shown in FIG. Since the first dielectric layer 13 is preferentially etched over the second dielectric layer 19 by anisotropic etching, the thickness of the first dielectric layer 13 is changed to the second dielectric layer. It can be made smaller than the thickness of the layer 19. Note that this step can be regarded as a thinning step for reducing the thickness of the first dielectric layer 13 between the step of forming the dielectric layer and the step of forming the light emitting portion 17.
- isotropic etching may be performed after the step of forming the dielectric layer shown in FIG. That is, the end portion of the first dielectric layer 13 is isotropically etched, so that the end portion of the first dielectric layer 13 is removed so as to be tapered.
- This step can be regarded as an electrode layer exposure step in which a part of the anode layer 12 is exposed between the step of forming the dielectric layer and the step of forming the light emitting portion 17.
- the side surface of the anode layer 12 in the through portion 16 may be covered more than necessary with a thin layer of the material forming the second dielectric layer 19. In this case, it may be difficult to inject charges from the anode layer 12 to the light emitting unit 17.
- etching similar to the etching in the electrode layer exposure step described above is performed, and such a thin layer is removed to appropriately expose the side surface of the anode layer 12.
- a part of the substrate 11 is further removed to remove it. Good. Thereby, the perforated part 16b can be formed.
- a part of the substrate 11 can be removed by a method using etching similar to the method described in FIG.
- the organic light emitting device 10 stably for a long period of time and to attach a protective layer or a protective cover (not shown) for protecting the organic light emitting device 10 from the outside.
- a protective layer polymer compounds, metal oxides, metal fluorides, metal borides, silicon compounds such as silicon nitride and silicon oxide, and the like can be used. And these laminated bodies can also be used.
- a glass plate, a plastic plate whose surface has been subjected to low water permeability treatment, a metal, or the like can be used as the protective cover.
- the protective cover is preferably bonded to the substrate 11 with a thermosetting resin or a photocurable resin and sealed.
- a spacer because a predetermined space can be maintained and the organic light emitting element 10 can be prevented from being damaged. If an inert gas such as nitrogen, argon, or helium is sealed in this space, it becomes easy to prevent the upper cathode layer 14 from being oxidized. In particular, when helium is used, heat conduction is high, and thus heat generated from the organic light emitting element 10 when voltage is applied can be effectively transmitted to the protective cover, which is preferable. Further, by installing a desiccant such as barium oxide in this space, it becomes easy to suppress the moisture adsorbed in the series of manufacturing steps from damaging the organic light emitting element 10.
- an inert gas such as nitrogen, argon, or helium
- E-2 iridium complex having a polymerizable substituent
- E-54 hole transporting compound
- E-66 Electron transporting compound
- the reaction solution was dropped into acetone to cause precipitation, and the reprecipitation purification with dehydrated toluene-acetone was repeated three times to purify the phosphorescent polymer compound.
- dehydrated toluene and acetone those obtained by further distilling a high-purity grade manufactured by Wako Pure Chemical Industries, Ltd. were used.
- the solvent after the third reprecipitation purification was analyzed by high performance liquid chromatography, it was confirmed that no substance having absorption at 400 nm or more was detected in the solvent. That is, this means that the solvent contains almost no impurities, which means that the phosphorescent polymer compound has been sufficiently purified.
- the purified phosphorescent polymer compound was vacuum dried at room temperature for 2 days. As a result, it was confirmed by high performance liquid chromatography (detection wavelength 254 nm) that the phosphorescent polymer compound (ELP) obtained had a purity exceeding 99.9%.
- the organic light emitting device 10 shown in FIG. 1 was produced by the following method. Specifically, an ITO film having a thickness of 150 nm was first formed on a glass substrate (25 mm square, 1 mm thickness) made of quartz glass using a sputtering apparatus (E-401s manufactured by Canon Anelva Inc.). Here, the glass substrate corresponds to the substrate 11. The ITO film corresponds to the anode layer 12.
- a photoresist (AZ 1500 made by AZ Electronic Materials Co., Ltd.) was formed to a thickness of about 1 ⁇ m by spin coating. After exposure with ultraviolet rays, the resist layer was patterned by developing with a 1.2% solution of TMAH (Tetra methyl ammonium hydroxide: (CH 3 ) 4 NOH). Thereafter, heat was applied at 130 ° C. for 10 minutes (post-baking treatment).
- TMAH Tetra methyl ammonium hydroxide: (CH 3 ) 4 NOH
- the ITO film was etched by dry etching using a reactive ion etching apparatus (RIE-200iP manufactured by Samco Corporation).
- RIE-200iP reactive ion etching apparatus
- the through holes 16c have a cylindrical shape with a diameter of 1 ⁇ m arranged in a hexagonal lattice pattern in the surface of the anode layer 12, and the distance between the edges of the through holes 16c is 1 ⁇ m.
- a silicon dioxide (SiO 2 ) layer was formed to 120 nm using a sputtering apparatus (E-401s manufactured by Canon Anelva Inc.). By this step, both the first dielectric layer 13 and the second dielectric layer 19 can be formed.
- the glass substrate was washed by spraying pure water and dried using a spin dryer.
- the solution A was applied by a spin coating method (rotation number: 3000 rpm), and then allowed to stand at 120 ° C. for 1 hour in a nitrogen atmosphere and dried to form the light emitting portion 17 and the extending portion 17a.
- the thickness at which the side surface of the light emitting portion 17 contacts the side surface 12a of the anode layer 12 was 30 nm.
- the organic light emitting element 10 was able to be produced through the above steps.
- Example 2 Other than using magnesium fluoride (MgF 2 ) as a material for forming the first dielectric layer 13 and the second dielectric layer 19 in place of silicon dioxide (SiO 2 ) and forming a magnesium fluoride layer Produced the organic light emitting device 10 in the same manner as in Example 1.
- the magnesium fluoride layer can be formed by sputtering in the same manner as the silicon dioxide layer.
- the film thickness was 120 nm.
- Example 3 Except for using sodium fluoride (NaF) instead of silicon dioxide (SiO 2 ) as a material for forming the first dielectric layer 13 and the second dielectric layer 19 and forming a sodium fluoride layer.
- NaF sodium fluoride
- SiO 2 silicon dioxide
- Example 3 an organic light emitting device 10 was produced.
- the sodium fluoride layer can be formed by vacuum deposition.
- the film thickness was 120 nm.
- RIE-200iP reactive ion etching apparatus
- the thickness of the second dielectric layer 19 was 140 nm, which was almost unchanged, but the first dielectric layer 13 was reduced to 90 nm and thinned.
- the thickness at which the side surface of the light emitting unit 17 contacts the side surface 12a of the anode layer 12 is 10 nm.
- the other steps were the same as in Example 1.
- RIE-200iP reactive ion etching apparatus
- Example 6 As the organic light emitting device, the organic light emitting device 10e shown in FIG. 5 was produced by changing the following points from Example 1.
- the first dielectric layer 13 and the second dielectric layer 19 were formed by a coating method. Specifically, coating type silicone (OCD Type 2 Si-49000-SG manufactured by Tokyo Ohka Kogyo Co., Ltd.) was diluted to 50 wt% using a solvent in which ethanol and ethyl acetate were mixed in a volume of 1: 1. And it apply
- coating type silicone OCD Type 2 Si-49000-SG manufactured by Tokyo Ohka Kogyo Co., Ltd.
- a silicone layer serving as a basis for the first dielectric layer 13 and the second dielectric layer 19 was formed as a continuous layer having a thickness of 130 nm on the anode layer 12 and a thickness of 160 nm on the bottom of the through portion 16. .
- anisotropic etching was performed.
- the end of the first dielectric layer 13 in contact with the penetrating portion 16 was etched to be tapered.
- This also formed the first dielectric layer 13 and the second dielectric layer 19 separately, and the thicknesses thereof were 100 nm and 140 nm, respectively.
- the light emitting portion 17 was brought into contact with the side surface 12a of the anode layer 12 with a thickness of 10 nm.
- the other steps were the same as in Example 1.
- Example 7 As the organic light-emitting element, the organic light-emitting element 10f shown in FIG. 6 was produced by changing the following points from Example 1. After the ITO film as the anode layer 12 was etched to form the penetrating upper portion 16a, dry etching was performed using a reactive ion etching apparatus (RIE-200iP manufactured by Samco Corporation). As the reaction conditions, oxygen gas was introduced into a reactive ion etching apparatus, an AC voltage was applied and discharged to generate oxygen plasma, and the glass substrate was irradiated. Here, the flow rate of oxygen gas introduced into the plasma generation apparatus was adjusted, and the treatment was performed at a pressure of 1 Pa and an input power of 150 W for 30 seconds.
- RIE-200iP reactive ion etching apparatus
- the type of gas to be introduced was switched from oxygen to CHF 3 gas.
- the pressure was set to 7 Pa by controlling the flow rate.
- a perforated portion 16b having a depth of 100 nm could be formed.
- the silicon dioxide (SiO 2 ) layer as the first dielectric layer 13 and the second dielectric layer 19 was 200 nm. Therefore, in the case of the embodiment, the thickness at which the side surface of the light emitting unit 17 contacts the side surface 12a of the anode layer 12 is 50 nm.
- the other steps were the same as in Example 1.
- Example 8 As the organic light emitting device, the organic light emitting device 10 shown in FIG. 1 was produced. At this time, the light emitting portion 17 was formed by a vacuum vapor deposition method. That is, in Example 1, instead of applying the solution A, the method described in the literature (Organic Electronics 2 (2001) P37-43), FIG. 1 was formed as a laminated structure disclosed as DEVICE II.
- the cleaned substrate is placed in a vacuum deposition apparatus, where ⁇ NPD (manufactured by Doujin Chemical Laboratory Co., Ltd.) is 50 nm, CBP (manufactured by Dojin Chemical Laboratory Co., Ltd.) and Ir (ppy) 3 20 nm of the layer co-deposited with 95: 5 (made by Doujin Chemical Laboratory Co., Ltd.), 10 nm of BCP (made by Doujin Chemical Laboratory Co., Ltd.), and 40 nm of Alq3 (made by Doujin Chemical Laboratory Co., Ltd.)
- the light emitting part 17 was formed by vapor-depositing in order.
- an Ag: Mg (weight ratio 25: 1) film 100 nm is formed as the cathode buffer layer and the cathode layer 14.
- the other steps were the same as in Example 1.
- Example 9 As the organic light emitting device, the organic light emitting device 10 shown in FIG. 1 was produced. At this time, it was made possible to extract light from both the lower surface (anode layer 12 side) and the upper surface (cathode layer 14 side) by producing by the following method.
- Example 1 instead of forming an ITO film as the anode layer 12 on a glass substrate (25 mm square, 1 mm thickness) made of quartz glass, a 150 nm silver (Ag) layer was formed using the same sputtering apparatus. Filmed. The silver layer thus formed was opaque to visible light.
- the film thickness was set to 10 nm, and an ITO film was formed to a thickness of 100 nm by resistance heating vapor deposition.
- the cathode layer 14 made of the aluminum layer and the ITO film thus formed was transparent to visible light. The other steps were the same as in Example 1.
- An organic light emitting device having the structure of FIG. 8 was produced by the following method. Specifically, first, on a glass substrate (25 mm square, thickness 1 mm) made of quartz glass, using a sputtering apparatus (E-401s manufactured by Canon Anelva Co., Ltd.), the ITO film is 150 nm, silicon dioxide (SiO 2 ). A layer was deposited to 120 nm.
- the glass substrate corresponds to the substrate 11.
- the ITO film corresponds to the anode layer 12, and the silicon dioxide (SiO 2 ) layer corresponds to the dielectric layer 132.
- a photoresist (AZ 1500 made by AZ Electronic Materials Co., Ltd.) was formed to a thickness of about 1 ⁇ m by spin coating. After exposure with ultraviolet rays, the resist layer was patterned by developing with a 1.2% solution of TMAH (Tetra methylammonium hydroxide: (CH 3 ) 4 NOH). Thereafter, heat was applied at 130 ° C. for 10 minutes (post-baking treatment).
- TMAH Tetra methylammonium hydroxide: (CH 3 ) 4 NOH
- the silicon dioxide layer was etched by dry etching using a reactive ion etching apparatus (RIE-200iP manufactured by Samco Corporation).
- RIE-200iP reactive ion etching apparatus
- the penetrating portion 16 penetrating the silicon dioxide layer as the dielectric layer 132 was formed. Then, the resist residue was removed with a resist removing solution.
- the penetrating portion 16 has a cylindrical shape with a diameter of 1 ⁇ m arranged in a hexagonal lattice pattern in the surface of the anode layer 12, and the distance between the edges of the penetrating portion 16 is 1 ⁇ m. Note that the ITO film as the anode layer 12 remains in the form of a solid film without being etched in the form of this comparative example.
- the glass substrate was washed by spraying pure water and dried using a spin dryer.
- the solution A was applied by a spin coating method (rotation number: 3000 rpm), and then allowed to stand at 120 ° C. for 1 hour in a nitrogen atmosphere and dried to form the light emitting portion 17 and the extending portion 17a.
- Comparative Example 2 An organic light emitting device having the same structure as the organic light emitting device described in Comparative Example 1 was produced. However, the light emitting portion 17 was formed by the vacuum vapor deposition method described in Example 8. The material and laminated structure used at this time were the same as in Example 8. In addition, an Ag: Mg (weight ratio 25: 1) film 100 nm was formed as the cathode buffer layer and the cathode layer 14.
- the formed through portion 16 was a columnar shape having a diameter of 1 ⁇ m arranged in a hexagonal lattice pattern in the surface of the anode layer 12, and the distance between the edges of the through portion 16 was 1 ⁇ m.
- Comparative Example 4 An organic light emitting device having the same structure as the organic light emitting device described in Comparative Example 3 was produced. However, the following points were changed with respect to Comparative Example 3. That is, instead of forming an ITO film as the anode layer 12, a 150 nm silver (Ag) layer was formed using the same sputtering apparatus. Then, a 120 nm silicon dioxide (SiO 2 ) layer was formed as the dielectric layer 132. Thereafter, the dielectric layer 132 was etched, and the silver film was further etched.
- a voltage was applied stepwise to the organic light emitting devices fabricated in Examples 1 to 9 and Comparative Examples 1 to 4 using a constant voltage power supply ammeter (SM2400 manufactured by Keith Instruments Inc.), and the light emission intensity of the organic light emitting device was measured with a luminance meter (BM-9 manufactured by Topcon Corporation). And luminous efficiency was determined from the ratio of luminous intensity to current density. However, in Example 9, since light is emitted from the upper surface (cathode layer 14 side) in addition to the lower surface (anode layer 12 side), the same measurement is performed on the upper surface, and the luminous efficiency is measured on the upper surface and the lower surface. The sum of the values.
- the refractive index of the second dielectric layer 19 was measured in the case of light having a wavelength of 550 nm. The results are shown in Table 1 below. In addition, the result of luminous efficiency is a numerical value normalized with Comparative Example 1 as 1.0. In Comparative Examples 1 to 4, the refractive index of the light-emitting portion 17 was described in comparison with the second dielectric layer 19. The refractive index of ITO was 1.75.
- Example 1 Comparative Example 3
- the organic light emitting device manufacturing method shown in Example 1 is etched only with the ITO film as the anode layer 12 as compared with the manufacturing method of Comparative Example 3. Therefore, in Example 1, since there is no need to continuously dry-etch the second dielectric layer 19 and the anode layer 12 as in Comparative Example 3, there is an advantage that an organic light-emitting element can be stably manufactured. is there.
- Example 2 the luminous efficiency of Example 2 is better than that of Example 1
- the luminous efficiency of Example 3 is better than that of Example 1. This is considered to be due to the difference in material forming the first dielectric layer 13 and the second dielectric layer 19. That is, the magnesium fluoride (MgF 2 ) and sodium fluoride (NaF) used in Examples 2 and 3 have a lower refractive index than the silicon dioxide (SiO 2 ) used in Example 1, It is considered that the light emission efficiency is improved by using a material having a lower refractive index.
- MgF 2 magnesium fluoride
- NaF sodium fluoride
- Example 3 even when water-soluble sodium fluoride (NaF), which is difficult to perform photolithography, is used as in Example 3, the luminous efficiency is improved, and materials that can be formed by the vacuum evaporation method can also be used. It can be said that.
- NaF water-soluble sodium fluoride
- Example 4 when Examples 4 to 7 are compared with Comparative Examples 1 and 3, it can be seen that the luminous efficiency of each of the Examples is higher than that of the Comparative Example. From this, it can be seen that the luminous efficiency is improved even when the first dielectric layer 13 is thinner than the second dielectric layer 19 as in Example 4. It can also be seen that the luminous efficiency is improved even when the light emitting portion 17 is also in contact with the upper surface of the anode layer 12 as in Example 5. Further, as in Example 6, the luminous efficiency is improved even when the first dielectric layer 13 and the second dielectric layer 19 are formed by a coating method, and the first dielectric layer 13 and the second dielectric layer 19 are improved. It can be said that a coating method can also be applied to form the dielectric layer 19.
- film formation by a coating method has an advantage that it is cheaper (equipment is cheaper) than vacuum film formation by sputtering or the like.
- Example 1 and Example 7 When Example 1 and Example 7 are used, it is understood that the luminous efficiency is better when the perforated part 16b is formed, and the luminous efficiency is further improved by forming the perforated part 16b.
- Example 9 is compared with Comparative Example 1 and Comparative Example 4.
- Example 9 and Comparative Example 4 light can be extracted from both sides of the anode layer 12 side and the cathode layer 14 side. Even in the case of Example 9, the luminous efficiency is higher than that of Comparative Example 1, and it can be seen that there is an effect of providing the first dielectric layer 13 and the second dielectric layer 19. However, since the light from the cathode layer 14 side passes through the ITO film, the light emission efficiency is reduced as compared with Example 1. In Example 9, since the materials and film thicknesses of Comparative Example 1 and anode layer 12 and cathode layer 14 are different, it can be seen that the luminous efficiency is improved as compared with Comparative Example 4 produced in the same manner.
- Example 9 compared with Comparative Example 4, the level difference between the bottom surface of the penetrating portion 16 of the light emitting portion 17 and the top of the first dielectric layer 13 and the dielectric layer 132 is reduced, and thus the light emitting portion 17 and the extending portion 17a. It is possible to improve the coverage when forming. Therefore, it is possible to stably produce an organic light emitting device with few short circuits and short circuits.
- Example 8 and Comparative Example 2 the light-emitting portion 17 was formed by vacuum deposition. From the results of Example 8 and Comparative Example 2, it can be seen that an organic light emitting device having excellent luminous efficiency can be produced by providing the first dielectric layer 13 and the second dielectric layer 19. However, comparing Example 8 and Example 1, the luminous efficiency is better when the light emitting portion 17 is formed by the coating method. This is considered to be because in the vacuum vapor deposition method, the light emitting material is less likely to be filled in the through portion 16 with a uniform film thickness as compared with the coating method.
- SYMBOLS 10 Organic light emitting element, 11 ... Board
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Abstract
Description
また特許文献2には、基板の屈折率より低い屈折率を有する物質からなる低屈折率領域を発光領域内に設けた有機発光素子が開示されている。
さらに特許文献3には、正孔注入電極層、電子注入電極層、および正孔注入電極層と電子注入電極層との間に挿入される誘電体層、ならびに少なくとも誘電体層および電極層の一つを通って延び、そして正孔注入電極領域、電子注入電極領域および誘電体領域を備える内部キャビティー表面を有するキャビティー、を備え、エレクトロルミネセンスコーティング材料は、内部キャビティー表面の正孔注入電極領域および電子注入電極領域と電気的に接触している、エレクトロルミネセンスデバイスが開示されている。
さらに特許文献4には、誘電体膜が形成された透明基板の上に、透明電極である陽極と、有機層と、陰極とがこの順に積層された有機LED素子であって、誘電体層の膜厚は0.5μm以上であり、450nm~650nmの波長域において、有機層の屈折率n1、陽極の屈折率n2および誘電体膜の屈折率n3の間に、|n3-n2|≦0.25および|n1-n2|≦0.20の関係が成立するものが開示されている。
さらに特許文献5には、基板の表層に回折格子を有し、この上に中間層を介して、陽極と陰極の間に発光層を含む有機EL層が設けられている有機エレクトロルミネセンス素子が開示されている。
さらに特許文献6には、マイクロレンズアレイ、基材、ストラクチャー層、平坦化層、第一のガスバリア層が順次積層された光学用部品であって、第一のガスバリア層が50dyn/cm未満(JIS K 6768)の濡れ指数を有する透明無機酸化物層である光学用部品が開示されている。
さらに特許文献7には、基板と、この基板上に形成された回路部とを有し、この回路部上に、各駆動用TFTに対応して、画素領域が形成され、各画素領域内には、それぞれ有機EL素子が設けられ、この有機EL素子が有する陽極バッファ層は、前駆体(モノマー)をプラズマ重合して得られたポリシロキサン誘導体の被膜に、紫外線を照射することにより、ポリシロキサン誘導体をSiO2に変化させて形成されたものであるアクティブマトリクス型表示装置が開示されている。
さらにキャビティー構造を形成する手段として、基板側電極と誘電体層をパターン化するためにエッチングを行うことがある。このとき誘電体層と電極のエッチング条件が一般的に異なるため工程が煩雑になりやすい。また一般に誘電体層より電極層のエッチングの方がエッチング条件が過酷であるため、マスクとして使用するレジストを厚くする必要がある。そのため、レジスト形成およびエッチング共に要する時間が長くなりやすいという欠点があった。またその結果、期待する形状を安定して作製することが困難であった。さらにエッチング可能な材料しか誘電体層として使用できないという材料選択における制限があった。
また低屈折率領域を発光領域内に設けた有機発光素子では、酸化インジウムスズ(以下、「ITO」とも記す。)からなる電極層が、低屈折率領域の下部に位置することになる。ITOの光の透過率は低屈折率領域の光の透過率より小さいため、低屈折率領域から電極層中に侵入した光は、強度が大きく減衰する。更に、ITOは、高い屈折率を有するため、電極層中に侵入した光は、全反射により電極層内部に閉じこめられやすい。そのため光の取り出し効率が低下する。
本発明の目的は、発光部から発した光が発光素子内部に閉じ込められることを抑制し、高い発光効率を有する有機発光素子等を提供することである。
さらに第1の誘電体層および第2の誘電体層の屈折率が、いずれも第1の電極層の屈折率よりも小さいことが好ましく、第1の誘電体層の屈折率が、発光部の屈折率よりも小さいことが好ましい。そして第1の誘電体層の厚さが、第2の誘電体層の厚さよりも小さいことが好ましい。また貫通部が、少なくとも第1の電極層および第1の誘電体層を貫通して形成される貫通上部と、基板に形成される穿孔部とからなるようにすることもできる。
以下、添付図面を参照して、本発明の実施の形態について詳細に説明する。
図1は、本実施の形態が適用される有機発光素子の第1の例を説明した部分断面図である。
図1に示した有機発光素子10は、基板11と、基板11側を下側とした場合に基板11上に形成され正孔を注入するための第1の電極層としての陽極層12と、電子を注入するための第2の電極層としての陰極層14と、陽極層12と陰極層14の間に形成される第1の誘電体層13とが積層した構造を採る。また、陽極層12および第1の誘電体層13を貫通して形成される貫通部16を有し、そして貫通部16内における基板11上面には、基板11の上面および陽極層12の側面に接して第2の誘電体層19が形成されている。また、貫通部16の内部に、陽極層12に接するように第2の誘電体層19上に形成され、電圧を印加することで発光する発光材料からなる発光部17を有する。この発光部17を形成する発光材料は、貫通部16から第1の誘電体層13の上面にも展開して延伸部17aを形成する。即ち、発光部17を形成する発光材料を、貫通部16から第1の誘電体層13と陰極層14の間に更に延伸して連続形成している。また、陰極層14は、この発光材料上に更に積層する形で形成されており、発光部17と同様に連続する膜として成膜されている。
有機発光素子10の基板11側から光を取り出す必要がない場合は、基板11の材料としては、可視光に対して透明であるものに限られず、不透明なものも使用できる。具体的には、上記材料に加えて、ケイ素(Si)、銅(Cu)、銀(Ag)、金(Au)、白金(Pt)、タングステン(W)、チタン(Ti)、タンタル(Ta)、もしくはニオブ(Nb)の単体、またはこれらの合金、あるいはステンレス、SiO2やAl2O3などの酸化物、n-Siなどの半導体などからなる材料も使用することができる。
基板11の厚さは、要求される機械的強度にもよるが、好ましくは、0.1mm~10mm、より好ましくは0.25mm~2mmである。
本実施の形態では、第1の誘電体層13の屈折率は、発光部17の屈折率より小さい。そのため、図2-1(発光部17から発した光の進路について説明した図)に示すように、発光部17から発した光L1は、第1の誘電体層13に入射する際に、より基板11の法線方向に近い角度に屈折する。即ち、図2-1においてθ1>θ2となる。その結果、第1の誘電体層13を設けない場合に比較して、陽極層12や基板11に達した光L1は、第1の誘電体層13と陽極層12の界面、および陽極層12と基板11の界面において全反射を生じにくくなる。よって、より陽極層12や基板11に入射しやすくなる。さらに、第1の誘電体層13の屈折率が陽極層12の屈折率より小さいと、光L1は第1の誘電体層13と陽極層12の界面でも同様に基板11の法線方向に近い角度に屈折し、さらに基板11に入射しやすくなる。つまり、第1の誘電体層13を設けることにより、発光部17から発した光を基板11側から、より多く取り出すことができ、光の取り出し効率が向上する。
ここで、短絡・電流リークを生じにくい有機発光素子10を再現よく製造するためには、第1の誘電体層13の厚さは厚いほど好ましい。つまり、第1の誘電体層13の厚さは厚い方が、短絡・電流リークを引き起こす第1の誘電体層13の欠陥の影響を除外あるいは抑制しやすくなる。このような短絡・電流リークを生じる原因としては、第1の誘電体層13を形成する陽極層12表面の突起や、第1の誘電体層13の製造工程で発生する第1の誘電体層13のピンホールなどが挙げられる。
他方、有機発光素子10全体の厚さを抑えるために第1の誘電体層13の厚さは、1μmを越えないことが好ましい。また、陽極層12と陰極層14との間隔が狭い方が、発光のために必要な電圧が低くて済むので、この観点からも第1の誘電体層13は薄い方がより好ましい。但し、薄すぎると有機発光素子10を駆動するための電圧に対し、絶縁耐力が十分でなくなるおそれがある。ここで絶縁耐力は、電極間に第1の誘電体層13を貫通部16が形成されない連続膜として形成した場合、有機発光素子10の駆動時の電圧よりも2V高い電圧を印加した時のこの誘電体層中を流れる電流の電流密度が、0.1mA/cm2以下であることが好ましく、0.01mA/cm2以下であることがより好ましい。これを満たす第1の誘電体層13の厚さは、上限としては、750nm以下であることが好ましく、400nm以下であることが更に好ましく、200nm以下であることがまた更に好ましい。また下限としては15nm以上であることが好ましく、30nm以上であることが更に好ましく、50nm以上であることがまた更に好ましい。
本実施の形態の有機発光素子10では、貫通部16で強く光る場合においては貫通部16の間隔を小さくすれば、それだけ単位面積当たりの貫通部16の数が増加するため、発光強度を大きくすることができる。また、発光部17は、陽極層12と陰極層14の近傍において発光しやすい。即ち貫通部16の中央部は、非発光部分となりやすく、この非発光部分の面積が大きいと有機発光素子10を高輝度で発光させにくい。よって、貫通部16の幅を小さくすれば、貫通部16の中央部の非発光部分が減少することになるため、発光強度を大きくしやすくなる。より具体的には、貫通部16の幅(W)が10μm以下であることが好ましく、2μm以下であることがより好ましく、1μm以下であることが更に好ましい。また、製造が容易であるという観点では0.1μm以上が好ましく、0.5μm以上がより好ましい。なお、ここで「貫通部16の幅」とは、第1の誘電体層13面上における貫通部16の形状の最大幅、すなわち当該形状を内包する最小円の直径を指す。
第1の誘電体層13上面における貫通部16の配置は、正方格子状や六方格子状など規則的な配置であっても、不規則な配置であってもよく、貫通部16は、第1の誘電体層13上の任意の1mm四方の面内において103~108個形成されていることが好ましい。この配置については、発光部17で発光する光の波長や、有機発光素子10から出射する光の配光分布やスペクトル制御などの観点から適宜選択される。
貫通部16の形状は互いに平行な複数の帯状であってもよい。この場合も貫通部16の幅は上記と同じ理由で上限は10μm以下であることが好ましく、2μm以下であることがより好ましく、1μm以下であることが更に好ましく、下限は0.1μm以上が好ましく、0.5μm以上がより好ましい。複数の帯状である貫通部16の間隔は、10μm以下であることが好ましく、2μm以下であることがより好ましく、1μm以下であることが更に好ましいが、製造が容易であるという観点では0.1μm以上が好ましく、0.5μm以上がより好ましい。
また、貫通部16内に発光部17を均一に形成するためには、塗布法で行うことが好ましい。即ち、塗布法では、貫通部16に発光材料を含む発光材料溶液を埋め込むことが容易であるため、凹凸を有する面においてもカバレッジ性を高めて成膜することが可能である。塗布法においては塗布性を向上させる目的で、主に重量平均分子量で1,000~2,000,000である材料が好適に用いられる。また、塗布性を向上させるためレベリング剤、脱泡剤などの塗布性向上添加剤を添加したり、電荷トラップ能力の少ないバインダー樹脂を添加することもできる。
ここで、塗布性に優れた材料の中でも、有機発光素子10の製造のプロセスが簡素化されるという点で発光性高分子化合物が好ましく、発光効率が高い点で燐光発光性化合物が好ましい。従って、特に燐光発光性高分子化合物が好ましい。なお、複数の材料同士を混合、あるいは塗布性を損なわない範囲で低分子発光材料(例えば、分子量1000以下)を添加することも可能である。この際の低分子発光材料の添加量は30wt%以下が好ましい。
また、発光性高分子化合物は、共役発光性高分子化合物と非共役発光性高分子化合物とに分類することもできるが、中でも非共役発光性高分子化合物が好ましい。
上記の理由から、本実施の形態で用いられる発光材料としては、燐光発光性非共役高分子化合物(燐光発光性高分子であり、かつ非共役発光性高分子化合物でもある発光材料)が特に好ましい。
この場合の正孔輸送性化合物の具体例としては、例えば、特開2006-76901号公報に記載されているTPD、α-NPD、m-MTDATA、フタロシアニン錯体、DTDPFL、spiro-TPD、TPAC、PDA等が挙げられる。
発光部17は、陽極層12と陰極層14の間に、発光材料により形成された1層の発光層のみからなる単層構造であってもよいが、発光層以外の層や複数の発光層を含む積層構造であってもよい。発光層以外の層を含む場合、発光層と陽極層12の間に形成される層としては、正孔注入層や正孔輸送層、電子ブロック層などが挙げられ、発光層と陰極層14の間に形成される層としては電子輸送層や正孔ブロック層などが挙げられる。これらの各層は、前述した公知の正孔輸送性化合物や電子輸送性化合物を、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、スピンコーティング法、ディップコーティング法、インクジェット法、印刷法、スプレーコーティング法、ディスペンサー法などの方法により成膜して形成することができる。
なお第1の誘電体層13および第2の誘電体層19は、共に絶縁性であるため、例えば、第2の誘電体層19は、陽極層12より厚さが小さくなるように形成し、発光部17の側面が、陽極層12の側面12aにて接触するようにする必要がある。これにより陽極層12と発光部17とは、電気的に導通し、陽極層12から発光部17へ電流を流すことが可能となる。
図3(a)で示した有機発光素子10aは、発光部17が貫通部16の内部に形成されるが、第1の誘電体層13の上面には形成せずに作製した場合を示している。
また、図3(b)で示した有機発光素子10bは、発光部17を第1の誘電体層13の上面には形成せず、そして貫通部16を全て埋めるように形成した場合を示している。この構成を採ることより、陰極層14を、平面状に形成することができる。
更に、図3(c)で示した有機発光素子10cでは、貫通部16が陰極層14をも貫通し、発光部17を第2の誘電体層19上の貫通部16の内部に沿わせる形で形成した場合を示している。この形態では、発光部17が貫通部16の一部にのみ充填する形となっている。そして、貫通部16が陰極層14に対しても形成されることで、陰極層14を不透明材料により形成する場合でも、基板11側のみならず、陰極層14側からも光の取り出しが可能となる。
このような有機発光素子10a,10b,10cにおいても第1の誘電体層13、第2の誘電体層19を設けることで、光の取り出し効率が向上する。
図4に示した有機発光素子10dは、基板11、陽極層12、第1の誘電体層13、陰極層14、貫通部16、発光部17、第2の誘電体層19の位置関係は、図1に示した有機発光素子10と同様である。ただし、第1の誘電体層13は、厚さが第2の誘電体層19の厚さより小さくなるように作製されている。このようにすることで、第1の誘電体層13と第2の誘電体層19との間で生じる段差をより小さくすることができる。そのため図6で後述するように発光材料を塗布して、発光部17および延伸部17aを形成する際のカバレッジ性がより向上する。そのためより安定的に発光部17および延伸部17aを形成することができる。
図5に示した有機発光素子10eは、基板11、陽極層12、第1の誘電体層13、陰極層14、貫通部16、発光部17、第2の誘電体層19の位置関係は、図1に示した有機発光素子10と同様である。ただし、第1の誘電体層13の断面形状が貫通部16と接する端部においてテーパ状となっている点が異なる。このようにすることで、陽極層12と陰極層14の間で発光する発光部17の容積が増大するため、発光部17から出射する光の量が増大しやすくなる。
更に有機発光素子10eは、有機発光素子10に対し、発光部17は、陽極層12の上面12bにて更に接触する点で異なる。このようにすることで発光部17の容積が増大しても陽極層12から十分な量の電流を供給することができる。
なお第1の誘電体層13の端部が本実施の形態のようになっていても、発光部17から発した光は、第1の誘電体層13に入射する際に、より基板11の法線方向に近い角度に屈折する。
図6に示した有機発光素子10fは、基板11、陽極層12、第1の誘電体層13、陰極層14、貫通部16、発光部17、第2の誘電体層19の位置関係は、図1に示した有機発光素子10と同様である。ただし、貫通部16は、陽極層12および第1の誘電体層13を貫通して形成される貫通上部16aと基板11に形成される穿孔部16bとからなる。このように穿孔部16bを形成することで、穿孔部16bの深さの分、第2の誘電体層19の厚さを大きくすることができる。つまり穿孔部16bの深さを調整することで、第2の誘電体層19の厚さを調整することができる。穿孔部16bは基板11の上面から1nm~1000nmの深さで形成することができる。
次に、本実施の形態が適用される有機発光素子の製造方法について、図1で説明を行った有機発光素子10を製造する場合を例に取り説明を行う。
図7(a)~(g)は、本実施の形態が適用される有機発光素子10の製造方法について説明した図である。
まず基板11上に、第1の電極層である陽極層12を形成する(図7(a))。本実施の形態では、基板11として、ガラス基板を使用した。また陽極層12を形成する材料としてITOを使用した。
陽極層12を基板11上に形成するには、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、イオンプレーティング法、CVD法などを用いることができる。また、塗布成膜方法、即ち、目的とする材料を溶剤に溶解させた状態で基板11に塗布し乾燥する方法が可能な場合は、スピンコーティング法、ディップコーティング法、インクジェット法、印刷法、スプレー法、ディスペンサー法などの方法を用いて成膜することも可能である。
なお第1の誘電体層13と第2の誘電体層19を別々に形成する場合は、例えば、基板11上に陽極層12を形成し、さらに陽極層12上に第1の誘電体層13を形成する。そして陽極層12および第1の誘電体層13を貫通する貫通部16を形成し、その後で、貫通部16内に第2の誘電体層19を形成すればよい。この場合、陽極層12、第1の誘電体層13、貫通部16、および第2の誘電体層19は、上述した場合と同様の方法により形成することができる。
本実施の形態による有機発光素子の製造方法では、陽極層12を形成する工程の次に貫通孔16cを形成する工程を設けている。そのため、陽極層12を形成する工程の次に第1の誘電体層13を形成し、それから陽極層12および第1の誘電体層13をエッチングすることで貫通部16を形成する場合に比べ、次の利点を有する。
(1)陽極層12および第1の誘電体層13の2層をエッチングする場合は、工程の途中でレジスト層71がエッチングにより消失してしまい、所期のパターン加工が達成できない場合があるが、本実施の形態の製造方法ではこのようなことが生じにくい。
(2)陽極層12および第1の誘電体層13の2層をエッチングする場合は、第1の誘電体層13を形成する材料は、貫通部16を形成する工程でパターン化可能なものに限定されるが、本実施の形態の製造方法では限定されない。
(3)陽極層12および第1の誘電体層13の2層をエッチングする場合は、第1の誘電体層13は、貫通部16を形成する工程でその物性が変化しないものに限定されるが、本実施の形態の製造方法では限定されない。
[燐光発光性高分子化合物の作製]
下記の式E-2で表される化合物(重合性置換基を有するイリジウム錯体)、式E-54で表される化合物(正孔輸送性化合物)、および式E-66で表される化合物(電子輸送性化合物)をE-2:E-54:E-66=1:4:5(質量比)の割合で脱水トルエンに溶解させ、更に重合開始剤として、V-601(和光純薬工業株式会社製)を溶解させた。そして、凍結脱気操作を行った後に真空密閉し、70℃で100時間攪拌して重合反応を行なった。反応後、反応液をアセトン中に滴下して沈殿を生じさせ、更に、この脱水トルエン-アセトンでの再沈殿精製を3回繰り返して燐光発光性高分子化合物を精製した。ここで、脱水トルエンおよびアセトンとしては、和光純薬工業株式会社製の高純度グレードのものを更に蒸留したものを用いた。
3回目の再沈殿精製後の溶剤を高速液体クロマトグラフィーで分析したところ、溶剤中に400nm以上での吸収を有する物質が検出されないことを確認した。即ち、このことは溶剤中に、不純物がほとんど含まれないということであり、燐光発光性高分子化合物を十分に精製できていることを意味する。そして、精製された燐光発光性高分子化合物を、室温で2日間かけて真空乾燥させた。その結果得られた燐光発光性高分子化合物(ELP)は、純度が99.9%を超えることを高速液体クロマトグラフィー(検出波長254nm)により確認した。
このように作製した発光性高分子化合物(重量平均分子量=52000)3重量部を97重量部のトルエンに溶解させ、発光材料溶液(以下、「溶液A」ともいう。)を調製した。
有機発光素子として、図1で示した有機発光素子10を、以下の方法で作製した。
具体的には、まず石英ガラスからなるガラス基板(25mm角、厚さ1mm)上に、スパッタ装置(キヤノンアネルバ株式会社製E-401s)を用いて、ITO膜を150nm成膜した。ここで、ガラス基板は、基板11に対応する。またITO膜は陽極層12に対応する。
第1の誘電体層13および第2の誘電体層19を形成する材料として、二酸化ケイ素(SiO2)の代わりにフッ化マグネシウム(MgF2)を使用し、フッ化マグネシウム層を形成したこと以外は、実施例1と同様にして、有機発光素子10を作製した。なおフッ化マグネシウム層は、二酸化ケイ素層と同様にスパッタにより形成することができる。また膜厚は、120nmとした。
第1の誘電体層13および第2の誘電体層19を形成する材料として、二酸化ケイ素(SiO2)の代わりにフッ化ナトリウム(NaF)を使用し、フッ化ナトリウム層を形成したこと以外は、実施例1と同様にして、有機発光素子10を作製した。なおフッ化ナトリウム層は、真空蒸着を行なうことにより形成することができる。また膜厚は、120nmとした。
有機発光素子として、図4で示した有機発光素子10dを、実施例1に対し、以下の点を変更することにより作製した。
第1の誘電体層13および第2の誘電体層19としての二酸化ケイ素(SiO2)層を140nm形成した後に、反応性イオンエッチング装置(サムコ株式会社製RIE-200iP)を用いて、異方性エッチングを実施した。エッチング条件としては、反応ガスとしてCHF3を使用し、圧力0.2Pa、出力Bias/ICP=120/100(W)で、10分間反応させた。
これにより第2の誘電体層19の膜厚は、140nmでありほとんど変化がなかったが、第1の誘電体層13は90nmとなり薄膜化された。なお本実施の形態の場合、発光部17の側面が、陽極層12の側面12aにて接触する厚さは、10nmとなる。また他は、実施例1と同様の工程を実施した。
有機発光素子として、図5で示した有機発光素子10eを、実施例1に対し、以下の点を変更することにより作製した。
第1の誘電体層13および第2の誘電体層19としての二酸化ケイ素(SiO2)層を140nm形成した後に、反応性イオンエッチング装置(サムコ株式会社製RIE-200iP)を用いて、等方性エッチングを実施した。エッチング条件としては、反応ガスとしてCHF3を使用し、圧力0.7Pa、出力Bias/ICP=40/100(W)で、15分間反応させた。
これにより第1の誘電体層13の貫通部16と接する端部がエッチングされテーパ状となった。またこれにより発光部17は、陽極層12の上面12bと20nmの幅で接触する状態となった。なお他は、実施例1と同様の工程を実施した。
有機発光素子として、図5で示した有機発光素子10eを、実施例1に対し、以下の点を変更することにより作製した。
第1の誘電体層13および第2の誘電体層19を塗布法で形成した。
具体的には、塗布型シリコーン(東京応化工業株式会社製OCD Type2 Si-49000-SG)を、エタノールと酢酸エチルとを1:1で体積混合した溶媒を使用して50wt%に希釈した。そして、スピンコーター(回転数2000rpmで30秒間)で塗布を行なった。その後、300℃で1時間熱処理した。その結果、第1の誘電体層13および第2の誘電体層19の基となるシリコーン層が陽極層12上で130nm、貫通部16の底部で160nmの厚さで連続する層として形成された。そしてこの状態で、異方性エッチングを実施した。これにより第1の誘電体層13の貫通部16と接する端部がエッチングされテーパ状となった。またこれにより第1の誘電体層13および第2の誘電体層19が分離して形成され、それぞれの厚さは、100nmおよび140nmであった。また発光部17は、陽極層12の側面12aにて10nmの厚さで接触する状態となった。なお他は、実施例1と同様の工程を実施した。
有機発光素子として、図6で示した有機発光素子10fを、実施例1に対し、以下の点を変更することにより作製した。
陽極層12としてのITO膜をエッチングして貫通上部16aを形成した後に、反応性イオンエッチング装置(サムコ株式会社製RIE-200iP)を用いてドライエッチングを行なった。反応条件としては、反応性イオンエッチング装置内に酸素ガスを導入し、交流電圧を印加し放電させることで酸素プラズマを生成させ、ガラス基板に照射することで行なった。ここでプラズマ生成装置内に導入する酸素ガス流量を調整し、圧力は1Pa、投入電力は150Wで30秒間になるようにして処理を行なった。次いで、導入するガスの種類を酸素からCHF3ガスに切り替えた。ここで流量を制御することで圧力を7Paとした。そしてPEモードで投入電力300Wにて10秒間処理を行なった。その結果、深さ100nmの穿孔部16bを形成することができた。
また第1の誘電体層13および第2の誘電体層19としての二酸化ケイ素(SiO2)層は200nmとした。よって実施の形態の場合、発光部17の側面が、陽極層12の側面12aにて接触する厚さは、50nmとなる。なお他は、実施例1と同様の工程を実施した。
有機発光素子として、図1で示した有機発光素子10を作製した。このとき発光部17を真空蒸着法で成膜した。
つまり、実施例1で、溶液Aを塗布する代わりに、文献(Organic Electronics 2(2001)P37-43)のFig.1においてDEVICE IIとして開示されている積層構造を形成した。具体的には、洗浄を行った基板を真空蒸着装置内に設置し、ここにαNPD(株式会社同人化学研究所製)を50nm、CBP(株式会社同人化学研究所製)とIr(ppy)3(株式会社同人化学研究所製)とを95:5の比率で共蒸着した層を20nm、BCP(株式会社同人化学研究所製)を10nm、Alq3(株式会社同人化学研究所製)を40nmの順序で蒸着することで、発光部17を形成した。
なお本実施の形態では、陰極バッファ層および陰極層14として、Ag:Mg(重量比率25:1)膜100nmを形成した。また他は、実施例1と同様の工程を実施した。
有機発光素子として、図1で示した有機発光素子10を作製した。このとき下記の方法で作製することで、光を下面(陽極層12側)と上面(陰極層14側)の両方から取り出すことができるようにした。
実施例1で、石英ガラスからなるガラス基板(25mm角、厚さ1mm)上に、陽極層12としてITO膜を成膜する代わりに、同スパッタ装置を用いて、銀(Ag)層を150nm成膜した。このようにして成膜した銀層は、可視光に対して不透明であった。
また銀膜のエッチング条件としては、反応ガスとしてCl2ガスを使用し、圧力1Pa、出力Bias/ICP=200/100(W)で、6分間反応させた。その結果、Ag層のない部分から光を取り出すことができるようになった。
そしてアルミニウム層を成膜する際に、その膜厚を10nmとし、これに重ねて抵抗加熱蒸着法によりITO膜を100nmを成膜した。このようにして成膜したアルミニウム層およびITO膜からなる陰極層14は、可視光に対して透明であった。また他は、実施例1と同様の工程を実施した。
図8の構造を有する有機発光素子を以下の方法により作製した。
具体的には、まず石英ガラスからなるガラス基板(25mm角、厚さ1mm)上に、スパッタ装置(キヤノンアネルバ株式会社製E-401s)を用いて、ITO膜を150nm、二酸化ケイ素(SiO2)層を120nm成膜した。ここで、ガラス基板は、基板11に対応する。またITO膜は陽極層12に、二酸化ケイ素(SiO2)層は誘電体層132に対応する。
有機発光素子として、比較例1で説明した有機発光素子と同様の構造を有するものを作製した。ただし、発光部17を実施例8で説明した真空蒸着法により成膜した。このとき使用した材料および積層構造は実施例8と同様にして実施した。また、陰極バッファ層および陰極層14として、Ag:Mg(重量比率25:1)膜100nmを形成した。
比較例1に対し、以下の点を変更することにより、図9の構造を有する有機発光素子を作製した。このとき陽極層12としてITO膜を形成した後に、誘電体層132として二酸化ケイ素(SiO2)層を120nm形成した。そして誘電体層132をドライエッチングによりパターン化した。その後、続けてITO膜をエッチングした。ITO膜のエッチング条件としては、反応ガスとしてCl2とSiCl4の混合ガスを使用し、圧力1Pa、出力Bias/ICP=200/100(W)で、8分間反応させた。このドライエッチング処理により、陽極層12としてのITO膜を貫通する貫通部16が形成された。そしてレジスト除去液によりレジスト残渣を除去した。形成された貫通部16は、陽極層12面内に六方格子状に配列された直径1μmの円柱形状であり、貫通部16のエッジ間の距離は1μmとなった。
有機発光素子として、比較例3で説明した有機発光素子と同様の構造を有するものを作製した。ただし、比較例3に対し以下の点を変更した。つまり陽極層12としてITO膜を成膜する代わりに、同スパッタ装置を用いて、銀(Ag)層を150nm成膜した。そして誘電体層132として二酸化ケイ素(SiO2)層を120nm形成した。その後誘電体層132をエッチングし、さらに続けて銀膜をエッチングした。銀膜のエッチング条件としては、反応ガスとしてCl2ガスを使用し、圧力1Pa、出力Bias/ICP=200/100(W)で、6分間反応させた。その結果、Ag層のない部分から光を取り出すことができるようになった。
そしてアルミニウム層を成膜する際に、その膜厚を10nmとし、これに重ねて抵抗加熱蒸着法によりITO膜を100nm成膜した。このようにして成膜したアルミニウム層およびITO膜からなる陰極層14は、可視光に対して透明であった。また他は、実施例3と同様の工程を実施した。
また第2の誘電体層19の屈折率を波長550nmの光の場合で測定した。
結果を以下の表1に示す。なお発光効率の結果は、比較例1を1.0として規格化した数値である。また比較例1~4については、第2の誘電体層19との比較で、発光部17の屈折率を記載した。なお、ITOの屈折率は1.75であった。
また実施例6のように、第1の誘電体層13および第2の誘電体層19を塗布法で形成した場合でも発光効率はよくなっており、第1の誘電体層13および第2の誘電体層19を形成するのに塗布法も適用可能であると言える。塗布法を採用することで、(1)塗布成膜でしか形成できない材料も使用できるため、適用できる材料の幅が広がる(つまり、スパッタ等による真空成膜より安価な材料あるいは特性の良い塗布材料があった場合でも適用できる)、(2)一般に塗布法による成膜は、スパッタ等による真空成膜より安価(設備が安価)である、という利点が生じる。
Claims (17)
- 基板上に形成された第1の電極層と、
前記第1の電極層上に形成された第1の誘電体層と、
前記第1の誘電体層上に形成された第2の電極層と、
少なくとも前記第1の電極層および前記第1の誘電体層を貫通する複数の貫通部と、
前記貫通部内における前記基板の上面および前記第1の電極層の側面に接して形成された第2の誘電体層と、
前記貫通部内における前記第1の電極層の側面、前記第2の誘電体層の上面および前記第2の電極層に接して形成された発光部と、
を有する有機発光素子。 - 前記基板上面を基準とした前記第2の誘電体層の厚さが、前記第1の電極層の厚さよりも小さい、請求項1に記載の有機発光素子。
- 前記貫通部が、前記第1の誘電体層上面において、最大幅が10μm以下の円形形状または多角形形状を有するか、または幅が10μm以下の互いに平行な複数の帯状に形成されている、請求項1または2に記載の有機発光素子。
- 円形形状または多角形形状の前記貫通部が、前記第1の誘電体層上の任意の1mm四方の面内において、103~108個形成されている、請求項3に記載の有機発光素子。
- 帯状の前記貫通部の間隔が10μm以下である、請求項3に記載の有機発光素子。
- 前記第2の誘電体層が、400nm~750nmの可視光に対して透明な材料により形成されている、請求項1~5のいずれか1つに記載の有機発光素子。
- 前記第1の誘電体層および前記第2の誘電体層の屈折率が、いずれも前記第1の電極層の屈折率よりも小さい、請求項1~6のいずれか1つに記載の有機発光素子。
- 前記第1の誘電体層の屈折率が、前記発光部の屈折率よりも小さい、請求項1~7のいずれか1つに記載の有機発光素子。
- 前記第1の誘電体層の厚さが、前記第2の誘電体層の厚さよりも小さい、請求項1~8のいずれか1つに記載の有機発光素子。
- 前記貫通部が、少なくとも前記第1の電極層および前記第1の誘電体層を貫通して形成される貫通上部と、前記基板に形成される穿孔部とからなる、請求項1~9のいずれか1つに記載の有機発光素子。
- 基板上に第1の電極層を形成する第1工程と、
前記第1の電極層を貫通する複数の貫通孔を形成する第2工程と、
前記第1の電極層上に第1の誘電体層を形成するとともに、前記貫通孔内に露出した前記基板の上面および当該第1の電極層の側面に接して第2の誘電体層を形成することにより、当該貫通孔を含み、当該第1の電極層および当該第1の誘電体層を貫通する複数の貫通部を形成する第3工程と、
前記貫通部内に露出した前記第1の電極層の側面および前記第2の誘電体層の上面に接して発光部を形成する第4工程と、
前記第1の誘電体層上および前記発光部上を覆い、当該発光部に接して第2の電極層を形成する第5工程と、
を有する、有機発光素子の製造方法。 - 前記第3工程と前記第4工程の間に、前記第1の誘電体層の厚さを小さくする薄膜化工程をさらに有する、請求項11に記載の有機発光素子の製造方法。
- 前記第3工程と前記第4工程の間に、前記第1の誘電体層および/または前記第2の誘電体層に覆われた前記第1の電極層の一部を露出させる工程をさらに有する、請求項11または12に記載の有機発光素子の製造方法。
- 前記第2工程において、前記貫通孔の底部の基板にさらに穿孔部を形成する、請求項11~13のいずれか1つに記載の有機発光素子の製造方法。
- 基板上に第1の電極層を形成する第1工程と、
前記第1の電極層上に第1の誘電体層を形成する第2工程と、
少なくとも前記第1の電極層および前記第1の誘電体層を貫通する複数の貫通部を形成する第3工程と、
前記貫通部内に、当該貫通部内に露出した前記基板の上面および前記第1の電極層の側面に接して第2の誘電体層を形成する第4工程と、
前記貫通部内に露出した前記第1の電極層の側面と前記第2の誘電体層の上面に接して発光部を形成する第5工程と、
前記第1の誘電体層上および前記発光部上を覆い、当該発光部に接して第2の電極層を形成する第6工程と、
を有する、有機発光素子の製造方法。 - 前記第4工程と前記第5工程の間に、前記第1の誘電体層および/または前記第2の誘電体層に覆われた前記第1の電極層の一部を露出させる工程をさらに有する、請求項15に記載の有機発光素子の製造方法。
- 前記第2工程において、前記貫通部の底部の基板にさらに穿孔部を形成する、請求項15または16に記載の有機発光素子の製造方法。
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US20150024519A1 (en) * | 2012-02-29 | 2015-01-22 | Showa Denko K.K. | Method for producing organic electroluminescent element |
TWI597863B (zh) * | 2013-10-22 | 2017-09-01 | 晶元光電股份有限公司 | 發光元件及其製造方法 |
CN104037357B (zh) * | 2014-06-05 | 2016-01-27 | 京东方科技集团股份有限公司 | 一种有机发光显示装置及其制造方法 |
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