WO2010032596A1 - Panneau à émission de lumière par la surface - Google Patents

Panneau à émission de lumière par la surface Download PDF

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Publication number
WO2010032596A1
WO2010032596A1 PCT/JP2009/064942 JP2009064942W WO2010032596A1 WO 2010032596 A1 WO2010032596 A1 WO 2010032596A1 JP 2009064942 W JP2009064942 W JP 2009064942W WO 2010032596 A1 WO2010032596 A1 WO 2010032596A1
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WIPO (PCT)
Prior art keywords
light
organic
group
substrate
layer
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PCT/JP2009/064942
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English (en)
Japanese (ja)
Inventor
康伸 小林
正数 遠西
賢司 新井
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コニカミノルタホールディングス株式会社
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Priority to JP2010529702A priority Critical patent/JP5381992B2/ja
Publication of WO2010032596A1 publication Critical patent/WO2010032596A1/fr

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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
    • H10K59/10—OLED displays
    • H10K59/18—Tiled displays
    • 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
    • H10K59/877—Arrangements for extracting light from the devices comprising scattering means
    • 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
    • H10K59/86—Series electrical configurations of multiple OLEDs

Definitions

  • the present invention relates to a surface light emitting panel as an illumination device capable of obtaining uniform light emission. Specifically, the present invention relates to a light scattering member for a lighting device in which panels of surface light sources using organic electroluminescence elements (hereinafter referred to as “organic EL elements”) are arranged, and a surface light emitting panel using the same.
  • organic EL elements organic electroluminescence elements
  • an illumination device that is a surface light source using a light emitting element
  • organic electroluminescence (hereinafter also referred to as “organic EL”) element is considered promising as the light emitting element because of its high luminous efficiency.
  • organic EL organic electroluminescence
  • the seam remains as a non-light-emitting portion.
  • each element when using an organic EL element that has been developed in recent years, each element must be sufficiently sealed. It is necessary to secure the interval between the light emitting surfaces of adjacent elements, and the method of arranging the elements in the in-plane lateral direction still has a limit in improving the visibility.
  • the present invention has been made in view of the above-described problems and situations, and its solution is to improve the darkness between panels when a plurality of surface light source panels using organic EL elements are connected to increase the light emitting area. And it is providing the surface emitting panel as an illuminating device which can obtain uniform light emission.
  • a large-sized light-emitting panel formed by bonding a plurality of organic EL elements, and having a light scattering member between the element substrates when the plurality of elements are arranged on the same substrate, It is intended to provide a surface light emitting panel as an illumination device that emits light at the joint portion between elements by diffusing light leaking into the light with a light scattering member and emitting it to the front surface.
  • the inventor of the present invention has arrived at the present invention as a result of earnestly studying the light scattering member, the light emitting layer material, and the like in order to solve the above problems.
  • An organic electroluminescence element (hereinafter referred to as “organic EL element”) having at least a first electrode, a second electrode and a light emitting layer provided between them on a substrate is referred to as another substrate (hereinafter referred to as “panel configuration substrate”). .),
  • a plurality of surface emitting panels arranged on the same surface, (1) having a light scattering member disposed between substrates of adjacent organic EL elements, and (2) a plurality of organic ELs
  • the angle formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed between the substrates of the element is 90 ° ⁇ ⁇ (where 5 ° ⁇ ⁇ 45 °).
  • Is 90 ° ⁇ ⁇ (where 5 ° ⁇ ⁇ ⁇ 45 °; ⁇ and ⁇ may be the same value).
  • a surface-emitting panel characterized by being.
  • a surface light-emitting panel in which a plurality of organic EL elements each having at least a first electrode, a second electrode, and a light-emitting layer provided therebetween are arranged on the same surface of a panel-constituting substrate on a substrate.
  • a light scattering member disposed between the substrates of the matching organic EL elements, and (2) of the side surfaces of the two substrates contacting the light scattering member disposed between the substrates of the plurality of organic EL elements When the angle formed between the side surface and the bottom surface of one substrate is 90 ° + ⁇ (5 ° ⁇ ⁇ ⁇ 45 °), the angle formed between the side surface and the bottom surface of the other adjacent substrate is 90 °.
  • the angle formed by the side surface and the bottom surface of one of the two substrates contacting the light scattering member disposed between the substrates of the plurality of organic EL elements Is 90 ° + ⁇ (where 5 ° ⁇ ⁇ ⁇ 45 °)
  • the other adjacent Surface emitting panel according to the 1 the angle of the angle formed by the side surface and the bottom surface of the plate is characterized in that it is a 90 ° + ⁇ .
  • the angle formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed between the substrates of the plurality of organic EL elements is 90 ° + ⁇ (where 5 ° ⁇ ⁇ 3.
  • the surface light emitting panel according to 1 or 2 above, wherein the angle formed by the side surface and the bottom surface of the other adjacent substrate is 90 ° ⁇ when it is set to ⁇ 45 °.
  • the surface as an illuminating device which can improve the darkness between panels when a plurality of surface light source panels using organic EL elements are connected to expand the light emitting area and obtain uniform light emission by the above-described means of the present invention.
  • a light-emitting panel can be provided.
  • FIG. 1 Schematic sectional view of a surface emitting panel Schematic cross-sectional view of an organic electroluminescence element ("organic EL element") Schematic sectional view of a surface emitting panel Schematic sectional view of a surface emitting panel Schematic sectional view of a surface emitting panel Schematic sectional view of a surface emitting panel The figure which shows the position of the anode in the surface emitting panel (illuminating device) which arranged the panel of the surface light source using an organic EL element. The figure which shows the position of the light emitting layer in the surface emitting panel (illuminating device) which arranged the panel of the surface light source using an organic EL element.
  • organic EL element organic electroluminescence element
  • the figure which shows the position of the cathode in the surface emitting panel (illuminating device) which arranged the panel of the surface light source using an organic EL element The figure which shows the position of the sealing material in the surface emitting panel (illuminating device) which arranged the panel of the surface light source using an organic EL element.
  • an organic electroluminescence element (hereinafter referred to as “organic EL element”) having at least a first electrode, a second electrode, and a light emitting layer therebetween is provided on another substrate (hereinafter referred to as “organic EL element”).
  • panel configuration substrate a plurality of surface emitting panels arranged on the same surface, (1) having a light scattering member arranged between substrates of adjacent organic EL elements, And (2) the angle formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed between the substrates of the plurality of organic EL elements is 90 ° ⁇ ⁇ (however, 5 ° ⁇ ⁇ ⁇ 45 °), the angle between the side surface and the bottom surface of the other adjacent substrate is 90 ° ⁇ ⁇ (where 5 ° ⁇ ⁇ ⁇ 45 °; ⁇ and ⁇ are the same value) It may be.).
  • This feature is a technical feature common to the inventions according to claims 1 to 6.
  • an organic EL element having at least a first electrode, a second electrode, and a light emitting layer provided between them on the substrate is the same as the panel configuration substrate.
  • a plurality of surface emitting panels arranged on a surface, (1) having a light scattering member arranged between substrates of adjacent organic EL elements, and (2) between substrates of a plurality of organic EL elements When the angle formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed at 90 ° + ⁇ (where 5 ° ⁇ ⁇ ⁇ 45 °), The angle formed by the side surface and the bottom surface of the other adjacent substrate is 90 ° - ⁇ , or (3) the two substrates in contact with the light scattering member disposed between the substrates of the plurality of organic EL elements.
  • the angle formed by the side surface and the bottom surface of one of the side surfaces is 9 ° + alpha (where, 5 ° ⁇ ⁇ ⁇ 45 °) when and, it is preferable angle formed with the side surface of the adjacent other substrate and bottom surface is 90 ° + ⁇ .
  • the angle formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed between the substrates of the plurality of organic EL elements is 90 ° + ⁇ (however, 5 ° ⁇ ⁇ ⁇ 45 °), it is more preferable that the angle formed by the side surface and the bottom surface of the other adjacent substrate is 90 ° ⁇ .
  • the “bottom surface of the substrate” of the organic EL element refers to the surface of the substrate of the organic EL element that is in contact with the panel configuration substrate.
  • the panel configuration substrate has a light diffusion function.
  • the electrode which connects the organic EL elements which comprise the said surface emitting panel is connected in series.
  • the said surface emitting panel is an aspect sealed so that the whole several light emitting layer in the surface on the opposite side to the light emission surface of the said surface emitting panel may be covered.
  • the surface light-emitting panel of the present invention is a surface light-emitting panel as a lighting device in which panels of surface light sources using organic EL elements (hereinafter also referred to as “organic EL elements” or simply “organic EL elements”) are arranged. Thus, the light emitting member is interposed between a plurality of adjacent organic EL elements, and the panel is connected and combined.
  • organic EL elements panels of surface light sources using organic EL elements
  • FIG. 1 is a schematic cross-sectional view of a surface emitting panel (lighting device).
  • the surface light emitting panel 2 is formed by arranging a plurality of organic EL elements 1.
  • nine organic EL elements 1 having substantially the same configuration are arranged in a matrix of 3 rows and 3 columns, and the adjacent organic EL elements 1 are arranged via the light scattering member according to the present invention.
  • the organic EL element 1 includes a transparent substrate 10, a light emitting layer 20 (22) sandwiched between electrodes on a panel configuration substrate 11, and a sealing material 40. It is joined. It is configured as a bottom emission type organic EL device in which light emitted from the light emitting layer 20 (22) is extracted (emitted) to the outside of the organic EL element through the transparent substrate 10.
  • the arrangement of the surface light emitting panels 2 is not limited to the 3 ⁇ 3 matrix shown in FIGS. 7 to 10 and may be arranged in one, two, or four or more columns. Further, the number of organic EL elements 1 can be arbitrarily changed according to the required irradiation area.
  • the preferable aspect of the illuminating device which concerns on this invention is the aspect which the light-scattering member which concerns on this invention interposes between adjacent panels in the surface emitting panel (illuminating device) which arranged the panel of the surface light source using the organic EL element. It is. Moreover, in the said surface emitting panel (illuminating device), it is preferable that the electrode which connects the elements which comprise a surface emitting panel is connected in series. Further, it is preferable that the panel constituting substrate has a light diffusion effect.
  • the light scattering part and member according to the present invention are for a lighting device in which a panel of a surface light source using an organic EL element composed of a transparent substrate, a light emitting layer sandwiched between an anode and a cathode, and a sealing member is arranged.
  • the light scattering member is characterized by satisfying the following requirements (1) and (2). (1)
  • the light scattering member is disposed between adjacent organic EL elements.
  • a preferable embodiment from the viewpoint of the effect of the present invention is an embodiment that satisfies the following requirement (3) or (4).
  • (3) The angle (plane angle) formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed between the substrates of the plurality of organic EL elements is 90 ° + ⁇ (However, when 5 ° ⁇ ⁇ ⁇ 45 °), the angle (plane angle) formed by the side surface and the bottom surface of the other adjacent substrate is 90 ° ⁇ .
  • the angle (plane angle) formed by the side surface and the bottom surface of one of the two substrates in contact with the light scattering member disposed between the substrates of the plurality of organic EL elements is 90 ° + ⁇ (However, when 5 ° ⁇ ⁇ ⁇ 45 °), the angle (plane angle) formed by the side surface and the bottom surface of the other adjacent substrate is 90 ° + ⁇ .
  • the angle formed between the side surface and the bottom surface of the substrate used in the present invention is 90 ° + ⁇ (provided that 5 ° ⁇ ⁇ ⁇ 45 °), if ⁇ is less than 5 °, it is difficult to obtain the effect of light scattering, and if ⁇ exceeds 45 °, the side surface of the substrate becomes thin and the strength is reduced, resulting in damage. It becomes easy. The same can be said for ⁇ .
  • the angle of the side of the element substrate that constitutes the surface light-emitting panel on the side in contact with the panel-constituting substrate varies depending on the wavelength of the light to be extracted, but the light with the highest reflectance is extracted.
  • ⁇ is 10 to 45 °, and more preferably 30 to 45 °.
  • the light scattering member 30 according to the present invention may be integrated with the transparent substrate 10 on the side from which light is extracted, or the transparent substrate 10 and the light scattering member 30 are separately manufactured and bonded with an adhesive (not shown). May be.
  • the material of the light scattering member used in the present invention is not particularly limited, and any material that can be processed into powder or particles and can diffuse light can be used without any problem.
  • hollow glass beads, acrylic resin, various plastic materials such as PET and polycarbonate, quartz powder, silicon resin, calcium carbonate, barium sulfate, fluorite, and the like can be used.
  • the shape is not particularly limited and may be indefinite or spherical, but is preferably spherical.
  • the average particle diameter is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m.
  • the said particle size can be measured with a particle size distribution analyzer (for example, Mastersizer 2000E by Malvern Instruments).
  • the light scattering member may be powder or particle alone, but may be solidified and shaped by mixing an adhesive or resin.
  • Adhesives and resins can be used without particular limitation as long as they do not impair the light transmission and light scattering properties.
  • the ratio of the light scattering particles to the adhesive or resin is preferably 10 to 100 vol%, more preferably 20 to 90 vol%.
  • the adhesive and resin for example, casein, natural rubber, starch, and glue can be used as the natural adhesive.
  • Synthetic adhesives include acrylic resin, ⁇ -olefin, urethane resin, ether cellulose, ethylene-vinyl acetate resin, epoxy resin, vinyl chloride resin, chloroprene rubber, vinyl acetate resin, cyanoacrylate , Silicone, aqueous polymer-isocyanate, styrene-butadiene rubber, nitrile rubber, nitrocellulose, phenol resin, modified silicone, polyamide resin, polyimide, polyolefin resin, polystyrene resin, polyvinyl Alcohol-based, polyvinylpyrrolidone-based, polyvinylbityral-based, polybenzimidazole-based, polymethacrylate resin-based, melamine-resin-based, urea-resin-based, resorcinol-resin-based, and the like.
  • the electrodes according to the present invention are preferably connected in series. In order to connect in series, the cathode of the organic EL element adjacent to the anode of the organic EL element is connected as shown in FIG. This configuration is repeated with a plurality of organic EL elements to form a single series wiring as a whole. A typical connection arrangement is shown in FIGS.
  • the “panel configuration substrate” according to the present invention is not limited to the function of holding a plurality of organic EL elements side by side, the function of diffusing light, the function of increasing the efficiency of extracting light from a transparent substrate, and the light distribution characteristics of the extracted light It includes a light condensing function that adjusts arbitrarily.
  • the brightness does not change even if the viewing angle changes because light is emitted in all directions.
  • a substrate glass substrate, resin substrate, etc.
  • part of the light emitted from the light emitting layer undergoes total reflection at the interface between the substrate and air, causing loss of light.
  • the prism surface or lens sheet is processed on the surface of the substrate, or the prism sheet or lens sheet is attached to the surface of the substrate, thereby suppressing total reflection and improving the light extraction efficiency. .
  • the light extraction efficiency can be improved by using these in a range that does not impair the target effect.
  • the light scattering member according to the present invention also has an effect of making it less noticeable when not emitting light.
  • a light diffusing plate is placed on a glass substrate
  • the substrate on the side opposite to the light emitting layer of the glass substrate A substrate and a first light diffusion plate (hereinafter also simply referred to as “diffusion plate”) are placed in contact with the surface.
  • a second light diffusion plate may be bonded.
  • a layer for diffusing light may be directly applied to the surface of the glass substrate, or a fine structure for diffusing light may be provided on the surface of the glass substrate.
  • the glass substrate has been described above, but the substrate may be a resin substrate.
  • a light diffusing plate and a prism sheet are placed on a glass substrate
  • a glass substrate for example, in an organic EL element comprising a glass substrate / transparent conductive film / organic light emitting layer / electrode / sealing layer, it is opposite to the light emitting layer of the glass substrate
  • the first diffusion plate is placed in contact with the substrate surface on the side.
  • a first lens sheet (for example, 3M BEF II) is arranged so as to be in contact with the diffusion plate so that the lens surface faces the opposite side of the glass substrate, and the second lens sheet is formed with a stripe of the first lens. It is arranged so as to be orthogonal to the stripe of the lens and the lens surface thereof facing away from the glass substrate.
  • a second diffusion plate is disposed so as to be in contact with the second lens sheet.
  • a ⁇ -shaped stripe having an apex angle of 90 degrees and a pitch of 50 ⁇ m is formed on an acrylic resin on a PET substrate.
  • a shape with a rounded apex angle (3M RBEF), a shape with a randomly changed pitch (3M BEF III), or other similar shapes may be used.
  • a film in which beads for diffusing light are mixed is formed on a PET substrate of about 100 ⁇ m, the transmittance is about 85%, and the haze value is about 75%.
  • the second diffusion plate a film in which beads for diffusing light are mixed is formed on a PET substrate of about 100 ⁇ m, the transmittance is about 90%, and the haze value is about 30%.
  • the diffusion plate arranged in contact with the glass substrate may be bonded to the glass substrate via an optical adhesive. Further, a layer for diffusing light may be directly applied to the surface of the glass substrate, or a fine structure for diffusing light may be provided on the surface of the glass substrate.
  • the glass substrate has been described above, but the substrate may be a resin substrate.
  • each microlens array sheet has a shape in which microlenses each having a square apex of 50 ⁇ m (pyramid shape) and an apex angle of 90 degrees are aligned at a pitch of 50 ⁇ m.
  • the sheet is manufactured by injecting UV curable resin between a metal mold that is the mother mold of the microlens array and a glass plate placed between 0.5 mm spacers, and UV exposure from the glass substrate. By doing so, the resin is cured to obtain a microlens array sheet.
  • a conical shape, a triangular pyramid shape, a convex lens shape, or the like is applicable as the shape of each microlens.
  • the microlens array sheet may be attached to the resin substrate.
  • the structure of providing a transparent electrode / organic light emitting layer / electrode / sealing layer on the surface opposite to the surface provided with the microlens array of the microlens array sheet may be used.
  • an organic light emitting layer of the glass substrate is provided.
  • the microlens array sheet is attached to the surface opposite to the surface on which the concave and convex surfaces of the microlens face the glass substrate side via an optical adhesive.
  • the microlens array sheet has a shape in which microlenses having a structure in which the apexes of a rectangular shape each having a side of 50 ⁇ m are flat are arranged at a pitch of 50 ⁇ m. The flat top portion is adhered to the surface of the glass substrate.
  • each microlens a conical shape, a triangular pyramid shape, a convex lens shape, or the like is applicable.
  • the microlens array sheet may be attached to the resin substrate.
  • a low refractive index layer between the transparent electrode and the transparent substrate.
  • a low refractive index medium is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
  • the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Furthermore, it is preferable that it is 1.35 or less.
  • the thickness of the low refractive index medium is preferably longer than the wavelength in the light medium, preferably twice or more. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate. Examples of the low refractive index layer according to the present invention will be described below. However, the present invention is not limited to these examples as long as the object effects are not impaired.
  • a method for producing a glass substrate in which a hollow silica is dispersed by a sol-gel method to form a low refractive index layer will be described.
  • a low refractive index layer can be formed on a glass substrate by the following procedure.
  • Metal alkoxide (original tetrasilicate Si (OC 2 H 5 ) 4 : abbreviated as “TEOS”) as a raw material compound, ethanol as a solvent, acetic acid as a catalyst, and water necessary for hydrolysis are added to a preparation liquid.
  • a liquid obtained by adding a refractive index material (catalyst chemical industry, silica particles (refractive index: 1.35)) to isopropyl alcohol is mixed and kept at several tens of degrees C to cause hydrolysis and polycondensation reaction. Generate.
  • a refractive index material catalogarilyst chemical industry, silica particles (refractive index: 1.35)
  • silica particles reffractive index: 1.35
  • spin coating is described as the solution coating method, but any method that can obtain a uniform film thickness may be used, such as dip coating.
  • a glass substrate is shown as the substrate, since the process temperature is 150 ° C. or less, it can be applied directly on the resin substrate. Further effects can be expected by selecting a lower refractive index as a raw material compound or a low refractive index material, and setting the refractive index of the resulting low refractive index layer to 1.37 or less.
  • the film thickness is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more.
  • silica airgel The transparent low refractive index layer is formed by silica airgel obtained by supercritical drying of a wet gel formed by a sol-gel reaction of silicon alkoxide.
  • Silica airgel is a light-transmitting porous body having a uniform ultrafine structure.
  • Liquid A was prepared by mixing tetramethoxysilane oligomer and methanol, and liquid B was prepared by mixing water, aqueous ammonia and methanol. An alkoxysilane solution obtained by mixing the A liquid and the B liquid is applied onto the substrate 2.
  • the alkoxysilane After the alkoxysilane is gelled, it is immersed in a curing solution of water, aqueous ammonia, and methanol and cured at room temperature for one day. Next, the cured gel-like compound is immersed in an isopropanol solution of hexamethyldisilazane, hydrophobized, and then subjected to supercritical drying to form a silica airgel.
  • porous silica As a low refractive index material, a film of a low relative dielectric constant material containing hexamethyldisiloxane or hexamethyldisilazane having water repellency is applied on a substrate to form a film.
  • a water-repellent material such as hexamethyldisiloxane or hexamethyldisilazane
  • alcohol or butyl acetate may be added as an additive to the solution of the low relative dielectric constant material used here. .
  • a low refractive index film made of a porous silica material is formed by evaporating the solvent, water, acid, alkali catalyst, surfactant, or the like in the solution of the low relative dielectric constant material by firing treatment or the like. This is washed to obtain a low refractive index film.
  • an intermediate layer is formed on the low refractive index film directly or with a transparent insulating film made of a SiO 2 film by, for example, RF sputtering, and then the intermediate layer is formed.
  • An ITO film is formed on the layer by DC sputtering to form a substrate with a transparent electrode.
  • This method is generated from the light emitting layer by utilizing the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction or second-order diffraction.
  • Bragg diffraction such as first-order diffraction or second-order diffraction.
  • the introduced diffraction grating desirably has a two-dimensional periodic refractive index.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength in the medium of the light to be amplified.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • a positive resist is applied to the surface after washing the glass substrate.
  • two parallel lights having a wavelength ⁇ that are coherent with each other are irradiated on the resist so as to face each other at an angle of ⁇ degrees from the substrate vertical direction.
  • interference fringes having a pitch d are formed in the resist.
  • d ⁇ / (2 cos ⁇ ).
  • a first interference fringe having a pitch of 300 nm is formed. Is done.
  • the substrate is rotated 90 degrees in the plane of the substrate to form a second interference fringe so as to be orthogonal to the first interference fringe. If the light beam to be exposed is maintained as it is, second interference fringes are formed at a pitch of 300 nm. Two interference fringes are superimposed on the resist and exposed to form a grid-like exposure pattern.
  • the development is performed so that the resist is removed only at the portion where the two interference fringes overlap and is strongly exposed.
  • a pattern in which the resist is removed in a substantially circular shape is formed in the overlapping portion of the lattices each having a vertical and horizontal pitch of 300 nm.
  • the diameter of the circle is, for example, 220 nm.
  • dry etching is performed to form a hole having a depth of 200 nm in the portion where the range is removed. Thereafter, the resist is removed and the glass substrate is washed.
  • a glass substrate in which holes having a depth of 200 nm and a diameter of 220 nm are arranged on the apexes of a square lattice having a pitch of 300 nm in length and width is formed on the surface.
  • an ITO film having a thickness of about 300 nm as measured from the bottom of the hole is formed by bias sputtering, and the surface unevenness can be flattened to 50 nm or less by appropriately controlling the bias sputtering conditions.
  • a glass mold is formed by a similar method, and a UV-curable resist is transferred onto the glass substrate by a nanoimprinting method.
  • An etching method is also possible.
  • the pattern formed on the glass substrate is transferred to a mold using a technique such as nickel electroforming, and the mold is transferred to a resin using a nanoimprint technique. Is possible.
  • the front luminance amplification factor is increased.
  • the so-called white light in the range of ⁇ 0.07 is adjusted.
  • the emission color is divided into 420-500 nm emission blue, 500-550 nm emission green, 600 nm-650 nm emission red. Therefore, although depending on the material (substantially dopant) that emits light, in the present invention, the front luminance peak value of the organic EL element when there is no light extraction and / or light collecting sheet is compared with the case where the sheet is present. Qualitatively, blue is the smallest ratio.
  • the blue color is generally rate-determined in the lifetime in continuous driving or the like, when such a light extraction and / or condensing sheet is used, a longer lifetime can be achieved in the organic EL element.
  • the driving voltage is limited by blue, which has the largest energy gap between HOMO and LUMO. Therefore, the organic EL element with improved light extraction has a design that requires less blue front luminance. Can be lowered.
  • the blue light emitting layer can be made thin and the driving voltage can be lowered, a longer life can be achieved compared to the case where there is no light extraction and / or light collecting sheet, and this combination provides a total of white light. Can be.
  • the amplification factor of the front luminance by the light extraction and / or condensing sheet is determined by using a spectral radiance meter (for example, CS-1000 (manufactured by Konica Minolta Sensing)) or the like to emit light from the front (2 ° field of view).
  • a spectral radiance meter for example, CS-1000 (manufactured by Konica Minolta Sensing)
  • the visible wavelength range is required so that the optical axis of the spectral radiance meter coincides with the normal from the light-emitting surface, with or without light extraction and / or condensing sheet. Measure and integrate the values and take the ratio.
  • the organic EL device according to the present invention is composed of components such as a substrate (base), electrodes, and organic layers having various functions. Specific examples of preferred configurations are shown below, but the present invention is not limited thereto.
  • carrier refers to electrons and holes
  • carrier transport layer is a layer made of a carrier transport material, but is preferably composed of a p-type or n-type semiconductor layer.
  • p-type or n-type semiconductor layer refers to an organic layer that contains an electron-accepting compound or an electron-donating compound and exhibits semiconductivity.
  • the “light emitting layer unit” is a structural unit having a plurality of light emitting layers, and refers to an organic layer laminated from the light emitting layer on the most anode side to the light emitting layer on the most cathode side. That is, each light emitting layer is composed of an organic layer containing a light emitting compound having a different emission color. In addition, it is preferable that the said unit has a nonluminous intermediate
  • the light emitting layer unit is a structural unit having a plurality of light emitting layers as described above.
  • the light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is within the layer of the light emitting layer. Even the interface between the light emitting layer and the adjacent layer may be used.
  • the layer thickness of the light emitting layer according to the present invention is not particularly limited, but it is possible to prevent layer homogeneity, application of unnecessary high voltage during light emission, and improvement in stability of light emission color with respect to driving current. Therefore, it is preferable to adjust to the range of 2 to 30 nm, and more preferably in the range of 5 to 25 nm.
  • a preferable deposition rate is 0.05 nm / second or less, particularly preferably 0.03 nm / second. This is because a light emitting dopant and a host compound are selectively deposited on a specific site by relatively slowing the deposition rate.
  • a preferable deposition amount can be adjusted according to a desired layer thickness or discontinuity. It is also preferable to use a mask corresponding to the deposition pattern in order to limit the deposition site.
  • the host compound and the light-emitting dopant also referred to as “light-emitting dopant” and “light-emitting dopant compound” contained in the light-emitting layer will be described.
  • the host compound contained in the light emitting layer of the organic EL device according to the present invention transfers the energy of excitons generated by recombination of carriers on the compound to the light emitting compound (light emitting dopant: guest compound), and As a result, a compound that emits the luminescent compound and a carrier that traps the carrier on the host compound in the luminescent compound, generates excitons on the luminescent compound, and as a result, a compound that emits the luminescent compound.
  • the compound is a compound whose phosphorescence quantum yield of phosphorescence emission at room temperature (25 degreeC) is less than 0.1, Preferably it is less than 0.01. Moreover, it is preferable that the ratio of the host compound in the compound contained in a light emitting layer is 20 mass% or more.
  • known host compounds may be used alone or in combination of two or more.
  • the organic EL element can be made highly efficient.
  • the organic compound of each layer constituting the organic electroluminescent device according to the present invention preferably contains at least 80% by mass or more of each layer of a material having a glass transition temperature (Tg) of 100 ° C. or higher.
  • the glass transition temperature (Tg) is a value determined by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).
  • the entire organic compound layer (also referred to as an organic layer) of the organic EL element is used.
  • uniform film properties are obtained, and furthermore, adjusting the phosphorescence emission energy of the host compound to be 2.9 eV or more effectively suppresses energy transfer from the dopant and obtains high luminance. I can do it.
  • the phosphorescence emission energy according to the present invention is the peak of the 0-0 transition band of the phosphorescence emission spectrum obtained when the photoluminescence of the deposited film of 100 nm is measured on the substrate (or simply the substrate) of the host compound. It refers to energy.
  • the delay time is set so short that it cannot be distinguished from fluorescence, phosphorescence and fluorescence cannot be separated. Therefore, it is necessary to select a delay time that can be separated.
  • any solvent that can dissolve the compound may be used (substantially, the solvent effect of the phosphorescence wavelength is negligible in the above measurement method).
  • the 0-0 transition band is obtained.
  • the emission maximum wavelength appearing on the shortest wavelength side in the phosphorescence spectrum chart obtained by the above-described measurement method is defined as the 0-0 transition band. To do. Since the phosphorescence spectrum usually has a low intensity, when it is enlarged, it may be difficult to distinguish between noise and peak.
  • the emission spectrum during excitation light irradiation (for convenience, this is referred to as a steady light spectrum) is expanded, and the emission spectrum 100 ms after excitation light irradiation (for convenience, this is referred to as a phosphorescence spectrum) is superimposed. It can be determined by reading the peak wavelength of the phosphorescence spectrum from the stationary light spectrum portion derived from the light spectrum. Further, by performing a smoothing process on the phosphorescence spectrum, it is possible to separate the noise and the peak and read the peak wavelength. As the smoothing process, a smoothing method of Savitzky & Golay can be applied.
  • Luminescent dopant As the luminescent dopant according to the present invention, a fluorescent compound or a phosphorescent compound (also referred to as “phosphorescent compound”, “phosphorescent substance”, or the like) can be used. From the viewpoint of obtaining an organic EL device, the above-mentioned host compound is used as a light-emitting dopant (also referred to simply as “light-emitting material”) used in the light-emitting layer or light-emitting unit of the organic EL device according to the present invention. At the same time, it contains at least one phosphorescent emitter. When using a fluorescent emitter together, it is preferable to select blue.
  • the phosphorescent emitter according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is Although defined as a compound of 0.01 or more at 25 ° C., a preferred phosphorescence quantum yield is 0.1 or more.
  • the phosphorescence quantum yield can be measured, for example, by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescent emitter according to the present invention has the phosphorescence quantum yield (0.01 or more) in any solvent. It only has to be achieved.
  • phosphorescent light emitters There are two types of phosphorescent light emitters. One type is the recombination of carriers on the host compound to which carriers are transported, generating an excited state of the host compound, and this energy is converted into phosphorus.
  • the energy transfer type that obtains light emission from the phosphorescent emitter by moving it to the light emitter, the other type is a carrier trap, the carrier recombination occurs on the phosphorescent emitter, although it is a carrier trap type in which light emission from the phosphorescent light emitter can be obtained, in any case, the excited state energy of the phosphorescent light emitter must be lower than the excited state energy of the host compound. .
  • the phosphorescent emitter according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex system). Compound) and rare earth complexes, and most preferred is an iridium compound.
  • the phosphorescent light emitter can be appropriately selected from known materials used for the light emitting layer of the organic EL element, and the blue light emitting layer has the above general formula (1) having a maximum emission wavelength of 480 nm or less. It is preferable to use a phosphorescent material represented by
  • the phosphorescent material also referred to as phosphorescent dopant
  • the general formula (1) represented by the general formula (1) will be described in detail.
  • examples of the substituent represented by R 1 include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert group, -Butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group) Group), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc.
  • an alkyl group for example, a methyl group, an ethyl group, a propyl group, an isoprop
  • an alkyl group or an aryl group is preferable.
  • Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring.
  • the 5- to 7-membered ring formed by Z include a benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring and thiazole ring. Of these, a benzene ring is preferred.
  • B 1 to B 5 represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and at least one represents a nitrogen atom.
  • the aromatic nitrogen-containing heterocycle formed by these five atoms is preferably a monocycle. Examples include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, oxadiazole ring, and thiadiazole ring. Among these, a pyrazole ring and an imidazole ring are preferable, and an imidazole ring is more preferable. These rings may be further substituted with the above substituents. Preferable substituents are an alkyl group and an aryl group, and more preferably an aryl group.
  • L 1 represents an atomic group forming a bidentate ligand together with X 1 and X 2 .
  • Specific examples of the bidentate ligand represented by X 1 -L 1 -X 2 include, for example, substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, picolinic acid And acetylacetone.
  • M1 represents an integer of 1, 2 or 3
  • m2 represents an integer of 0, 1 or 2
  • m1 + m2 is 2 or 3.
  • m2 is 0 is preferable.
  • a transition metal element of Group 8 to Group 10 of the periodic table (also simply referred to as transition metal) is used, among which iridium and platinum are preferable, and iridium is more preferable.
  • the phosphorescent compound represented by the general formula (1) according to the present invention may or may not have a polymerizable group or a reactive group.
  • the nitrogen-containing heterocycle formed by B 1 to B 5 is preferably an imidazole ring.
  • the general formula (1) is more preferably represented by the following general formula (2).
  • R 1 , R 2 and R 3 represent a substituent.
  • Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring.
  • n1 represents an integer of 0 to 5.
  • M 1 represents a group 8 to group 10 metal in the periodic table.
  • X 1 and X 2 each represent a carbon atom, a nitrogen atom, or an oxygen atom, and L 1 represents an atomic group that forms a bidentate ligand together with X 1 and X 2 .
  • m1 represents an integer of 1, 2 or 3
  • m2 represents an integer of 0, 1 or 2
  • m1 + m2 is 2 or 3.
  • the substituents represented by R 1 , R 2 and R 3 have the same meanings as the substituents represented by R 1 in the general formula (1).
  • Z, M 1 , X 1 and X 2 , L 1 and the like are also synonymous with those in the general formula (1).
  • m1 and m2 are also synonymous.
  • the group represented by R 2 in the general formula (2) is preferably an aromatic hydrocarbon ring group (aromatic carbocyclic group), more preferably a substituted aryl group, and the substituted aryl represented by the following general formula (3) The group represented by these is preferable.
  • R 4 represents a substituent having a steric parameter value (Es value) of ⁇ 0.5 or less.
  • R 5 is the same as R 1 and n5 represents an integer of 0 to 4. Note that * represents a bonding position.
  • the Es value is a steric parameter derived from chemical reactivity, and the smaller this value, the more sterically bulky substituent can be said.
  • the Es value will be described.
  • ester hydrolysis under acidic conditions it is known that the influence of substituents on the progress of the reaction may only be considered as steric hindrance.
  • the Es value is obtained by quantifying the steric hindrance.
  • the Es value of the substituent X is expressed by the following chemical reaction formula: X—CH 2 COOR X + H 2 O ⁇ X—CH 2 COOH + R X OH
  • Es log (kX / kH)
  • the reaction rate decreases due to the steric hindrance of the substituent X, and as a result, kX ⁇ kH, so the Es value is usually negative.
  • the above two reaction rate constants kX and kH are obtained and calculated by the above formula.
  • Es values include Unger, S. H. Hansch, C .; , Prog. Phys. Org. Chem. 12, 91 (1976). Also, the specific numerical values are described in “Structure-activity relationship of drugs” (Chemical domain extra number 122, Nankodo) and “American Chemical Society Reference Book, 'Exploring QSAR' p.81 Table 3-3”. There is. Next, a part is shown in Table 1.
  • the Es value as defined in this specification is not defined by defining that of a methyl group as 0, but by assuming that a hydrogen atom is 0, and an Es value where a methyl group is 0. Minus 1.24.
  • R 4 represents a substituent having a steric parameter value (Es value) of ⁇ 0.5 or less.
  • Es value a steric parameter value
  • the keto moiety converts the Es value as an enol isomer. Even when other tautomerism exists, the Es value is converted by the same conversion method.
  • fluorescent compound Fluorescent substance
  • fluorescent compounds also referred to as “fluorescent emitters”, “fluorescent dopants”, etc.
  • fluorescent compounds are coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes. Examples thereof include dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • conventionally known dopants can also be used in the present invention.
  • WO 00/70655 pamphlet JP 2002-280178 A, JP 2001-181616 A, JP 2002-280179 A, JP 2001-181617 A, JP 2002-280180 A, JP 2001-247859 A, JP 2002-299060 A, JP 2001-313178 A, JP 2002-302671 A, JP JP 2001-345183 A, JP 2002-324679 A, WO 02/15645 pamphlet, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002 2002 A.
  • JP-A No. 2002-241751 JP-A No. 2001-319779, JP-A No. 2001-319780, JP-A No. 2002-62824, JP-A No. 2002-1000047, JP-A No. 2002-2002 No. 203679, JP-A No. 2002-343572, JP-A No. 2002-203678, and the like.
  • Non-light emitting intermediate layer it is preferable to provide a non-light emitting intermediate layer as the carrier control layer.
  • the layer thickness of the non-light emitting intermediate layer is preferably in the range of 1 to 15 nm, and more preferably in the range of 3 to 10 nm to suppress interaction such as energy transfer between adjacent light emitting layers, and This is preferable from the viewpoint of not applying a large load to the current-voltage characteristics of the element.
  • the material used for the non-light emitting intermediate layer may be the same as or different from the host compound of the light emitting layer, but may be the same as the host material of at least one of the adjacent light emitting layers. preferable.
  • the non-light emitting intermediate layer may contain a compound common to each light emitting layer (for example, a host compound).
  • a compound common to each light emitting layer for example, a host compound.
  • Each of the common host materials means phosphorescence emission. In which the physicochemical characteristics such as energy and glass transition temperature are the same or the molecular structure of the host compound is the same.),
  • the injection barrier between the light-emitting layer and the non-light-emitting layer can be reduced. Thus, even if the voltage (current) is changed, the effect of easily maintaining the injection balance of holes and electrons can be obtained. It has also been found that the effect of improving the color shift when a voltage (current) is applied can be obtained.
  • the excitation triplet energy of the blue phosphorescent emitter is the largest, but the blue A light emitting layer and a non-light emitting intermediate layer may contain a host material having an excitation triplet energy larger than that of the phosphorescent light emitter as a common host material.
  • the host material is responsible for carrier transportation, a material having carrier transportation ability is preferable.
  • Carrier mobility is used as a physical property representing carrier transport ability, but the carrier mobility of an organic material generally depends on the electric field strength. Since a material having a high electric field strength dependency easily breaks the balance of hole and electron injection / transport, it is preferable to use a material having a low electric field strength dependency of mobility for the intermediate layer material and the host material.
  • the non-light emitting intermediate layer functions as a blocking layer, that is, a hole blocking layer and an electron blocking layer. It is done.
  • the light emitting layer which is a constituent layer of the organic EL element according to the present invention, is arbitrarily selected from emission colors emitting blue, green, yellow, and red to extract white light. .
  • the effect of the present invention can be further obtained by adding a plurality of dopants emitting different emission colors in the same layer.
  • a luminescent compound having a close emission wavelength is contained in the same layer.
  • blue-green-red at least one of blue-green and green-red is contained in the same layer.
  • blue-green-yellow-red at least one of blue-green, green-yellow, yellow-red is contained in the same layer, and the luminescent color containing a longer wave luminescent compound is contained in the same layer Is preferred.
  • yellow-red and green-yellow it is preferable that there are a plurality of light-emitting layers containing a plurality of light-emitting compounds having different emission colors. This is because it is more advantageous to have a plurality of configurations that favor energy transition.
  • the volume concentration of the luminescent compound of a longer wave light is 4% or less among several luminescent compounds from which luminescent color differs.
  • Long wave luminescent compounds often have a lower ionization potential and a higher HOMO energy level. In other words, it is easy to hold holes and the conductivity decreases, so if the content is low, the hole holding is relaxed, which is advantageous in terms of conductivity, the driving voltage for obtaining the desired luminance is lowered, and the power consumption is improved.
  • the energy level of HOMO and the structure of the luminescent compound is 4% or less among several luminescent compounds from which luminescent color differs.
  • the light emitting layer containing a light emitting compound having a high HOMO energy level is preferably stacked on the most cathode side in the light emitting layer.
  • the light emitting compound is a red light emitting compound.
  • the blue light emitting compound has the highest HOMO energy level among the light emitting colors selected to be white, light emission containing the blue light emitting compound is present.
  • the layer is laminated on the most cathode side. Two kinds of luminescent compounds having different luminescent colors to be contained in the same luminescent layer are preferable. This is because it is difficult to control the deposition conditions when the number is 3 or more.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport layer is preferably a so-called p-type semiconductor layer.
  • the effect of lowering the driving voltage is recognized, and it is interpreted that doping of the carrier (electron) acceptor increases the hole density or forms a high HOMO level to increase the hole mobility by hopping conduction. .
  • the hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
  • a known material can be used as the carrier (electron) acceptor material according to the present invention.
  • Jpn. Huang et. al. Authors Applied Physics Letters 80 (2002), p. 139
  • JP-A-4-297076 JP-A-2000-196140
  • JP-A-2001-102175 JP-A-2004-281371
  • J. Pat. Appl. Phys. 95, 5773 (2004) and the like.
  • general formulas (1) to (7) in Japanese Patent Application No. 2004-215727 are also preferably used.
  • the hole transport material and the carrier (electron) acceptor are formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can do.
  • the acceptor-containing average volume concentration according to the present invention is 0.1% to 30%, and it is preferable that there is a region where the concentration differs by at least 3% from the average concentration.
  • the difference between the highest density and the lowest density is 1% to 30%, preferably 1% to 20%, and more preferably 1% to 10%.
  • the layer thickness ratio in the highest concentration region is 1% to 50%, more preferably 2% to 45%.
  • the layer thickness is usually about 1 nm to 1 ⁇ m, preferably 5 nm to 200 nm. Within 5 nm from the interface between the hole transport layer and the organic layer adjacent to the cathode side according to the present invention, the lower the carrier (electron) acceptor concentration is within the range not impairing the conductivity, the more preferable from the viewpoint of continuous drive life.
  • the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transport layer is preferably a so-called n-type semiconductor layer.
  • the effect is recognized in the drive voltage, and it is interpreted that doping of the carrier (electron) donor increases the electron density or forms a high LUMO level to increase the electron mobility by hopping conduction.
  • any material that has a function of transmitting electrons injected from the cathode to the light emitting layer may be used.
  • examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material.
  • distyrylpyrazine derivatives exemplified as the material for the light emitting layer can also be used as the electron transporting material.
  • a compound represented by the general formula (1) described in the host section can also be preferably applied.
  • the carrier donor material As the carrier donor material according to the present invention, known materials can be used. For example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like. Further, general formulas (8) to (10) in Japanese Patent Application No. 2004-215727 are also preferably used. In the present invention, an element having low power consumption can be produced by using such an electron transport layer having a high n property in combination with the p property semiconductor layer according to the present invention.
  • the electron transport material and the carrier (electron) donor can be formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.
  • the donor-containing average volume concentration according to the present invention is 5% to 95%, and there is a region where the difference between at least the maximum concentration and the minimum concentration is 5% or more. It is preferable.
  • the difference between the highest density and the lowest density is preferably 20% to 90%.
  • a preferred maximum concentration is 15% to 95%, more preferably 25% to 90%.
  • the film thickness ratio of the highest concentration region in the electron transport layer is 1% to 50%, more preferably 2% to 45%.
  • the layer thickness is usually about 1 nm to 1 ⁇ m, preferably 5 nm to 200 nm.
  • the carrier donor concentration is preferably as low as possible without impairing conductivity, from the viewpoint of continuous drive life. Depending on the material, it is often 5 or less.
  • the light emission efficiency may be further improved, and one example thereof is a case of continuous change.
  • the term “local” as used in the present invention refers to, for example, a case where film thickness configurations of 1 nm or more having different donor volume concentrations are arbitrarily combined. Even in this case, the difference in the donor volume concentration between the maximum concentration and the minimum concentration is 5% or more.
  • An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
  • Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • the injection layer may be provided as necessary, and may be present between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer as described above.
  • anode buffer layer hole injection layer
  • copper phthalocyanine is used.
  • examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • the details of the cathode buffer layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like.
  • the buffer layer is preferably a very thin film, and the film thickness is preferably in the range of 0.1 to 5 ⁇ m, depending on the material.
  • the hole blocking layer has a function of an electron transport layer and is composed of a hole blocking material having a function of transporting electrons and having a remarkably small ability to transport holes, while transporting electrons. By blocking holes, the recombination probability of electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer of the organic EL device according to the present invention is preferably provided adjacent to the light emitting layer.
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film.
  • the basic constituent layer of the organic compound thin film For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237.
  • the compound contained in the hole blocking layer has an ionization potential of 0.2 eV or more higher than the host compound of the shortest wave emitting layer.
  • the hole blocking layer according to the present invention contains the electron donor, the electron density increases, which is preferable for further lowering the voltage.
  • the ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.
  • Gaussian 98 Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.
  • the ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *.
  • the reason why this calculated value is effective is that there is a high correlation between the calculated value obtained by this method and the experimental value.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
  • the electron blocking layer preferably used in the present invention is a material for the hole transport layer. Further, when the electron acceptor is contained, the effect of further lowering the voltage can be obtained.
  • the thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • an electrode substance include conductive transparent materials such as metals such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as metals such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a film thickness of 1 to 20 nm. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
  • Organic EL device substrate Transparent substrate
  • the substrate of the organic EL element according to the present invention is not particularly limited in the type of glass, plastic, etc., but the substrate is preferably transparent.
  • the transparent substrate preferably used include glass, quartz, and a transparent resin film.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or
  • an inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film.
  • the oxygen transmission rate is 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less, and the water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is 1 ⁇ 10 ⁇ 3 It is preferable that it is a highly barrier film of g / (m 2 ⁇ 24h) or less.
  • any material may be used as long as it has a function of suppressing intrusion of an element such as moisture or oxygen that causes deterioration of the element.
  • Silicon, silicon dioxide, silicon nitride, or the like can be used.
  • the thickness of the substrate used in the present invention is preferably 50 to 1000 ⁇ m, more preferably 100 to 900 ⁇ m.
  • the method for forming the barrier film is not particularly limited.
  • a combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque substrate include a metal plate / film such as aluminum and stainless steel, an opaque resin substrate, a ceramic substrate, and the like.
  • the external extraction efficiency at room temperature of light emission of the organic EL device according to the present invention is preferably 1% or more, more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • Examples of the sealing means used for sealing the organic EL element according to the present invention include a method of bonding a sealing member, an electrode, and a substrate with an adhesive.
  • the sealing member is preferably sealed so as to cover the entire plurality of light emitting layers on the surface opposite to the light emitting surface of the surface light emitting panel in which a plurality of organic EL elements are arranged.
  • thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curable adhesives such as 2-cyanoacrylates.
  • fever and chemical curing types such as an epoxy type
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable.
  • a desiccant may be dispersed in the adhesive.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of the element such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like is used. it can.
  • the method for forming these films is not particularly limited.
  • a polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil is injected in the gas phase and the liquid phase. Is preferred.
  • a hygroscopic compound can also be enclosed inside.
  • the hygroscopic compound include metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.).
  • Metal halides eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.
  • perchloric acids eg, barium perchlorate,
  • anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.
  • a protective film or a protective plate may be provided outside the sealing film or the sealing film on the side facing the substrate with the organic layer interposed therebetween.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • Method for producing organic EL element As an example of the method for producing an organic EL device according to the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode will be described. .
  • a desired electrode material for example, a thin film made of an anode material is formed on a suitable support substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably 10 to 300 nm, thereby producing an anode.
  • a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably 10 to 300 nm, thereby producing an anode.
  • a method for thinning the organic compound thin film there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within a range of 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a film thickness of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • the organic EL element is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
  • a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • An organic EL element emits light within a layer having a refractive index higher than that of air (refractive index of about 1.6 to 2.1), and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side surface of the device.
  • a technique for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the transparent substrate and the air interface (for example, US Pat. No. 4,774,435), A method for improving efficiency by providing light condensing property (for example, Japanese Patent Laid-Open No. 63-134795), a method for forming a reflective surface on the side surface of an element (for example, Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (for example, Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device according to the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate A method of forming a diffraction grating between any layers of the transparent electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
  • the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Furthermore, it is preferable that it is 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any medium is characterized by a high effect of improving light extraction efficiency.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction, such as first-order diffraction or second-order diffraction.
  • the light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating into any layer or medium (in the transparent substrate or transparent electrode). , Trying to extract light out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any layer or in the medium (in the transparent substrate or transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL device according to the present invention is processed to provide a structure on a microlens array, for example, on the light extraction side of a support substrate (substrate), or in combination with a so-called condensing sheet, for example, a specific direction, By condensing in the front direction with respect to the element light emitting surface, the luminance in a specific direction can be increased.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction is generated and colored, and if it is too large, the thickness becomes too thick.
  • the condensing sheet it is possible to use, for example, an LED backlight of a liquid crystal display device that has been put into practical use.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • the shape of the prism sheet for example, the substrate may be formed with a triangle stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded, and the pitch is randomly changed. It may be a shape or other shapes.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the organic EL element according to the present invention is used in a multicolor or white display device.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like.
  • the method is not limited, but a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.
  • the cathode, the electron transport layer, the hole blocking layer, and the light emitting layer unit (having at least three layers of the above light emitting layers A, B, and C, and a non-light emitting intermediate layer between the light emitting layers) It is also possible to produce the hole transport layer and the anode in this order.
  • a DC voltage is applied to the multicolor or white display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the organic EL device according to the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display that directly recognizes a still image or a moving image. It may be used as a device (display).
  • the driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
  • patterning only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.
  • the light emitting dopant used in the light emitting layer is not particularly limited.
  • the platinum complex according to the present invention is adapted so as to conform to the wavelength range corresponding to the CF (color filter) characteristics. Any one of known light-emitting dopants may be selected and combined, and combined with the light extraction and / or light collecting sheet according to the present invention to be whitened.
  • the white organic EL element according to the present invention is combined with a CF (color filter), and the element and the driving transistor circuit are arranged in accordance with the CF (color filter) pattern, so that it is described in claim 7.
  • white light extracted from the organic EL element is used as a backlight, and blue light, green light, and red light are obtained through a blue filter, a green filter, and a red filter.
  • An organic electroluminescence display is preferable and preferable.
  • the organic EL element according to the present invention can be used as a display device, a display, and various light sources.
  • light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, and light sources for optical sensors. Although it is not limited to this, it can be effectively used for backlights of various display devices combined with color filters, light diffusion plates, light extraction films, etc., and as a light source for illumination.
  • the organic EL element Utilizing the characteristics of the organic EL element according to the present invention, it can be applied to various lighting fixtures and light emitting displays as shown below.
  • Store merchandise displays include decorative displays, showcases, POPs and signs for the store itself.
  • high-end brand shops, precious metals, fashion, high-end restaurants, and other stores that place emphasis on the brand image have a great influence on the store image that lighting gives, so lighting has been selected with strong attention
  • organic EL the space for the light source and equipment can be omitted in the field of indirect lighting, which has created an atmosphere by devising the structure of the building so that the light source can not be seen directly, and no complicated structure is required
  • the space between the light source and the diffusion plate can be omitted because the shape of the light source cannot be seen through when creating diffused light in interiors or signs, and so on.
  • Frozen and refrigerated showcases are placed in supermarkets and convenience stores to make fresh foods such as vegetables, fruits, fresh fish, and meats full of beauty and freshness, making them easier to see, vivid, and easier to take.
  • Lighting equipment is another important component.
  • an organic EL light source low temperature emission has little effect on the cooling function, and since it is thin, the light source space can be greatly reduced, so the storage space can be expanded, and it is easy to select food with a smart design. It can be made easier.
  • it can appeal to consumers with colored light that makes it easy to understand the goodness of food, contributing to sales.
  • Transportation advertisements include posters and signboards in public spaces, internal posters and screens such as trains and buses, and advertisements on the car body.
  • posters and billboards are box-type fluorescent lamps using a backlight, and the box itself can be made thinner and lighter by changing to organic EL.
  • thinning the box will eliminate the accumulation of dust and debris and prevent fecal damage from birds.
  • Hierarchitectural lighting a combination of floors, walls, ceilings, etc. and lighting is called “architectural lighting”.
  • Typical examples of “architectural lighting” include cornice lighting, troffer lighting, cove lighting, light ceiling, and louver ceiling, depending on the method. These require lighting sources to be built into the ceiling, walls and floors, extinguish their presence and signs as lighting, and the building materials themselves to emit light.
  • Light sources using organic EL elements are the most suitable light sources for “architecture lighting” due to their thinness, lightness, color adjustment, and design variability, and can be applied to interiors, furniture, and fixtures. It is. Conventionally, such architectural lighting, which has been used only in stores and museums, can be extended to ordinary houses by developing organic EL light sources, and new demand can be found.
  • organic EL light sources are used in semi-underground shops, arcade ceilings, etc., and by changing the brightness and color temperature of lighting, it is possible to construct an optimal commercial space that is not affected by the weather or day and night.
  • Examples of interiors, furniture and furniture include storage of desks and chairs, cupboards, shoe boxes and lockers, vanities, altars, bedlights, footlights, handrails, doors, shojis and shojis, etc. It is not limited to that.
  • a transparent electrode for the organic EL light source it is possible to switch between transparent and opaque by using a transparent electrode for the organic EL light source and turning it off / emitting light.
  • a transparent electrode for the organic EL light source it can be used as any window, door, curtain, blind, and partition.
  • organic EL elements can be used for external lighting fixtures and light-emitting display bodies, in-vehicle lighting fixtures and light-emitting display bodies, and the like.
  • the former is a front (sub-classification) headlamp, auxiliary light, vehicle width light, fog lamp, direction indicator light, etc.
  • the rear is a rear combination lamp as stop lamp, vehicle width light, back light, direction indicator light, and There are license plate lights.
  • by forming a single rear combination lamp using an organic EL element and attaching it to the rear part it is possible to reduce the space for the rear lamp and widen the trunk room.
  • the visibility of the vehicle can be increased by widening the area of the vehicle width lights and stop lamps.
  • the visibility from the side surface can be enhanced by causing the wheel to emit light with the organic EL element.
  • the entire body can be made of organic EL elements to emit light, and new ideas can be incorporated into the body color and design.
  • the latter in-vehicle lighting fixtures and light-emitting displays include room lights, map lights, boarding lights at the bottom of doors, meter displays, car navigation displays, warning lights, and the like.
  • a sunroof can be used during the daytime and light can be emitted during the nighttime to provide a room light with a gentle surface light source.
  • a lighting system consisting of organic EL elements is pasted on the back of the front seat, creating a handy lighting system that is easy for customers to use without hindering driver driving and sacrificing indoor space. Can be built.
  • the characteristics of the organic EL according to the present invention can be utilized in lighting and display bodies in vehicles in public transportation such as trains, subways, buses, airplanes, and ships.
  • Fluorescent lamps and light bulbs are used for room lighting, but these ceilings use indirect lighting reflected from the sides, giving the room a calm atmosphere and breaking glass in the event of a trouble. Has been devised so that does not fall into the audience seats.
  • an organic EL light source makes it easy to make indirect lighting because of its thinness, and there is no danger of cracking and debris scattering even when direct lighting is used, and it is possible to create a calm atmosphere with diffuse light.
  • an organic EL light source with low power consumption and light weight is preferable. These benefits not only illuminate the customer, but are also demonstrated in the lighting inside the baggage storage, and can contribute to the reduction of leftovers.
  • Display and lighting to guide customers can also be used at facilities such as stations, bus stops, and airports attached to public transportation.
  • facilities such as stations, bus stops, and airports attached to public transportation.
  • a person waiting for the bus can be detected to brighten the lighting, thereby contributing to crime prevention.
  • Light source for OA equipment Examples of light sources for office automation equipment include facsimiles, copying machines, scanners, printers, and multi-function machines equipped with reading sensors.
  • the reading sensor is divided into a contact type sensor (CIS) combined with an equal magnification optical system and a reduction type sensor (CCD linear) combined with a reduction optical system.
  • CIS contact type sensor
  • CCD linear reduction type sensor
  • CIS contact image sensor module
  • CISM contact image sensor module
  • the existing sensor chip may be called CIS.
  • LEDs, xenon, CCFL lamps, LDs and the like are used.
  • Illumination light sources used for image sensors include fluorescent lamps, LEDs, and halogens. Among them, as a backlight for illuminating a transparent container or a lead frame from the background, uniform light is required in a planar shape.
  • the detection of the stain on the sheet requires light that illuminates the front surface in the width direction of the sheet with linearly uniform light.
  • an organic EL light source in this field, for example, in the bottling process, it is possible to illuminate all 360 degrees around the bottle and illuminate and shoot at once, enabling inspection in a short time Become. Moreover, the space taken by the light source itself in the inspection equipment can be greatly reduced. Further, since the surface light source is used, it is possible to avoid a detection error due to difficulty in determining a captured image due to light reflection.
  • the plant factory is “an annual plant production system using high technology such as environmental control and automation”.
  • LED and LD have been increasingly used as light sources for plant cultivation.
  • Light sources such as high-pressure sodium lamps that have been widely used in the past have a poor spectral balance between red light and blue light, and a large amount of heat radiation increases the air conditioning load and requires a sufficient distance from the plant. There is a drawback that the facility becomes larger.
  • the organic EL light source has no light source thickness, can be installed with many shelves, and has a low calorific value, so it is highly efficient when placed close to plants and can increase the amount of cultivation.
  • Halogen, tungsten, strobe light, fluorescent light, etc. are used as light sources used in photo studios, studios, and lighting photo boxes. Applying these light sources directly to the subject to add a strong shadow, or diffuse light to create soft light with little shadow, a combination of two types of light from various angles. Is made.
  • In order to diffuse light there are methods such as sandwiching a diffuser between a light source and a subject, or using reflected light applied to another surface (reflective plate or the like).
  • the organic EL light source is diffuse light, and can emit light corresponding to the former without using a diffuser. In that case, the space between the light source and the diffuser required by the existing light source becomes unnecessary, and the light that has been adjusted with a fine angle by adjusting the direction of the light with a reflex plate etc. is flexible There is an advantage that it can be implemented by bending the type of organic EL itself.
  • Color rendering properties may be required for light sources used in photography. If the difference in the color appearance when viewed with sunlight is large, the color rendering is poor, and if the difference is small, the color rendering is evaluated as good. Fluorescent lamps used in general households are not preferable for photographing because of their wavelength characteristics, and the portions that are exposed to light tend to be green. The color of skin, makeup, hair, kimono, jewelry, etc. is often required to be reflected in its own color, and color rendering is one of the important factors for light. An organic EL light source is excellent in color rendering, and is preferable for photographing that requires color fidelity as described above. This feature is also used in places where it is desired to faithfully evaluate colors such as printing and dyeing.
  • a surface light source such as an organic EL light source
  • children and pets can freely play indoors when shooting children and pets, etc., and free and natural expressions do not have to bother moving the light source Can shoot with natural colors.
  • Household appliances are often equipped with light sources for ease of viewing details, ease of work, and design.
  • sewing machines, microwave ovens, dishwashers / dryers, refrigerators, AV equipment, etc. have a light source than before, but in the new ones, the washing / dryer is a horizontal model, and the light source is attached because it is left behind. It became so.
  • incandescent bulbs and LEDs are attached to existing ones.
  • Such home appliances are required to be light and small as a whole and have a large storage space, and the light source part is required to be able to illuminate the whole with as little space as possible.
  • the organic EL thin surface light source can sufficiently meet the demand.
  • Organic EL is particularly advantageous because of its low emission temperature. It is also possible to detect the position of the skater and emit light according to the movement of the skater. Combination effects with spotlights and light emission linked to the rhythm of music are also effective for show-ups.
  • illumination lighting In general, the term “illumination” generally refers to illumination of trees, but in recent years there have been many cases of transition to decoration of objects such as houses, gates, and fences from the viewpoint of environmental protection. Yes. The mainstream of this is the use of a large number of point light sources, decorated in a line shape, and is expected to be even more widespread with the advent of LEDs.
  • the prism type also has the same function, but the lens structure is different.
  • the glass bead type and the prism type feature that the glass bead type has a high reflection effect on light from an oblique direction, and the prism type reflects light from the front than the glass bead type, but from an oblique direction. The light may have a relatively low reflection effect.
  • the material and the bonding method can also be selected depending on the hardness of the place to be attached. In any case, in order to make pedestrians aware of light, it is necessary to be exposed to light. It was necessary to devise such as pasting.
  • an organic EL light source for these alternatives, it is possible to make the driver recognize the pedestrian before the headlight hits the area, thereby ensuring safety. Further, from the point of being light and thin with respect to other light sources, the effect can be obtained while maintaining the merit of the seal.
  • These can be used not only for humans but also for pet clothes.
  • the present invention can be applied to clothes for identifying a person, and can be used for early protection of a deaf person, for example. By making the wet suit for diving emit light, there is a possibility of confirming the location of the diver and protecting himself from the trap. Of course, it can also be used for stage costumes and wedding dresses at shows.
  • Luminescent bodies using organic EL elements can be effectively used in “visible light tags” that send simple messages and information using visible light. That is, by emitting a signal due to blinking for an extremely short time, a large amount of information can be sent to the receiving side.
  • the light emitter Even if the light emitter emits a signal, since it is extremely short time, it is recognized as simple illumination on human vision. Lighting installed at each location, such as roads, stores, exhibition halls, hotels, and amusement parks, can send information signals specific to each location and provide necessary information to the receiver.
  • a single light emitter provides a plurality of different information by incorporating a plurality of light emitting dopants having different wavelengths into one light emitter and generating different signals for different wavelengths. You can also. Also in this case, the organic EL having a stable emission wavelength and color tone is superior.
  • the “visible light tag” can be incorporated together as a lighting facility, so there is no need for complicated additional installation work.
  • Organic EL for endoscopes that currently use halogen lamps and illumination for abdominal surgery that operates with a wire inserted will contribute to miniaturization, weight reduction, and application expansion.
  • it can be used for endoscope capsules (drinking endoscopes) that are attracting attention in recent years and are used for in-vivo examinations and treatments.
  • a light-emitting body incorporating the organic EL element according to the present invention can easily select a color tone, does not flicker like a fluorescent lamp, and has a stable color tone with low power consumption.
  • Japanese Patent Application Laid-Open No. 2001-269105 As a pest control apparatus as shown in JP-A-2001-286373, as a mirror illumination as shown in JP-A-2001-286373, as a bathroom lighting system as shown in JP-A-2003-28895, as disclosed in JP-A-2004-321074.
  • a light-sensitive agent as shown in Japanese Laid-Open Patent Publication No. 2004-358063 is used as a light emitter of a water pollution measuring apparatus as shown in Japanese Laid-Open Patent Publication No. 2004-354232. This is useful as a medical surgical light as disclosed in JP-A-2005-322602.
  • Example 1 Production of organic EL element >> (Organic EL element (E-1))
  • ITO indium tin oxide
  • the transparent support substrate with the ITO transparent electrode was superposed with isopropyl alcohol.
  • Sonic cleaning, drying with dry nitrogen gas, and UV ozone cleaning were performed for 5 minutes.
  • This transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
  • the optimal amount was filled.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • the deposition crucible containing CuPc was energized and heated, and CuPc was deposited on the ITO electrode side of the transparent substrate at a deposition rate of 0.1 nm / second, A 15 nm hole injection layer was provided.
  • NPD was deposited on the hole injection layer at a deposition rate of 0.1 nm / second at a deposition rate of 0.1 nm / second to provide a 25 nm hole transport layer.
  • a blue light emitting layer having a film thickness of 15 nm was provided by co-evaporating on the hole transport layer at a total deposition rate of 0.1 nm / sec using Fir (pic) as 3 mass% and DPVBi as a host.
  • Ir (ppy) 3 was set to 5 mass%, CBP was used as a host, and co-evaporated on the intermediate layer at a total deposition rate of 0.1 nm / second to provide a green light emitting layer having a thickness of 10 nm.
  • CBP was deposited as an intermediate layer by 5 nm on green light emission at a deposition rate of 0.1 nm / second.
  • Ir (piq) 3 was 8 mass%
  • CBP was used as a host
  • the red light emitting layer having a thickness of 10 nm was provided by co-evaporation on the intermediate layer at a total deposition rate of 0.1 nm / second.
  • BAlq was deposited as a hole blocking layer on the red light emitting layer at a deposition rate of 0.1 nm / second for 15 nm.
  • Alq was deposited as an electron transport layer on the hole blocking layer at a deposition rate of 0.1 nm / second for 30 nm.
  • LiF was deposited as an electron injection layer on the electron transport layer by 1 nm at a deposition rate of 0.1 nm / second.
  • the organic EL element (E-1) was produced in a glove box (in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more) in a nitrogen atmosphere without being exposed to the air.
  • the angle formed between the side surface and the bottom surface of the substrate was 90 °, and the other adjacent angle was 90 ° (see FIG. 3).
  • Organic EL device (E-2) The organic EL element (E-1) was the same as E-1 except that the angle between the side surface and the bottom surface of the substrate was 120 ° and the other adjacent angle was 60 ° (see FIG. 4).
  • Organic EL element (E-3) The organic EL element (E-1) was the same as E-1 except that the angle between the side surface and the bottom surface of the substrate was 120 °, and the other adjacent angle was also 120 ° (see FIG. 5).
  • Resin The following materials were used as the resin for molding the light scattering member.
  • Polycarbonate resin Panlite L-1225L manufactured by Teijin Chemicals Ltd. Production of Light Scattering Member The produced hollow silica particles and the polycarbonate resin were blended so as to have a volume ratio of 7: 3, and were mixed so as to be heated to 320 ° C. to be uniform. Thereafter, a molded article of the light scattering member was produced so that the shape was as shown in FIG. 3, FIG. 4, and FIG.
  • Light-scattering particle size distribution measuring method The average particle size of the light-scattering particles was measured with the following apparatus, and the mode of the particle size distribution was taken as the average particle size of the powder.
  • Particle size distribution measuring device Mastersizer 2000E, manufactured by Malvern Instruments ⁇ Production of surface emitting panel> Hollow silica having an average particle diameter of 50 ⁇ m was solidified with polycarbonate, and a molded product of the light diffusing member was produced so that the shape of the light scattering member was as shown in FIGS.
  • Two organic EL elements are arranged on a 0.3 mm panel construction substrate made of glass and fixed with an adhesive, and the molded products of the various light diffusion members are placed between the transparent substrates of the organic EL elements.
  • the electrodes of adjacent organic EL elements were connected to produce the following various surface-emitting panels.
  • a light extraction sheet is attached to the light scattering member.

Landscapes

  • Electroluminescent Light Sources (AREA)

Abstract

L'invention porte sur un panneau à émission de lumière par la surface tel qu'un dispositif d'éclairage qui est capable d'améliorer l'obscurité entre des panneaux lorsqu'une pluralité de panneaux source de lumière surfacique utilisant des éléments électroluminescents organiques sont reliés afin d'agrandir une aire d'émission de lumière pour obtenir une émission de lumière uniforme. Le panneau à émission de lumière par la surface, dans lequel une pluralité des éléments électroluminescents organiques dans lesquels au moins une première électrode, une seconde électrode et une couche d'émission de lumière entre les première et seconde électrodes sont formées sur un substrat sont agencés sur la même surface d'un substrat pour une configuration de panneau, est caractérisé en ce que (1) le panneau à émission de lumière par la surface comprend des éléments diffuseurs de lumière agencés entre les substrats d'éléments électroluminescents organiques adjacents, et est caractérisé en ce que (2) lorsque l'angle entre les surfaces latérales et les surfaces inférieures d'un substrat des surfaces latérales des deux substrats en contact avec les éléments diffuseurs de lumière agencés entre les substrats de la pluralité d'éléments électroluminescents organiques est réglé à 90° ± α (où 5° ≤ α ≤ 45°), l'angle entre les surfaces latérales et les surfaces inférieures de l'autre des substrats adjacents est de 90° ± β (où 5° ≤ β ≤ 45°; α et β pouvant être de la même valeur).
PCT/JP2009/064942 2008-09-22 2009-08-27 Panneau à émission de lumière par la surface WO2010032596A1 (fr)

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WO2013048680A1 (fr) * 2011-09-30 2013-04-04 General Electric Company Dispositifs d'oled comprenant des objets creux
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WO2013128108A1 (fr) * 2012-02-29 2013-09-06 Saint-Gobain Placo Panneau lumineux et paroi de batiment
JP2014127311A (ja) * 2012-12-26 2014-07-07 Mitsubishi Rayon Co Ltd 面発光体及びその製造方法
WO2014148409A1 (fr) * 2013-03-21 2014-09-25 コニカミノルタ株式会社 Dispositif émetteur de lumière électroluminescent organique
JP2015005552A (ja) * 2013-06-19 2015-01-08 株式会社小糸製作所 車両用灯具
JPWO2014017242A1 (ja) * 2012-07-27 2016-07-07 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子
EP2648240A3 (fr) * 2012-04-06 2016-07-27 Corning Precision Materials Co., Ltd. Substrat pour dispositif électroluminescent organique présentant une efficacité d'extraction de lumière améliorée, son procédé de fabrication et dispositif électroluminescent organique ayant celui-ci
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US20130026461A1 (en) * 2010-04-08 2013-01-31 Asahi Glass Company, Limited Organic led element, translucent substrate, and method for manufacturing organic led element
US9419248B2 (en) 2010-04-08 2016-08-16 Asahi Glass Company, Limited Organic LED element, translucent substrate, and method for manufacturing organic LED element
WO2012132782A1 (fr) * 2011-03-31 2012-10-04 パナソニック株式会社 Élément organique électroluminescent, module organique électroluminescent unité et dispositif d'éclairage
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US9316369B2 (en) 2012-02-29 2016-04-19 Saint-Gobain Placo Luminous panel and building wall
EP2648240A3 (fr) * 2012-04-06 2016-07-27 Corning Precision Materials Co., Ltd. Substrat pour dispositif électroluminescent organique présentant une efficacité d'extraction de lumière améliorée, son procédé de fabrication et dispositif électroluminescent organique ayant celui-ci
JPWO2014017242A1 (ja) * 2012-07-27 2016-07-07 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子
JP2014127311A (ja) * 2012-12-26 2014-07-07 Mitsubishi Rayon Co Ltd 面発光体及びその製造方法
WO2014148409A1 (fr) * 2013-03-21 2014-09-25 コニカミノルタ株式会社 Dispositif émetteur de lumière électroluminescent organique
JPWO2014148409A1 (ja) * 2013-03-21 2017-02-16 コニカミノルタ株式会社 有機エレクトロルミネッセンス発光装置
JP2015005552A (ja) * 2013-06-19 2015-01-08 株式会社小糸製作所 車両用灯具
US11139345B2 (en) * 2017-12-07 2021-10-05 Boe Technology Group Co., Ltd. Display panel, display apparatus, and method of fabricating display panel

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