WO2010084923A1 - 電子デバイス用基板およびこれを用いた電子デバイス - Google Patents
電子デバイス用基板およびこれを用いた電子デバイス Download PDFInfo
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- WO2010084923A1 WO2010084923A1 PCT/JP2010/050729 JP2010050729W WO2010084923A1 WO 2010084923 A1 WO2010084923 A1 WO 2010084923A1 JP 2010050729 W JP2010050729 W JP 2010050729W WO 2010084923 A1 WO2010084923 A1 WO 2010084923A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—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
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/77—Coatings having a rough surface
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to an electronic device substrate and an electronic device using the same, and more particularly to an electronic device substrate such as an organic LED (Organic Light Emitting Diode).
- an organic LED Organic Light Emitting Diode
- An organic LED element is a process in which an organic layer is sandwiched between electrodes, a voltage is applied between the electrodes, holes and electrons are injected, recombined in the organic layer, and a light emitting molecule moves from an excited state to a ground state. Extracts the generated light and is used in displays, backlights, and lighting applications.
- the refractive index of the organic layer is about 1.8 to 2.1 at a wavelength of 430 nm.
- ITO Indium Tin Oxide
- the refractive index differs depending on the ITO film forming conditions and composition (Sn—In ratio), but 1.9 to 2.1. The degree is common.
- Patent Document 1 proposes a structure in which a light scattering layer, which is a semi-transparent material layer, is provided on one side of a substrate (paragraphs 0039 to 0040).
- the structure (paragraph 0070) etc. which provided the light-scattering part between the board
- the reflective electrode surface is not visually recognized like a mirror surface, and the appearance is improved.
- the scattering property is reduced, or when there is no light scattering portion, the reflective electrode is visually recognized as a mirror surface, which may be undesirable in appearance.
- the glass substrate formed by the float method may be used.
- undulation is likely to occur in the substrate due to waves generated in the molten metal bath, contact with a roll carrying the glass ribbon, temperature change in the cooling process, and the like. Therefore, it is known to mechanically polish the substrate surface in order to obtain the flatness of the substrate surface.
- the polished glass substrate has minute polishing flaws formed on the surface, which causes a short circuit between the anode and the cathode.
- Patent Document 2 an organic LED element has been proposed in which an electrode is formed on a surface having undulations
- An object of the present invention is to provide an optical device capable of suppressing specular visibility by paying attention to the undulation of the substrate surface.
- the present invention is an electronic device substrate comprising a substrate having first and second opposing main surfaces and an electrode pattern on the first main surface of the substrate,
- the first principal surface is a surface constituting the undulation constituted by a curved surface
- the wave undulation wavelength R ⁇ a of the surface is larger than 50 ⁇ m
- the ratio Ra / R ⁇ a of the roughness Ra to the undulation wavelength R ⁇ a is 1.0 ⁇ 10 ⁇ 4 or more and 3.0 ⁇ 10 ⁇ 2 or less. According to this configuration, specular visibility can be suppressed by the undulation of the surface.
- this invention is the said board
- substrate comprises a glass substrate and the glass layer formed in the 1st main surface of the said glass substrate,
- the said glass layer is the said glass substrate.
- a second surface abutting on the first main surface side and a first surface facing the second surface, wherein the first surface is a surface constituting a swell formed of a curved surface.
- the scattering layer is made of glass, so that stability and high strength can be realized, and the scattering property is increased without increasing the thickness as compared with a light-transmitting substrate made of original glass. It is possible to provide a translucent substrate having excellent resistance.
- the present invention is the above electronic device substrate, wherein an organic LED element is formed on the first main surface. Since the organic LED element is a device that emits light by applying a voltage to an organic layer sandwiched between electrodes, a local change in the distance between the electrodes tends to cause deterioration of the organic layer due to concentration of an electric field. However, according to the said structure, the local change of the distance between electrodes can be suppressed.
- the present invention provides the electronic device substrate, wherein the second main surface is flatter than the first main surface. According to this configuration, it is possible to prevent the reflected image from being distorted when viewed from the second main surface side of the substrate when no light is emitted.
- the first main surface of the substrate is a surface constituting a swell composed of a curved surface
- the second main surface is a surface flatter than the first main surface, whereby an element
- the sealing material on the base is also mounted when the substrate on which the element is formed is placed on the base, the sealing material is applied to the outer periphery, and the sealing substrate is overlaid and cured.
- the surface to be bonded is flat, and sufficient adhesiveness can be ensured.
- the substrate has a glass substrate and a glass layer formed on the first main surface of the glass substrate
- the second surface that contacts the first main surface side of the glass substrate faces the second surface.
- glass is also applied when a sealing material is applied to the outer periphery of the glass substrate where the glass layer (scattering layer) is not formed and the sealing substrate is overlaid and cured.
- the surface to which the sealing material on the substrate adheres is flat, and sufficient adhesion can be secured. That is, when the substrate has a glass substrate and a glass layer having waviness, the sealing material on the glass substrate is bonded by not providing the glass layer having waviness on the portion where the sealing substrate is overlapped to form a seal.
- the surface to be performed can be a flat surface, and sufficient adhesiveness can be ensured.
- the electronic device of the present invention includes a substrate that is a surface constituting a undulation in which at least the first main surface is formed of a curved surface, of the first and second main surfaces facing each other, and the substrate
- the ratio Ra / R ⁇ a of the undulation roughness Ra to the undulation wavelength R ⁇ a is 1.0 ⁇ 10 ⁇ 4 or more and 3.0 ⁇ 10 ⁇ 2 or less.
- the present invention includes the electronic device described above, wherein the surface roughness Ra of the surface constituting the swell is 30 nm or less.
- the present invention is the above electronic device, wherein the first electrode is formed on the scattering layer and has a third refractive index that is the same as or lower than the first refractive index. Including those that are
- the scattering material density ⁇ 4 includes those satisfying ⁇ 4 > ⁇ 3 .
- the present invention is the above electronic device, wherein the scattering layer is expressed in mol%, P 2 O 5 15-30%, SiO 2 0-15%, B 2 O 3 0-18%, Nb 2 O 5 5-40%, TiO 2 0-15%, WO 3 0-50%, Bi 2 O 3 0-30%, provided that Nb 2 O 5 + TiO 2 + WO 3 + Bi 2 O 3 20-60%, Li 2 O 0-20%, Na 2 O 0-20%, K 2 O 0-20%, but Li 2 O + Na 2 O + K 2 O 5-40%, MgO 0-10%, CaO 0-10%, SrO 0 -10%, BaO 0-20%, ZnO 0-20%, Ta 2 O 5 0-10%.
- the present invention is the above electronic device, wherein the scattering layer is formed on the translucent substrate and has a base having a first refractive index at at least one wavelength of light emitted from the LED element. And a plurality of scattering materials located inside the base material and having a second refractive index different from that of the base material, formed on the scattering layer, and the same or lower than the first refractive index
- a transparent electrode as a first electrode having a third refractive index at the wavelength, a layer having a photoelectric conversion function formed on the transparent electrode, and a layer having a light emitting function.
- a reflective electrode as a second electrode.
- the present invention includes the electronic device as described above, wherein the layer having a photoelectric conversion function is a layer having a light emitting function.
- the present invention includes the electronic device, wherein the layer having the photoelectric conversion function is a layer having a light detection function.
- the present invention includes the electronic device described above, wherein the layer having the photoelectric conversion function is a layer having a power generation function.
- the present invention includes the electronic device described above, wherein the functional layer is a dielectric layer.
- the roughness Ra and the average wavelength R ⁇ a are based on the JISB0601 (2001) standard (ISO97 translation standard) with a short wavelength cutoff value of 25.0 ⁇ m and a long wavelength cutoff value of 2.5 mm. Indicates the calculated value.
- the surface roughness Ra is a microscopic surface roughness, and is a value calculated according to JIS B0601 (1994) with a long wavelength cutoff value of 10 ⁇ m.
- the present invention when an optical device is formed by forming a reflective film on the translucent substrate side as an electronic device, the visibility of the reflective film can be suppressed due to the presence of waviness.
- the scattering layer by constituting the scattering layer with glass, stability and high strength can be realized, and the scattering property is excellent without increasing the thickness as compared with a transparent substrate made of original glass. It becomes possible to provide a translucent substrate.
- (A) shows the measurement result of the surface of the scattering layer which has not been polished
- (B) is a graph showing the measurement result of the surface of the polished scattering layer.
- FIG. 1A is a substrate for an electronic device according to an embodiment of the present invention
- FIG. 1B is a cross-sectional view showing the structure of an organic LED element provided with the substrate for an electronic device.
- the substrate for an electronic device for forming the organic LED element of the present invention was formed on a glass substrate 101 and a surface 101a on the first main surface side of the glass substrate 101 as shown in FIG.
- a translucent electrode 103 is formed on the first surface 102a.
- FIG. 1A shows a state before the electrode is formed.
- this surface has a undulation wavelength R ⁇ a larger than 50 ⁇ m, and the ratio Ra / R ⁇ a of the surface roughness Ra of the undulation surface to the undulation wavelength R ⁇ a is 1.0 ⁇ 10 ⁇ 4 or more and 3.0. It is desirable that it is 10 ⁇ 2 or less.
- Reference numeral 101b denotes a second main surface.
- the organic LED element of this invention is comprised by the translucent board
- the translucent substrate with electrode 100 includes a substrate 101 made of a translucent glass substrate, a scattering layer 102, and a translucent electrode 103.
- the translucent substrate with electrode 100 used in the present invention comprises a translucent glass substrate 101, a scattering layer 102 made of glass formed on the glass substrate, and a translucent electrode 103, and the scattering layer Includes a base material having a first refractive index with respect to one wavelength of transmitted light, and a plurality of scattering materials 104 having a second refractive index different from the base material and dispersed in the base material. And the distribution of the scattering material in the scattering layer is reduced from the inside of the scattering layer toward the translucent electrode.
- the translucent electrode 103 has a third refractive index that is the same as or lower than the first refractive index.
- the density ⁇ 1 of the scattering material at half the thickness ( ⁇ / 2) of the scattering layer 102 made of glass, and the surface of the scattering layer on the side facing the translucent electrode (that is, the surface on the substrate side) satisfies ⁇ 1 ⁇ ⁇ 2 .
- ⁇ 4 > ⁇ 3 is satisfied.
- the layer having a light emitting function can be uniformly formed, and a light-transmitting electrode and a reflection formed on the layer having a light emitting function are formed.
- the distance between the electrodes with respect to the surface of the conductive electrode (second electrode) is also uniform.
- a large voltage is not locally applied to the layer having a light emitting function, the life can be extended.
- a display device composed of fine pixels such as a high-resolution display, it is necessary to form a fine pixel pattern, and surface irregularities cause variations in pixel positions and sizes.
- the organic LED element is short-circuited by the unevenness, but a fine pattern can be formed with high accuracy.
- the scattering layer is formed directly on the glass substrate, it may be formed via a barrier layer, for example, by forming a silica thin film on the glass substrate by sputtering and then forming a scattering layer.
- a barrier layer for example, by forming a silica thin film on the glass substrate by sputtering and then forming a scattering layer.
- FIG. 2 the schematic diagram of the state which apply
- This state can be obtained, for example, by dispersing the glass particles G in a solvent or a mixture of a resin and a solvent and applying it to a desired thickness.
- the maximum size of the glass particles G is about 0.1 to 10 ⁇ m.
- the state shown in FIG. 2 is obtained by heating the resin film in which the glass particles G are dispersed and decomposing the resin.
- FIG. 2 is simply described, there is a gap between the glass grains.
- the softening and flow of the glass proceed, and the gap inside the glass forms spherical bubbles.
- the dent caused by the gap between the glass particles G is smoothed. This is shown in FIG.
- gas may be generated when the glass is softened to form air bubbles.
- an organic substance is attached to the surface of the glass layer, it may be decomposed to generate CO 2 and generate bubbles.
- a substance that decomposes by heat as described above may be introduced to actively generate bubbles. Such a state is usually obtained near the softening temperature.
- the viscosity of the glass is as high as 10 7.6 poise at the softening temperature, and if the bubble size is several ⁇ m or less, it cannot float. Therefore, the material composition is adjusted so as to generate small bubbles, and the surface can be further smoothed while suppressing the bubbles from rising by further increasing the temperature or increasing the holding time.
- the density of the scattering material as shown in FIG.
- the outermost surface of the glass layer forms a curved surface having waviness.
- a schematic diagram thereof is shown in FIG.
- the waviness is one having a period R ⁇ a of 10 ⁇ m or more.
- the size (roughness) of the swell is about 0.01 to 5 ⁇ m in Ra. Even when such undulation is present, micro smoothness is maintained.
- R ⁇ a> 10 ⁇ m and Ra / R ⁇ a 1.0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 1
- the firing temperature is desirably about 40 to 100 ° C. higher than the glass transition temperature.
- the temperature in the case of non-crystallized glass, it is desirable that the temperature be higher by about 40 ° C to 60 ° C. If the temperature is too low, sintering will be insufficient and the surface will not be smooth. Therefore, it is more desirable that the firing temperature be about 50 ° C. to 60 ° C. higher than the glass transition temperature.
- the scattering layer can suppress a decrease in aesthetics due to reflection when the organic LED element formed in the upper layer is a reflective electrode by forming a undulation whose surface forms a curved surface.
- reflection by the reflective electrode occurs at the time of non-light emission, and it has been a problem to impair the beauty. However, such reflection is eliminated and the beauty at the time of non-light emission is maintained. be able to.
- the surface roughness Ra of the scattering layer surface is preferably 30 nm or less. More preferably, the scattering layer has a surface roughness of 10 nm or less.
- the surface roughness is 30 nm or less, preferably 10 nm or less. If the surface roughness exceeds 30 nm, the coverage of the organic layer formed thereon may be deteriorated, and a short circuit is caused between the translucent electrode formed on the glass scattering layer and the other electrode. May occur. Although the element is not lit due to the short circuit between the electrodes, it may be possible to repair it by applying an overcurrent.
- the roughness of the glass scattering layer is preferably 10 nm or less, and more preferably 3 nm or less. It has been found that the surface roughness of a certain material system can be 10 nm or less when the firing temperature is 570 ° C. or more (see Table 1). Although the optimum firing conditions differ depending on the material system, it is possible to suppress the presence of the scattering material on the outermost surface by controlling the kind and size of the scattering material, and to obtain a scattering layer having excellent surface smoothness.
- the size of the scattering material is such that when there are bubbles in the scattering layer, if the bubbles increase, the buoyancy increases during the scattering layer formation process, such as the firing process, and the buoyancy tends to rise. Can rupture and significantly reduce surface smoothness. In addition, since the number of scattering substances in the portion is relatively reduced, the scattering property is lowered only in that portion. If such large bubbles are aggregated, they become uneven and can be visually recognized. Furthermore, the ratio of bubbles having a diameter of 5 ⁇ m or more is desirably 15 vol% or less, more desirably 10 vol% or less, and further desirably 7 vol% or less.
- the ratio of the scattering material having the maximum length of 5 ⁇ m or more is desirably 15 vol% or less, desirably 10 vol% or less, and more desirably 7 vol% or less.
- the swell and reflection were evaluated using eight types of samples with different swells. For the swell evaluation, measurement was performed with a SURFCOM 1400D manufactured by Tokyo Seimitsu using a glass substrate with a scattering layer. Here, the long wavelength cut-off value was 2.5 mm. Next, the reflection was evaluated by visual observation using a glass substrate with a scattering layer deposited with aluminum. The results are shown in Table 1.
- a and B are glasses whose compositions are shown in Table 11
- C and D are glasses whose compositions are shown in Tables 12 and 13, respectively.
- the glass transition temperature Tg of A is 499 ° C
- B is 481 ° C
- C is 465 ° C
- D is 445 ° C.
- an Al film having a thickness of 80 nm was formed on the glass substrate with a scattering layer by vacuum deposition.
- a transparent electrode is formed on the scattering layer, an organic layer such as a hole transport layer, a light emitting layer, and an electron transport layer is further stacked thereon, and an Al layer of the electrode is further stacked thereon.
- the transparent electrode and the organic layer are omitted.
- the total thickness of the organic layer is about several hundred nanometers and follows the irregularities of the scattering layer. Therefore, the presence or absence of the organic layer does not affect the undulation of the surface, so there is no problem even if it is omitted.
- the reflection evaluation method was determined by placing a 0.5 mm diameter mechanical pencil core about 5 mm above the evaluation sample and judging whether the image of the core reflected on the Al surface appeared distorted. This evaluation is carried out by six people a to f. The evaluation results are indicated as ⁇ when the mechanical pencil core appears to be distorted, x when the core appears straight without distortion, and ⁇ when the judgment is difficult.
- the content of the scattering material in the scattering layer is preferably at least 1 vol%. From this experimental result, it can be seen that a sufficient light scattering property can be obtained when the scattering material is contained in an amount of 1 vol% or more.
- the crystal size is 0.1 ⁇ m or more, it functions as a light scattering material.
- the state at this time is shown in FIG.
- the firing temperature is more desirably about 60 ° C. to 80 ° C. higher than the glass transition temperature, and most desirably 60 ° C. to 70 ° C.
- the material composition and firing conditions it is possible to obtain a light-transmitting substrate in which the density of the scattering material on the outermost surface of the scattering layer is smaller than the density of the scattering material inside the scattering layer.
- the scattering at x where the density ⁇ 1 of the scattering material at half the thickness ( ⁇ / 2) of the scattering layer made of glass and the distance x from the outermost surface of the scattering layer satisfy 0 ⁇ x ⁇ ⁇ / 2.
- the scattering material may be a bubble, a material particle having a composition different from that of the base layer, or a precipitated crystal of the base layer. These may be a single substance or a mixture.
- the size, bubble distribution, and density of the bubbles can be adjusted by adjusting the baking conditions such as the baking temperature.
- the size, distribution and density of the scattering material can be adjusted by adjusting the material composition and the firing conditions such as the firing temperature.
- the size, bubble distribution, and density of bubbles can be adjusted by adjusting the firing conditions such as the firing temperature.
- the first refractive index of the base layer at at least one wavelength among wavelengths ⁇ (430 nm ⁇ ⁇ 650 nm) is 1.8 or more.
- the refractive index can be easily adjusted by adjusting the material composition of the glass material.
- a material having a high visible light transmittance is a plastic substrate in addition to a glass substrate.
- the material of the glass substrate include inorganic glass such as alkali glass, non-alkali glass, and quartz glass.
- the plastic substrate material include polyester, polycarbonate, polyether, polysulfone, polyethersulfone, polyvinyl alcohol, and fluorine-containing polymers such as polyvinylidene fluoride and polyvinyl fluoride.
- the plastic substrate may have a barrier property.
- the thickness of the light-transmitting substrate 101 is preferably 0.1 mm to 2.0 mm in the case of glass. However, if the thickness is too thin, the strength decreases, so that the thickness is particularly preferably 0.5 mm to 1.0 mm.
- the thermal expansion coefficient is 50 ⁇ 10 ⁇ 7 / ° C. or higher, preferably 70 ⁇ 10 ⁇ 7 / ° C. or higher, more preferably 80 ⁇ . 10 ⁇ 7 / ° C. or higher is preferable.
- the average thermal expansion coefficient of the scattering layer from 100 ° C. to 400 ° C. is from 70 ⁇ 10 ⁇ 7 / ° C. to 95 ⁇ 10 ⁇ 7 / ° C.
- the glass transition temperature is from 450 ° C. to 550 ° C. Is desirable.
- the calculation software used is a software SPEOS manufactured by OPTIS. While this software is a ray tracing software, the scattering layer can apply the theoretical formula of Mie scattering. Actually, the thickness of the organic layer used as a layer having a light emitting function such as a charge injection / transport layer and a light emitting layer is actually about 0.1 ⁇ m to 0.3 ⁇ m in total. Therefore, the minimum thickness allowed by software is set to 1 ⁇ m. For the same reason, the total thickness of the glass substrate and the scattering layer was set to 100 ⁇ m.
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode. Although these refractive indexes are assumed to be the same in the calculation, the refractive indexes of the organic layer and the translucent electrode are approximately the same value, and the calculation results are not greatly changed.
- the organic layer is thin, a waveguide mode due to interference stands when considered strictly, but even if handled geometrically, the result does not change greatly, so it is enough to estimate the effect of the present invention by calculation It is.
- emitted light is emitted from a total of six surfaces without directivity.
- the calculation was made assuming that the total luminous flux was 1000 lm and the number of light beams was 100,000 or 1 million.
- the light emitted from the translucent substrate was captured by the light receiving surface installed on the upper 10 ⁇ m of the translucent substrate, and the extraction efficiency was calculated from the illuminance.
- the scattering layer 102 is formed by forming a glass powder on a glass substrate by a method such as coating and baking at a desired temperature, and has a base having a first refractive index. And a plurality of scattering materials 104 having a second refractive index different from that of the base material 105 and dispersed in the base material 105, from the inside of the scattering layer to the outermost surface, the scattering material 104
- the distribution of the scattering material in the layer is small, and by using the glass layer, as described above, the surface smoothness can be maintained while having excellent scattering characteristics, and the light emitting device For example, it is possible to realize light extraction with extremely high efficiency.
- a material (base material) having a coated main surface and high light transmittance is used.
- the base material glass, crystallized glass, translucent resin, or translucent ceramic is used.
- the glass material include soda lime glass, borosilicate glass, alkali-free glass, and quartz glass.
- a plurality of scattering substances 104 (for example, there are bubbles, precipitated crystals, material particles different from the base material, and phase separation glass) are formed inside the base material.
- the particle refers to a small solid substance such as a filler or ceramic.
- Air bubbles refer to air or gas objects.
- phase-separated glass means the glass comprised by two or more types of glass phases.
- the refractive index of the base material is equal to or not higher than the refractive index of the translucent electrode material. This is because when the refractive index is low, a loss due to total reflection occurs at the interface between the base material and the translucent electrode material. However, even if the refractive index of the base material is small, the extraction efficiency is compensated by the distribution of the scattering material so that the refractive index of the entire scattering layer is equal to or higher than the refractive index of the translucent electrode. It can also be increased.
- the refractive index of the scattering layer only needs to exceed at least a part of the emission spectrum range of the light emitting layer (for example, red, blue, green, etc.), but exceeds the entire emission spectrum range (430 nm to 650 nm). Preferably, it exceeds the entire visible light wavelength range (360 nm to 830 nm).
- the main surface of the scattering layer needs to be smooth to prevent a short circuit between the electrodes of the organic LED.
- the scattering material protrudes from the main surface of the scattering layer.
- the scattering material does not protrude from the main surface of the scattering layer, it is preferable that the scattering material does not exist within 0.2 ⁇ m from the main surface of the scattering layer.
- the arithmetic average roughness (Ra) defined in JIS B0601-1994 of the main surface of the scattering layer is preferably 30 nm or less, more preferably 10 nm or less (see Table 1), and particularly preferably 1 nm or less.
- Both the scattering material and the base material may have a high refractive index, but the difference in refractive index ( ⁇ n) is preferably 0.2 or more in at least a part of the emission spectrum range of the light emitting layer. In order to obtain sufficient scattering characteristics, the difference in refractive index ( ⁇ n) is 0.2 or more over the entire emission spectrum range (430 nm to 650 nm) or the entire visible light wavelength range (360 nm to 830 nm). More preferred.
- the high light transmittance material has a high refractive index glass and the scattering material has a gaseous object, that is, a bubble.
- the refractive index of the base material may be smaller than the refractive index of the translucent electrode. For this reason, the freedom degree in selection of the material which can be used becomes high.
- the refractive index of the base material be as high as possible, so that the base material is preferably made of glass having a high refractive index.
- a high refractive index component one or more components selected from P 2 O 5 , SiO 2 , B 2 O 3 , Ge 2 O, and TeO 2 are used as a high refractive index component as a network former. , TiO 2 , Nb 2 O 5 , WO 3 , Bi 2 O 3 , La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , ZrO 2 , ZnO, BaO, PbO, Sb 2 O 3 Alternatively, a high refractive index glass containing two or more kinds of components can be used.
- alkali oxides, alkaline earth oxides, fluorides, and the like may be used as long as the physical properties required for the refractive index are not impaired.
- Specific glass systems include B 2 O 3 —ZnO—La 2 O 3 system, P 2 O 5 —B 2 O 3 —R ′ 2 O—R ′′ O—TiO 2 —Nb 2 O 5 —WO 3 —.
- R ′ represents an alkali metal element
- R ′′ represents an alkaline earth metal element.
- the above is an example, and if it is the structure which satisfy
- the color of light emission can be changed.
- known ones such as transition metal oxides, rare earth metal oxides and metal colloids can be used alone or in combination.
- Whitening is a method of spatially painting red, blue, and green (painting method), a method of laminating light emitting layers having different emission colors (lamination method), and providing blue light that is separated spatially.
- a method (color conversion method) for performing color conversion with a color conversion material is known.
- a white layer can be obtained uniformly, so a lamination method is common.
- the light emitting layer to be stacked uses a combination that turns white by additive color mixing. For example, a blue-green layer and an orange layer may be stacked, or red, blue, and green may be stacked.
- the lamination method has an advantage that there is no need to spatially change the color arrangement, it has the following two problems.
- the first problem is that since the organic layer is thin as described above, the extracted emitted light is affected by interference. Therefore, the color changes depending on the viewing angle. In the case of white, such a phenomenon may be a problem because the sensitivity to the color of human eyes is high.
- the second problem is that the carrier balance is shifted while the light is emitted, the light emission luminance of each color is changed, and the color is changed.
- organic LED elements do not have the idea of dispersing the phosphor in the scattering layer or the diffusion layer, and thus cannot solve the problem that the above-mentioned color changes. For this reason, conventional organic LED elements are still insufficient for backlight and illumination applications.
- the organic LED element substrate and the organic LED element of the present invention can use a fluorescent substance as a scattering substance or a base material. Therefore, the effect of changing the color by performing wavelength conversion can be brought about by the light emission from the organic layer. In this case, the light emission color of the organic LED can be reduced, and the emitted light is scattered and emitted, so that the angle dependency of the color and the temporal change of the color can be suppressed.
- the scattering layer is produced by coating and baking.
- the glass is made into a frit paste. Is preferred.
- the glass softening point (Ts) of the scattering layer is lower than the strain point (SP) of the substrate glass, and the difference in thermal expansion coefficient ⁇ . Is desirable to be small.
- the difference between the softening point and the strain point is preferably 30 ° C. or higher, and more preferably 50 ° C. or higher.
- the difference in expansion coefficient between the scattering layer and the substrate glass is preferably ⁇ 10 ⁇ 10 ⁇ 7 (1 / K) or less, and more preferably ⁇ 5 ⁇ 10 ⁇ 7 (1 / K) or less.
- the frit paste refers to a glass powder dispersed in a resin, a solvent, a filler or the like.
- the glass layer can be coated by patterning and baking the frit paste using a pattern forming technique such as screen printing. The technical outline is shown below.
- (Frit paste material) Glass powder
- the particle diameter of the glass powder is 1 ⁇ m to 10 ⁇ m.
- a filler may be added. Specifically, zircon, silica, alumina or the like is used as the filler, and the particle size is 0.1 ⁇ m to 20 ⁇ m.
- each component is as follows in terms of mol%.
- P 2 O 5 is an essential component that forms this glass-based skeleton and vitrifies it, but if the content is too small, the devitrification of the glass becomes large and it becomes impossible to obtain glass, so 15% or more Is preferable, and 18% or more is more preferable.
- the content is preferably 30% or less, and more preferably 28% or less.
- B 2 O 3 is an optional component that is a component that improves devitrification resistance and decreases the coefficient of thermal expansion by adding it to the glass, but if the content is too large, the refractive index decreases. Therefore, 18% or less is preferable and 15% or less is more preferable.
- SiO 2 is an optional component that is a component that stabilizes the glass by adding a small amount and improves the devitrification resistance. However, if the content is too large, the refractive index decreases, so 15% Or less, more preferably 10% or less, and particularly preferably 8% or less.
- Nb 2 O 5 is an essential component that simultaneously has the effects of improving the refractive index and enhancing weather resistance. Therefore, the content is preferably 5% or more, and more preferably 8% or more. On the other hand, if the content is too large, devitrification becomes stronger and glass cannot be obtained. Therefore, the content is preferably 40% or less, more preferably 35% or less.
- TiO 2 is an optional component that improves the refractive index.
- the content is preferably 15% or less, and more preferably 13% or less.
- WO 3 is an optional component that improves the refractive index, lowers the glass transition temperature, and lowers the firing temperature. However, when it is introduced excessively, the glass is colored, resulting in a decrease in light extraction efficiency. Is preferably 50% or less, more preferably 45% or less.
- Bi 2 O 3 is a component improving the refractive index, can be introduced in a relatively large amount in the glass while maintaining the stability of the glass. However, when it introduce
- Nb 2 O 5 , TiO 2 , WO 3 and Bi 2 O 3 must be included.
- the total amount of (Nb 2 O 5 + TiO 2 + WO 3 + Bi 2 O 3 ) is preferably 20% or more, and more preferably 25% or more.
- coloring or devitrification becomes too strong, so that it is preferably 60% or less, and more preferably 55% or less.
- Ta 2 O 5 is an optional component that improves the refractive index. However, if the amount added is too large, devitrification resistance is lowered and the price is high, so the content is 10% or less. Preferably, 5% or less is more preferable.
- Alkali metal oxides (R 2 O) such as Li 2 O, Na 2 O, K 2 O have the effect of improving the meltability and lowering the glass transition temperature, and at the same time, increasing the affinity with the glass substrate. , Has the effect of increasing the adhesion. Therefore, it is desirable to contain one or more of these.
- the total amount of Li 2 O + Na 2 O + K 2 O is preferably 5% or more, and more preferably 10% or more. However, if it is contained excessively, the stability of the glass is impaired, and since both are components that lower the refractive index, the refractive index of the glass is lowered, and the desired light extraction efficiency is improved. I can't expect it. Therefore, the total content is preferably 40% or less, and more preferably 35% or less.
- Li 2 O is a component for decreasing the glass transition temperature and improving the solubility.
- the content is desirably 20% or less, and more desirably 15% or less.
- Both Na 2 O and K 2 O are optional components that improve the meltability, but if they are contained excessively, the refractive index is lowered, and the desired light extraction efficiency cannot be achieved. Therefore, each content is preferably 20% or less, and more preferably 15% or less.
- BaO is a component that improves the refractive index and at the same time improves the solubility. However, if added excessively, the stability of the glass is impaired, so its content is preferably 20% or less, and 18% or less. More preferably. MgO, CaO, and SrO are optional components that improve the meltability. However, since they are components that simultaneously reduce the refractive index, they are preferably 10% or less, and more preferably 8% or less.
- a small amount of a refining agent, a vitrification promoting component, a refractive index adjusting component, a wavelength converting component, or the like may be added within a range that does not impair the required glass properties.
- Sb 2 O 3 and SnO 2 are exemplified as the fining agent, GeO 2 , Ga 2 O 3 , In 2 O 3 as the vitrification promoting component, ZrO 2 as the refractive index adjusting component
- Examples of Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and wavelength conversion component include rare earth components such as CeO 2 , Eu 2 O 3 , and Er 2 O 3 .
- SiO 2 is a component that improves the stability of the glass when added to this type of glass. However, if the amount introduced is too large, the refractive index decreases and the glass transition temperature increases. Therefore, the content is preferably 20% or less, and more preferably 18% or less. Li 2 O is a component that lowers the glass transition temperature. However, when the introduction amount is too large, the devitrification resistance of the glass is lowered. Therefore, the content is preferably 20% or less, and more preferably 18% or less.
- Na 2 O and K 2 O improve the solubility.
- each is preferably 10% or less, more preferably 8% or less.
- ZnO is an essential component that improves the refractive index of the glass and lowers the glass transition temperature. Therefore, the introduction amount is preferably 5% or more, and more preferably 7% or more.
- the amount is preferably 50% or less, and more preferably 45% or less.
- La 2 O 3 is an essential component that achieves a high refractive index and improves weather resistance when introduced into B 2 O 3 glass. Therefore, the content is preferably 5% or more, and more preferably 7% or more. On the other hand, when the introduction amount is too large, the glass transition temperature becomes high, or the devitrification resistance of the glass is lowered, so that a homogeneous glass cannot be obtained. Therefore, the content is preferably 25% or less, and more preferably 22% or less.
- Gd 2 O 3 is a component that achieves a high refractive index and improves weather resistance when introduced into B 2 O 3 glass, and improves the stability of the glass by coexisting with La 2 O 3 , If the amount introduced is too large, the stability of the glass will decrease, so the content is preferably 25% or less, more preferably 22% or less.
- Y 2 O 3 and Yb 2 O 3 achieve a high refractive index, improve the weather resistance when introduced into B 2 O 3 glass, and improve the stability of the glass by coexisting with La 2 O 3 .
- the content is preferably 20% or less, and preferably 18% or less.
- Rare earth oxides such as La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 are essential components for achieving a high refractive index and improving the weather resistance of glass.
- the total amount of these components, La 2 O 3 + Gd 2 O 3 + Y 2 O 3 + Yb 2 O 3 is preferably 5% or more, and more preferably 8% or more.
- the introduction amount is too large, the devitrification resistance of the glass is lowered, and it becomes impossible to obtain a homogeneous glass.
- Ta 2 O 5 is a component for improving the refractive index.
- the content is 20% or less. It is preferable that it is, and it is more preferable that it is 15% or less.
- Nb 2 O 5 is a component for improving the refractive index.
- the content is too large, the devitrification resistance is lowered or the liquidus temperature is excessively improved, so the content is 20% or less. It is preferable that it is, and it is more preferable that it is 15% or less.
- WO 3 is a component for improving the refractive index. However, if the content is too large, the devitrification resistance is lowered or the liquidus temperature is excessively improved, so the content is 20% or less. It is preferably 15% or less.
- BaO is a component that improves the refractive index. However, if the content is too large, the devitrification resistance is lowered, so that it is preferably 20% or less, and more preferably 15% or less.
- the total amount of the components described above is desirably 90% or more, and more preferably 95% or more. Even components other than those described above may be added within the range not impairing the effects of the present invention for the purpose of clarifying and improving solubility. Examples of such components include Sb 2 O 3 , SnO 2 , MgO, CaO, SrO, GeO 2 , Ga 2 O 3 , In 2 O 3 , and fluorine.
- a scattering layer containing SiO 2 as an essential component and containing one or more components of Nb 2 O 5 , TiO 2 , and Bi 2 O 3 is expressed in terms of mol%, SiO 2 20 to 50%, B 2 O 3 0 to 20%, Nb 2 O 5 1-20%, TiO 2 1-20%, Bi 2 O 3 0-15%, ZrO 2 0-15%, Nb 2 O 5 + TiO 2 + Bi 2 O 3 + ZrO 2 5-40 %, Li 2 O 0-40%, Na 2 O 0-30%, K 2 O 0-30%, Li 2 O + Na 2 O + K 2 O 1-40%, MgO 0-20%, CaO 0-20%, Glasses having a composition range of SrO 0-20%, BaO 0-20%, ZnO 0-20% are preferred.
- SiO 2 is an essential component that acts as a network former for forming glass, and if its content is too small, it will not form glass, and it is preferably 20% or more, more preferably 22% or more. preferable.
- B 2 O 3 helps to form glass by adding a relatively small amount with SiO 2 to reduce devitrification. However, if the content is too large, the refractive index is lowered, so the content is 20% or less. It is preferable that it is 18% or less.
- Nb 2 O 5 is an essential component for improving the refractive index, and the content thereof is preferably 1% or more, and more preferably 3% or more. However, since excessive addition reduces the devitrification resistance of the glass and makes it impossible to obtain a homogeneous glass, its content is preferably 20% or less, more preferably 18% or less. preferable.
- TiO 2 is an essential component for improving the refractive index, and the content thereof is preferably 1% or more, and more preferably 3% or more.
- the content is desirably 20% or less, and more desirably 18% or less.
- Bi 2 O 3 is a component for improving the refractive index.
- the content is desirably 15% or less, and more desirably 12% or less.
- Li 2 O, Na 2 O, and K 2 O are components that improve the solubility and lower the glass transition temperature, and further increase the affinity with the glass substrate. Therefore, the total amount Li 2 O + Na 2 O + K 2 O of these components is preferably 1% or more, and more preferably 3% or more.
- the content of the alkali oxide component is preferably 40% or less, and 35% or less. It is more preferable that
- MgO, CaO, SrO, and ZnO are components that improve the solubility of the glass. If added appropriately, the devitrification resistance of the glass can be reduced, but if it is excessively contained, the devitrification becomes high and homogeneous. 20% or less is preferable, and 15% or less is more preferable.
- the total amount of the components described above is desirably 90% or more.
- components other than those described above may be added within the range not impairing the effects of the present invention for the purpose of clarifying and improving solubility. Examples of such components include Sb 2 O 3 , SnO 2 , GeO 2 , Ga 2 O 3 , In 2 O 3 , WO 3 , Ta 2 O 5 , La 2 O 3 , Gd 2 O 3 , Y 2 O. 3 and Yb 2 O 3 .
- the scattering layer containing Bi 2 O 3 as a main component and containing SiO 2 , B 2 O 3 or the like as a glass forming aid is expressed in terms of mol%, Bi 2 O 3 10 to 50%, B 2 O 3 1 40%, SiO 2 0-30%, but B 2 O 3 + SiO 2 10-40%, P 2 O 5 0-20%, Li 2 O 0-15%, Na 2 O 0-15%, K 2 O 0-15%, TiO 2 0-20%, Nb 2 O 5 0-20%, TeO 2 0-20%, MgO 0-10%, CaO 0-10%, SrO 0-10%, BaO 0 Glasses having a composition range of ⁇ 10%, GeO 2 0-10%, and Ga 2 O 3 0-10% are preferred.
- B 2 O 3 is an essential component that works as a network former and assists glass formation in a glass containing a large amount of Bi 2 O 3 , and its content is preferably 1% or more, and more preferably 3% or more. However, when the addition amount is too large, the refractive index of the glass is lowered, so 40% or less is preferable, and 38% or less is more preferable.
- total amount thereof is preferably 5% or more, more preferably 10% or more.
- the refractive index is lowered, so that it is preferably 40% or less, more preferably 38%.
- Li 2 O, Na 2 O, and K 2 O are components for improving the glass solubility and further lowering the glass transition temperature.
- the devitrification resistance of the glass is lowered and is homogeneous. It becomes impossible to obtain glass. For this reason, 15% or less is preferable respectively, and 13% or less is more preferable.
- the total amount of the above alkali oxide components, Li 2 O + Na 2 O + K 2 O is too large, the refractive index is lowered, and the devitrification resistance of the glass is further lowered. The following is more preferable.
- TiO 2 is a component that improves the refractive index. However, when the content is too large, coloring occurs or the devitrification resistance is lowered, so that a homogeneous glass cannot be obtained. Therefore, the content is preferably 20% or less, and more preferably 18% or less.
- Nb 2 O 5 is a component that improves the refractive index.
- the content is preferably 20% or less, and more preferably 18% or less.
- TeO 2 is a component that improves the refractive index without deteriorating the degree of coloring. However, excessive introduction reduces the devitrification resistance and causes coloring when fired after frit formation.
- the content is preferably 20% or less, and more preferably 15% or less.
- GeO 2 is a component that improves the stability of the glass while maintaining a relatively high refractive index. However, since it is extremely expensive, the content is preferably 10% or less, and more preferably 8% or less. More preferably, it is not included.
- Ga 2 O 3 is a component that improves the stability of the glass while maintaining a relatively high refractive index.
- the content is preferably 10% or less, and preferably 8% or less. More preferably, it is even more preferable not to include it.
- the total amount of the components described above is preferably 90% or more, and more preferably 95% or more. Even components other than those described above may be added within the range not impairing the effects of the present invention for purposes such as clarifying, improving solubility, and adjusting the refractive index. Examples of such components include Sb 2 O 3 , SnO 2 , In 2 O 3 , ZrO 2 , Ta 2 O 5 , WO 3 , La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , Yb 2 O. 3 and Al 2 O 3 .
- the glass composition for forming the scattering layer is not particularly limited as long as desired scattering characteristics can be obtained and can be fired by frit paste, but in order to maximize the extraction efficiency, for example, P 2 O 5 is used.
- Nb 2 O 5 , Bi 2 O 3 , TiO 2 , WO 3 a system containing one or more components, B 2 O 3 , La 2 O 3 as essential components, Nb 2 O 5 , ZrO 2 , A system containing one or more components of Ta 2 O 5 and WO 3 , a system containing SiO 2 as an essential component, a system containing one or more components of Nb 2 O 5 and TiO 2 , and containing Bi 2 O 3 as a main component
- a system containing SiO 2 , B 2 O 3 or the like as a glass forming aid.
- R 2 O—RO—BaO—B 2 O 3 —SiO 2 , RO—Al 2 O 3 —P 2 O 5 , R 2 O—B 2 O 3 — SiO 2 (R 2 O is Li 2 O, Na 2 O, or K 2 O, and RO is MgO, CaO, or SrO) or the like can be used.
- Resin Resin supports glass powder and filler in the coating after screen printing.
- Specific examples include ethyl cellulose, nitrocellulose, acrylic resin, vinyl acetate, butyral resin, melamine resin, alkyd resin, and rosin resin.
- ethyl cellulose and nitrocellulose There are ethyl cellulose and nitrocellulose as main agents.
- Butyral resin, melamine resin, alkyd resin, and rosin resin are used as additives for improving the strength of the coating film.
- the binder removal temperature during firing is 350 ° C. to 400 ° C. for ethyl cellulose and 200 ° C. to 300 ° C. for nitrocellulose.
- Solvent Dissolves the resin and adjusts the viscosity required for printing. Also, it does not dry during printing, and dries quickly in the drying process. A boiling point of 200 ° C to 230 ° C is desirable. Blend to adjust viscosity, solid content ratio, drying speed. Specific examples include ether solvents (butyl carbitol (BC), butyl carbitol acetate (BCA), diethylene glycol di-n-butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether due to the dry compatibility of the paste during screen printing.
- ether solvents butyl carbitol (BC), butyl carbitol acetate (BCA), diethylene glycol di-n-butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether due to the dry compatibility of the paste during screen printing.
- Butyl acetate cellosolve alcohol solvents ( ⁇ -terpineol, pine oil, dawanol), ester solvents (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), phthalate ester solvents (DBP) (Dibutyl phthalate), DMP (dimethyl phthalate), DOP (dioctyl phthalate)).
- DBP dibutyl phthalate
- DMP dimethyl phthalate
- DOP dioctyl phthalate
- Mainly used are ⁇ -terpineol and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate).
- DBP dibutyl phthalate
- DMP dimethyl phthalate
- DOP dioctyl phthalate
- a surfactant may be used to adjust viscosity and promote frit dispersion.
- a silane coupling agent may be used to modify the frit surface.
- Frit paste Prepare glass powder and vehicle.
- the vehicle refers to a mixture of resin, solvent, and surfactant. Specifically, a resin, a surfactant, or the like is put into a solvent heated to 50 ° C. to 80 ° C., and then allowed to stand for about 4 to 12 hours, followed by filtration. Next, the glass powder and the vehicle are mixed with a planetary mixer and then uniformly dispersed with three rolls. Thereafter, the mixture is kneaded with a kneader to adjust the viscosity.
- the vehicle is 20 to 30 wt% with respect to 70 to 80 wt% of the glass material.
- the frit paste produced in (1) is printed using a screen printer. It is possible to control the film thickness of the frit paste film formed by the mesh mesh roughness of the screen plate, the emulsion thickness, the pressing pressure during printing, the squeegee pressing amount, and the like. It is dried in a baking furnace after printing.
- Firing The substrate printed and dried in a firing furnace is fired. Firing consists of a binder removal process for decomposing and disappearing the resin in the frit paste and a firing process for sintering and softening the glass powder.
- the binder removal temperature is 350 ° C. to 400 ° C. for ethyl cellulose and 200 ° C. to 300 ° C. for nitrocellulose, and heating is performed in an air atmosphere for 30 minutes to 1 hour. Thereafter, the temperature is raised to sinter and soften the glass.
- the firing temperature is from the softening temperature to the softening temperature + 20 ° C., and the shape and size of the bubbles remaining inside vary depending on the treatment temperature. Then, it cools and a glass layer is formed on a board
- the thickness of the obtained film is 5 ⁇ m to 30 ⁇ m, but a thicker glass layer can be formed by laminating at the time of printing.
- a thicker film can be formed by using a doctor blade printing method or a die coat printing method as described above (green sheet printing).
- green sheet printing When a film is formed on a PET film or the like and then dried, a green sheet is obtained. Next, the green sheet is thermocompression-bonded on the substrate with a roller or the like, and a fired film is obtained through a firing process similar to that of a frit paste.
- the thickness of the obtained film is 50 ⁇ m to 400 ⁇ m, a thicker glass film can be formed by stacking and using green sheets.
- FIG. 11 is a graph showing the relationship between light extraction efficiency (%) and scattering material content (vol%).
- the calculation was performed by dividing the organic layer and the light-transmitting electrode into three parts: an electron injection / transport layer and a light-emitting layer, a hole injection / transport layer, and a light-transmitting electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- Thickness 1 ⁇ m, refractive index: 1.9), scattering layer (thickness: 30 ⁇ m, base material refractive index: 1.9, scattering material refractive index: 1.0), translucent substrate (thickness: 100 ⁇ m) , Refractive index: 1.54), and calculated by dividing 1000 lm of luminous flux into 100,000 (wavelength 550 nm).
- the content of the scattering material in the scattering layer is preferably 1 vol% or more. Although the behavior varies depending on the size of the scattering material, if the content of the scattering material in the scattering layer is 1 vol%, the light extraction efficiency can be 40% or more.
- the graph also shows the relationship between the diameter of the scattering material and the light extraction efficiency. Specifically, when the diameter of the scattering material is 1 ⁇ m, the light extraction efficiency can be made 70% or more even when the scattering material content is in the range of 1 vol% to 20 vol%. Is in the range of 2 vol% to 15 vol%, the light extraction efficiency can be increased to 80% or more. If the diameter of the scattering material is 2 ⁇ m, the light extraction efficiency can be made 65% or more even when the scattering material content is in the range of 1 vol% to 20 vol%. In particular, the scattering material content is 5 vol%. If it is above, light extraction efficiency can be 80% or more.
- the light extraction efficiency can be 60% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 5 vol%. If it is above, light extraction efficiency can be 80% or more. In addition, when the diameter of the scattering material is 5 ⁇ m, the light extraction efficiency can be 50% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 10 vol%. If it is above, light extraction efficiency can be 80% or more.
- the light extraction efficiency can be 45% or more even when the scattering material content is in the range of 1 vol% to 20 vol%. In particular, the scattering material content is 10 vol%. If it is above, light extraction efficiency can be 80% or more. In addition, if the diameter of the scattering material is 10 ⁇ m, the light extraction efficiency can be made 40% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 15 vol%. If it is above, light extraction efficiency can be 80% or more. From the above, it can be seen that when the diameter of the scattering material is large, the light extraction efficiency improves as the content increases. On the other hand, it can be seen that when the diameter of the scattering material is small, the light extraction efficiency is improved even if the content is small.
- FIG. 12 is a graph showing the relationship between the light extraction efficiency (%) and the refractive index of the scattering material.
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection / transport layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- Thickness 1 ⁇ m, refractive index: 1.9
- scattering layer thickness: 30 ⁇ m, base material refractive index: 2.0, scattering material diameter: 2 ⁇ m, number of scattering materials: about 36 million, scattering material (Content: 15 vol%), translucent substrate (thickness: 100 ⁇ m, refractive index: 1.54)
- luminous flux 1000 lm was divided into 100,000 and calculated (wavelength 550 nm).
- the difference between the refractive index of the base material (2.0) and the refractive index of the scattering material is 0.2 or more (the refractive index of the scattering material is 1.8 or less)
- the light extraction efficiency can be made 80% or more, which is particularly preferable.
- Even if the difference between the refractive index of the base material and the refractive index of the scattering material is 0.1 (the refractive index of the scattering material is 1.9), the light extraction efficiency can be 65% or more.
- FIG. 14 is a graph showing the relationship between the light extraction efficiency (%) and the number of scattering materials (particles) (pieces / mm 2 ).
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection / transport layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- the light extraction efficiency varies depending on the number of scattering materials regardless of the thickness of the scattering layer. As shown in the graph, if the number of scattering substances per 1 mm 2 of the scattering layer is 1 ⁇ 10 4 or more, the light extraction efficiency can be 55% or more, which is preferable.
- the number of scattering substances per 1 mm 2 of the scattering layer is 2.5 ⁇ 10 5 or more because the light extraction efficiency can be 75% or more. Further, it is particularly preferable that the number of scattering materials per 1 mm 2 of the scattering layer is 5 ⁇ 10 5 to 2 ⁇ 10 6 because the light extraction efficiency can be 80% or more.
- the diameter of the scattering material is 60 ⁇ m or more or 3 ⁇ 10 6 , the light extraction efficiency can be made 70% or more.
- FIG. 15 is a graph showing the relationship between the light extraction efficiency (%) and the transmittance at 1 mmt% of the base material of the scattering layer.
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection / transport layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- Thickness 1 ⁇ m, refractive index: 1.9
- scattering layer (thickness: 30 ⁇ m, base material refractive index: 2.0, scattering material diameter: 2 ⁇ m, scattering material refractive index: 1.0, scattering material Number: about 36 million, content of scattering material: 15 vol%)
- translucent substrate (thickness: 100 ⁇ m, refractive index: 1.54)
- luminous flux of 1000 lm was divided into 100,000.
- the transmittance of the base material of the scattering layer is 50%
- the light extraction efficiency can be 55% or more.
- the transmittance of the base material of the scattering layer is 90%
- the light extraction efficiency can be 80% or more.
- the base material is glass, its transmittance is about 98%, so that the light extraction efficiency can exceed 80%.
- FIG. 16 is a graph showing the relationship between light extraction efficiency (%) and cathode reflectance (%).
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection / transport layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- Thickness 1 ⁇ m, refractive index: 1.9), scattering layer (thickness: 30 ⁇ m, base material refractive index: 2.0, scattering material diameter: 2 ⁇ m, scattering material refractive index: 1.0, scattering material Number: about 36 million, scattering material content: 15 vol%), translucent substrate (thickness: 100 ⁇ m, refractive index: 1.54), luminous flux 1000 lm divided into 100,000 (wavelength 550 nm) ).
- the reflectance of the cathode decreases, the light extraction efficiency also decreases.
- the light extraction efficiency can be 40% to 50%.
- the organic LED element of Patent Document 1 assumes a reflectance of 100%, and its light extraction efficiency is about 50%.
- the reflectance of the organic LED element of the present invention is set to 100% and the reflectance is the same as that of the organic LED element of Patent Document 1, the light extraction efficiency exceeds 80% as can be seen from the graph. That is, it can be seen that the light extraction efficiency of the organic LED element of the present invention is improved 1.6 times compared to the light extraction efficiency of the organic LED element of Patent Document 1. Therefore, the organic LED of the present invention can be used as an illumination light source instead of a fluorescent lamp.
- FIG. 17 is a graph showing the relationship between the ratio of light emitted to the scattering layer and the refractive index of the base material of the scattering layer.
- the calculation was performed by dividing the organic layer and the light-transmitting electrode into three parts: an electron injection / transport layer and a light-emitting layer, a hole injection / transport layer, and a light-transmitting electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- Thickness 1 ⁇ m, refractive index: 1.9
- scattering layer thickness: 30 ⁇ m, scattering material diameter: 2 ⁇ m, scattering material refractive index: 1.0, number of scattering materials: about 36 million, scattering material (Content: 15 vol%)
- translucent substrate thickness: 100 ⁇ m, refractive index: 1.54
- luminous flux 1000 lm was divided into 100,000 and calculated (wavelength 550 nm).
- the refractive index of the anode is larger than the refractive index of the scattering layer, total reflection occurs on the surface of the scattering layer, and the amount of light entering the scattering layer is reduced. Therefore, it can be seen that the light extraction efficiency is lowered.
- the refractive index of the scattering layer of the present invention is preferably equal to or higher than the refractive index of the anode.
- the refractive index of the anode is larger than the refractive index of the scattering layer, 40% of light can be extracted.
- 50% light can be extracted if the difference in refractive index between the anode and the scattering layer is 0.2 or less. Therefore, the refractive index of the scattering layer of the present invention may be effective even when it is not equal to or lower than the refractive index of the anode.
- FIG. 18 is a graph showing the relationship between the wavelength and the refractive index of the base material of the scattering layer.
- FIG. 19 shows the result of the relationship between the wavelength and the light receiving surface illuminance. 19 (a) corresponds to Case 1 in FIG. 18, FIG. 19 (b) corresponds to Case 2 in FIG. 18, FIG. 19 (c) corresponds to Case 3 in FIG. 18, and FIG. 19 (d) corresponds to Case 4 in FIG. FIG.
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection / transport layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode.
- the graph shows an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness).
- Thickness 1 ⁇ m, refractive index: 1.9
- scattering layer thickness: 30 ⁇ m, base material refractive index: 2.0, scattering material diameter: 2 ⁇ m, scattering material refractive index: 1.0, scattering material Number: about 36 million, content of scattering material: 15 vol%)
- translucent substrate thickness: 100 ⁇ m, refractive index: 1.54
- luminous flux of 1000 lm was divided into 100,000.
- the refractive index of the translucent electrode was set to 1.9. As FIG. 19 shows, when the refractive index of the base material of a scattering layer is lower than the refractive index of an organic layer and a translucent electrode, the taking-out efficiency in the wavelength falls and a color changes. I understand.
- the luminous efficiency decreases when the refractive index is 1.9 or less. That is, the characteristics deteriorate in the reddishness of the organic LED element. In this case, it is necessary to form an element with enhanced redness as the element configuration.
- Method for measuring refractive index of scattering layer There are the following two methods for measuring the refractive index of the scattering layer. One is to analyze the composition of the scattering layer, then to make a glass of the same composition, and evaluate the refractive index by the prism method. The other is that the scattering layer is thinly polished to 1 to 2 ⁇ m, and the refractive index is evaluated by ellipsometry in a region of about 10 ⁇ m ⁇ without bubbles. In the present invention, it is assumed that the refractive index is evaluated by the prism method.
- the scattering layer has a main surface on which a translucent electrode is provided.
- the scattering layer of the present invention contains a scattering material.
- the diameter of the scattering material is larger, the light extraction efficiency can be improved even if the content is small.
- the larger the diameter the larger the surface roughness of the main surface of the scattering layer, that is, the arithmetic average roughness Ra, when protruding from the main surface of the scattering layer.
- the translucent electrode is provided on the main surface of the scattering layer.
- Patent Document 1 discloses that in paragraph 0010, even if the unevenness formed on the substrate is about several ⁇ m, it is a problem, but according to the experiments by the inventors, the organic LED element is in units of ⁇ m. It was found that it was difficult to obtain luminescence.
- the translucent electrode (anode) 103 is required to have a translucency of 80% or more in order to extract light generated in the organic layer 110 to the outside.
- a high work function is required to inject many holes.
- ITO, SnO 2 , ZnO, IZO (Indium Zinc Oxide), AZO (ZnO—Al 2 O 3 : zinc oxide doped with aluminum), GZO (ZnO—Ga 2 O 3 : doped with gallium) Zb oxide), Nb-doped TiO 2 , Ta-doped TiO 2 and the like are used.
- the thickness of the anode 103 is preferably 100 nm or more.
- the refractive index of the anode 103 is about 1.9 to 2.2.
- the refractive index of ITO can be lowered.
- SnO 2 has a standard of 10 wt%. From this, the refractive index of ITO can be lowered by increasing the Sn concentration.
- the refractive index of ITO is preferably determined in consideration of the refractive index of the base material 105 constituting the scattering layer 102 and the refractive index of the reflective electrode 120.
- the refractive index of ITO is preferably smaller than or equal to the refractive index of the base material 105 constituting the scattering layer 102, but may be slightly larger. Considering the waveguide calculation, the reflectance of the reflective electrode 120, and the like, the difference between the refractive index of ITO and the refractive index of the base material 105 is preferably 0.2 or less. Needless to say, the translucent electrode may be a cathode.
- the organic layer 110 is a layer having a light emitting function, and includes a hole injection layer 111, a hole transport layer 112, a light emitting layer 113, an electron transport layer 114, and an electron injection layer 115.
- the refractive index of the organic layer 110 is about 1.7 to 1.8.
- the hole injection layer 111 is required to have a small difference in ionization potential in order to lower the hole injection barrier from the anode 103. Improvement of the charge injection efficiency from the electrode interface in the hole injection layer 111 lowers the drive voltage of the element and increases the charge injection efficiency.
- PEDOT polyethylene dioxythiophene
- PSS polystyrene sulfonic acid
- CuPc phthalocyanine-based copper phthalocyanine
- the light-emitting layer 113 is formed using a material that provides a field where injected electrons and holes are recombined and has high emission efficiency. More specifically, the light-emitting host material and the light-emitting dye doping material used for the light-emitting layer 113 function as recombination centers for holes and electrons injected from the anode and the cathode, and to the host material in the light-emitting layer. Doping of the luminescent dye obtains high luminous efficiency and converts the emission wavelength. These are required to have an appropriate energy level for charge injection, excellent in chemical stability and heat resistance, and to form an amorphous thin film homogeneously.
- Light emitting materials that are organic materials include low-molecular materials and high-molecular materials. Further, it is classified into a fluorescent material and a phosphorescent material according to the light emission mechanism.
- the light-emitting layer 113 includes tris (8-quinolinolato) aluminum complex (Alq 3 ), bis (8-hydroxy) quinaldine aluminum phenoxide (Alq ′ 2 OPh), bis (8-hydroxy) quinaldine aluminum.
- the electron transport layer 114 serves to transport electrons injected from the electrodes.
- the electron transport layer 114 includes a quinolinol aluminum complex (Alq3), an oxadiazole derivative (for example, 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND) and 2 -(4-t-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole (PBD) and the like), triazole derivatives, bathophenanthroline derivatives, silole derivatives and the like are used.
- the electron injection layer 115 is required to increase the electron injection efficiency. Specifically, the electron injection layer 115 is provided with a layer doped with an alkali metal such as lithium (Li) or cesium (Cs) at the cathode interface.
- an alkali metal such as lithium (Li) or cesium (Cs) at the cathode interface.
- the reflective electrode (cathode) 120 is made of a metal having a small work function or an alloy thereof.
- the cathode 120 include alkali metals, alkaline earth metals, and metals belonging to Group 3 of the periodic table.
- aluminum (Al), magnesium (Mg), or alloys thereof are preferably used because they are inexpensive and have good chemical stability.
- a laminated electrode or the like obtained by depositing Al on a co-deposited film of Al or MgAg, a thin film deposited film of LiF or Li20, or the like is used.
- a laminate of calcium (Ca) or barium (Ba) and aluminum (Al) is used.
- the reflective electrode may be an anode.
- a translucent substrate is prepared (step 1100).
- a glass substrate or a plastic substrate is used as the translucent substrate.
- a scattering layer forming material comprising a base material having a first refractive index at the wavelength of light emitted from the organic LED element, and a plurality of scattering materials provided inside the base material and having a refractive index different from that of the base material prepare.
- the prepared scattering layer forming material is applied and baked to form a scattering layer in which the scattering material is uniformly distributed in the plane on the translucent substrate (step 1110).
- a translucent electrode preferably, a translucent electrode having a second refractive index equal to or lower than the first refractive index is formed on the scattering layer (step 1120). More specifically, it is formed by depositing ITO on a substrate and etching the ITO film. ITO can be formed on the entire surface of the glass substrate with good uniformity by sputtering or vapor deposition. An ITO pattern is formed by photolithography and etching. This ITO pattern becomes a translucent electrode (anode). A phenol novolac resin is used as the resist, and exposure development is performed. Etching may be either wet etching or dry etching. For example, ITO can be patterned using a mixed aqueous solution of hydrochloric acid and nitric acid. As the resist stripping material, for example, monoethanolamine can be used.
- FIG. 21 is a flowchart showing a method for manufacturing an organic LED element of the present invention.
- the organic LED element manufacturing method of the present invention includes a step of preparing a translucent substrate (step 1100), and a base material having a first refractive index on the translucent substrate at the wavelength of the emitted light of the organic LED element.
- a step of forming a scattering layer provided inside the base material and a plurality of scattering materials having a refractive index different from that of the base material (step 1110), and a step of forming a translucent electrode on the scattering layer ( Step 1120), a step of forming an organic layer on the translucent electrode (Step 1200), and a step of forming a reflective electrode on the organic layer (Step 1210).
- an organic layer is formed on the translucent electrode (Step 1200).
- the organic layer is formed by a combination of a coating method and a vapor deposition method.
- the other layers are formed by a vapor deposition method.
- concentration drying and curing are performed before the organic layer is formed by the vapor deposition method.
- the organic layer may be formed only by the coating method and the vapor deposition method.
- a reflective electrode is formed on the organic layer (step 1210). More specifically, the reflective electrode is formed by evaporating a metal material such as aluminum on the organic layer.
- a glass substrate different from the element substrate is prepared.
- the glass substrate is processed to form a water catching material storage for storing the water catching material.
- the water catching material storage part applies a resist to the glass substrate and exposes a part of the substrate by exposure and development.
- the exposed part is formed by etching to form a water catching material storage part.
- FIG. 22 is sectional drawing which shows the structure of an organic LED display apparatus typically.
- the sealing material 1330 is applied to the surface of the counter substrate 1320 on which the water catching material storage portion 1300 is provided using a dispenser.
- the sealing material 1330 for example, an epoxy-based ultraviolet curable resin can be used.
- the sealing material 1330 is apply
- the sealing material is cured by irradiating ultraviolet rays, and the substrates are bonded to each other. Thereafter, in order to further accelerate the curing of the sealing material, for example, heat treatment is performed for 1 hour in a clean oven at 80 ° C.
- heat treatment is performed for 1 hour in a clean oven at 80 ° C.
- the scattering layer is not formed on the outer peripheral portion of the organic LED element substrate, the surface is smoother. Therefore, the sealing property is further enhanced by the improvement in the adhesion due to the smoothness and the level difference with the laminated portion such as the scattering layer in the inner element forming portion.
- the sealing material and the pair of substrates separate the substrate where the organic LED element exists from the outside of the substrate.
- the optical sheet 1340 is affixed to the surface of the substrate 101 opposite to the surface on which the organic LED elements are formed, that is, the emission surface.
- the optical sheet 1340 has a polarizing plate and a quarter-wave plate and functions as an antireflection film. Light from the organic thin film layer is extracted on the surface side on which the optical sheet 1340 is provided.
- the unnecessary portion near the outer periphery of the substrate is cut and removed, the signal electrode driver is connected to the anode wiring 1350, and the scanning electrode driver is connected to the cathode connection wiring.
- a terminal portion connected to each wiring is formed at the substrate end.
- An anisotropic conductive film (ACF) is attached to this terminal part, and TCP (Tape Carrier Package) provided with a drive circuit is connected. Specifically, ACF is temporarily crimped to the terminal portion. Next, the TCP with the built-in drive circuit is finally bonded to the terminal portion. Thereby, a drive circuit is mounted.
- This organic LED display panel is attached to the housing, and the organic LED display device is completed.
- the above shows a case of a dot matrix display element, but a character display may be used, and the configuration is not limited to the above depending on the element specification.
- the first main surface is a surface constituting a swell formed of a curved surface
- the second main surface is a surface flatter than the first main surface.
- the organic LED element of this Embodiment 1 uses the glass layer as a scattering layer, it has high moisture resistance and can endure long-term use. Further, since the surface is smooth and has a desired refractive index, the light extraction efficiency is high and the reliability is high. Further, since the optimum range is defined by various experiments and considerations regarding the size of the swell for preventing reflection of the reflective electrode, it is possible to obtain a highly reliable organic LED element. ing.
- Patent Document 1 the semi-transparent material layer has paraffin or the like fixed on the substrate with a resin binder (paragraph 0040). That is, the light-scattering part of patent document 1 is resin, and it is easy to absorb a water
- the light scattering part used here increases the number of glass particles that are scattering materials, and when trying to improve the scattering properties, irregularities are formed on the surface due to the presence of the scattering materials, so that the element is directly applied to the surface. It was difficult to form.
- the light scattering portion is formed on the surface facing the element formation surface, there is a problem that sufficient light scattering properties cannot be obtained because there is a distance from the light emitting region to the light scattering portion.
- Patent Document 2 Although swell is suggested, there is no mention of unevenness on the surface of the scattering layer.
- irregularities if there are irregularities on the surface, irregularities are likely to be formed on the surface of the first electrode formed on this upper layer, and if a layer having a light emitting function or the like is formed on this upper layer by vapor deposition or the like, these organic layers As a result, the film thickness of the organic layer varies, and as a result, the interelectrode distance between the first electrode and the surface of the second electrode formed on the organic layer is reduced. Variation will occur.
- the organic LED element of the present embodiment solves the above problem.
- FIG. 23 is a cross-sectional view showing another structure of a light-transmitting substrate for an organic LED element of the present invention and an organic LED element formed using the same.
- Another organic LED element of the present invention includes a translucent substrate 1400 with a translucent electrode, an organic layer 1410, and a reflective electrode 120.
- the translucent substrate 1400 with a translucent electrode includes the translucent substrate 101, the scattering layer 1401, and the translucent electrode 103.
- the organic layer 1410 includes a hole injection / transport layer 1411, a light emitting layer 1412, and an electron injection / transport layer 1413.
- the light emitting layer 113 of the organic LED element of FIG. 1 is composed of three layers. Any one of the three layers is formed so as to emit any one of the three emission colors (red, green, and blue).
- the light-emitting layer 1412 of the organic LED element of FIG. 23 uses only a plurality of scattering materials 1420 provided in the scattering layer 1401 as fluorescent light-emitting materials (for example, fillers) that emit red and green light, so that only blue light is emitted.
- the structure in which the organic layer is sandwiched between the translucent electrode and the reflective electrode has been described.
- both electrodes are translucent to form a double-sided light emitting organic LED layer.
- the substrate for electronic devices of the present invention is not limited to organic LED elements, but can improve the efficiency of optical devices such as various light emitting devices such as inorganic EL elements and liquid crystals, or light receiving devices such as light quantity sensors and solar cells. It is valid.
- Example 1 (Demonstration of scattering layer effect) Hereinafter, the demonstration that the scattering layer is effective for improving the light extraction efficiency will be described.
- Sample 1 is an example provided with a scattering layer having the undulations of the present invention
- sample 2 is a comparative example provided with a scattering layer in which no scattering material is provided.
- the calculation method is the same as the calculation method of the scattering layer described above.
- the conditions and results are shown in Table 2 below.
- FIG. 24 shows a comparison result of the front surface extraction efficiency between the example and the comparative example.
- 24 (a) and 24 (b) are diagrams showing results observed from the front under the conditions of Sample 2 and Sample 1, respectively.
- the light extraction efficiency of about 20% can be improved to about 80% when not treated.
- FIGS. 25 and 26 were prepared.
- FIG. 25 is a cross-sectional view taken along line AA in FIG. 26, showing the structure of the evaluation element.
- FIG. 26 is a top view of the evaluation element viewed from the direction B in FIG. Note that FIG. 26 shows only the glass substrate 1610 and the scattering layer 1620 in order to clarify the positional relationship between the glass substrate 1610 and the scattering layer 1620.
- the evaluation element includes a glass substrate 1610, a scattering layer 1620, an ITO film 1630, an Alq 3 (tris (8-quinolinolate) aluminum complex) film 1640, and an Ag film 1650.
- the evaluation element was divided into two regions, a region 1600A with a scattering layer and a region 1600B without a scattering layer.
- the scattering layer 1620 is formed on the glass substrate 1610.
- an ITO film 1630 is formed on the glass 1610.
- a glass substrate manufactured by Asahi Glass Co., Ltd. [trade name: PD200, hereinafter referred to as PD200] was used.
- This glass has a strain point of 570 ° C. and a thermal expansion coefficient of 83 ⁇ 10 ⁇ 7 (1 / ° C.).
- a glass substrate having such a high strain point and a high thermal expansion coefficient is suitable when a scattering layer is formed by baking a glass frit paste.
- the scattering layer 1620 is a high refractive index glass frit paste layer.
- a glass having the composition shown in Table 3 was manufactured as the scattering layer 1620.
- This glass has a glass transition temperature of 483 ° C., a yield point of 528 ° C., and a thermal expansion coefficient of 83 ⁇ 10 ⁇ 7 (1 / ° C.).
- the refractive index nF of this glass at the F-line (486.13 nm) is 2.03558
- the refractive index nd at the d-line (587.56 nm) is 1.99810
- the refractive index nC at the C-line (656.27 nm) is 1.98344.
- the refractive index was measured with a refractometer (trade name: KRP-2, manufactured by Kalnew Optical Industry Co., Ltd.).
- the glass transition point (Tg) and the bending point (At) were measured by a thermal analysis method (trade name: TD5000SA, manufactured by Bruker) at a temperature rising rate of 5 ° C./min.
- the scattering layer 1620 was formed by the following procedure.
- the powder raw material was prepared so that it might become a composition shown by the ratio of Table 3.
- the prepared powder raw material was dry pulverized with an alumina ball mill for 12 hours to produce a glass powder having an average particle size (d50, particle size of 50% integrated value, unit ⁇ m) of 1 to 3 ⁇ m.
- 75 g of the obtained glass powder was kneaded with 25 g of an organic vehicle (about 10% by mass of ethyl cellulose dissolved in ⁇ -terpineol or the like) to prepare a paste ink (glass paste).
- This glass paste was printed uniformly on the above glass substrate so that the film thickness after firing was 15 ⁇ m, 30 ⁇ m, 60 ⁇ m, and 120 ⁇ m, dried at 150 ° C. for 30 minutes, and then returned to room temperature. The temperature is raised to 45 ° C. in 45 minutes, held at 450 ° C. for 10 hours, then heated to 550 ° C. in 12 minutes, held at 550 ° C. for 30 minutes, and then cooled to room temperature in 3 hours. A glass layer was formed. About the scattering layer with a film thickness of 120 ⁇ m, the surface was polished until the film thickness was 60 ⁇ m. The glass film formed thereby contains many bubbles, which cause scattering. On the other hand, although there was a wave on the outermost surface of the scattering layer glass, there was no local unevenness that would cause a short circuit between the electrodes of the organic LED, such as the opening of bubbles.
- FIG. 27 is a graph showing the undulation of the surface of the scattering layer.
- 27A shows the undulation of the surface of the scattering layer having a thickness of 60 ⁇ m
- FIG. 27B shows the undulation of the surface of the scattering layer having a thickness of 60 ⁇ m obtained by polishing the scattering layer having a thickness of 120 ⁇ m.
- FIG. 28 is a graph obtained by calculating the angle of the undulating slope in FIG. 27A and 27B were measured using a surface roughness meter (manufactured by Tokyo Seimitsu, SURFCOM 1400D).
- the angle of the slope of the scattering layer due to waviness is about 27 ° at the maximum, and this angle is smaller than the taper angle (40 to 50 °) of the edge portion of the opening insulating film used in the passive organic LED panel. It is considered that there is no problem with the coverage of metal films.
- this swell does not classify the glass particles at the time of producing the frit, and contains large particles. This is thought to be due to the fact that large particle portions remain as waviness during firing. Therefore, when other conditions are the same, the swell can be reduced by making the size of the particles small and uniform, and the swell can be adjusted to be increased by increasing the size of the particles.
- An example of the measurement result of local roughness is shown in FIG. FIG.
- FIG. 29A shows the case where the surface of the scattering layer is not polished
- FIG. 29B shows the case where the surface is polished.
- the arithmetic average roughness Ra of the surface of the unpolished scattering layer was 31.0 nm
- the polished arithmetic average roughness Ra was 23.5 nm.
- FIG. 29A shows the surface of the scattering layer that has been mirror-polished.
- the measurement result (FIG. 29B) is an uneven shape. This is because the scatterer is a bubble and the bubble does not exist on the surface.
- the scattering material may be exposed on the surface. It is necessary to prevent a short circuit of the organic LED element.
- the polished surface has a smooth surface.
- the total light transmittance and haze value of each substrate with a scattering layer were measured.
- Suga Test Instruments Haze Meter HGM-2 was used as a measuring device.
- the base plate of the glass substrate [PD200] described above was measured. Table 4 shows the measurement results.
- An ITO film 1630 was formed on the glass substrate 1610 on which the scattering layer 1620 and the scattering layer 1620 were not formed by sputtering so that the film thickness was 150 nm. Sputtering was performed at room temperature, Ar 99.5 SCCM, O 2 0.5 SCCM, pressure 0.47 Pa, input power 2.35 W / cm 2 . Thereafter, using an evaporation apparatus, an Alq 3 film 1640 was formed on the ITO film 1630 and an Ag film 1650 was formed on the Alq 3 film 1640 so that the film thicknesses were 200 nm and 70 nm, respectively.
- the light emission luminance measurement evaluation method is shown in FIG.
- a mercury xenon lamp (trade name: SUNCURE202-LS) 2100 manufactured by Asahi Glass Co., Ltd. was used. Since there is a visible component from the light source, it was removed using a visible light filter 2110.
- a stainless steel aperture (15 mm ⁇ 10 mm) 2120 was arranged to shape the ultraviolet beam. Part of the ultraviolet light incident on the evaluation element 1600 passes through the Ag film 1650 and excites the Alq 3 film 1640 to emit fluorescence.
- Ultraviolet light was irradiated to a region with a scattering layer and a region without a scattering layer of the evaluation element 1600, and the respective fluorescence luminances were measured with a luminance meter 2140.
- a luminance meter manufactured by Konica Minolta (trade name: LS-110) was used, and an ultraviolet filter 2130 was inserted in front of the luminance meter.
- FIG. 31 corresponds to FIG. As shown in FIG. 31, there are a total of five measurement points at the center and four corners of the ultraviolet irradiation region.
- the ultraviolet irradiation region and the fluorescence emission region are the same, but when the scattering layer 1620 is present, the fluorescence emission region goes to the strong central emission region 2210 that hits the ultraviolet irradiation region and to the periphery on the outside. Accordingly, it can be classified into the peripheral light emission region 2220 in which the light emission becomes weaker.
- An example of the luminance distribution of the central light emitting area 2210 and the peripheral light emitting area 2220 is shown in FIG. Here, the luminance at the line DD in FIG.
- the peripheral light emitting area 2220 As shown in FIG. 32, the light extracted from the periphery decreases in luminance as it gets farther from the central light emitting area, and becomes almost zero at about 8 mm from the end of the central light emitting area. Considering a product to which the present invention is applied, if the size of the light emitting portion is sufficiently larger than 8 mm, the light extracted from the peripheral light emitting area may be considered as the extracted light flux.
- FIG. 34 shows the luminance when the five-point average value is corrected by changing the thickness of the scattering layer (15 ⁇ m, 30 ⁇ m, 60 ⁇ m, 60 ⁇ m after polishing), measuring the amount of light in each peripheral light emitting region.
- the luminance distribution in the peripheral light emitting area is measured, and the total luminous flux is calculated.
- a value obtained by dividing the value by the area of the central light emitting area is added to the luminance of the central light emitting area to be corrected. It can be seen that in the region where there is no scattering layer, there is no peripheral light emitting region, so the front luminance ratio with the region where there is a scattering layer is further increased.
- FIG. 37 shows a graph in which the spectrum intensity of the region without the scattering layer is doubled and overwritten with the spectrum of the region with the scattering layer.
- the measurement method was the same as the measurement method shown in FIG. 30.
- the luminance was measured while changing the position of the luminance meter, and the luminous intensity was calculated from the value.
- the measurement results are shown in FIG. FIG. 39 is obtained by normalizing the data of FIG. 38 with the front luminous intensity.
- the angle dependency of the luminous intensity did not change regardless of the presence or absence of the scattering layer, and the omnidirectionality was strong. From this, it was confirmed that the improvement of the light extraction efficiency of the present invention confirmed by the front luminance was similarly improved for the total luminous flux.
- the particle size distribution of the bubbles in the scattering layer produced this time was measured. If the thickness of the scattering layer is 15 ⁇ m, all bubbles in the scattering layer can be identified under a microscope. Bubbles in a 90.5 ⁇ m ⁇ 68.1 ⁇ m visual field were identified and counted by image processing. Table 5 shows the measurement results at arbitrary three locations of the scattering layer.
- FIG. 40 shows the bubble diameter distribution at measurement point # 2.
- the bubble diameter was often 2 ⁇ m or less, and the average diameter, that is, the average bubble diameter was 1.3 to 1.4 ⁇ m.
- the number of bubbles per 1 mm 2 of the scattering layer was 1.1 ⁇ 10 5 to 2.2 ⁇ 10 5 .
- the number of bubbles when the scattering layer thickness is 30 ⁇ m is 2.2 ⁇ .
- the number of bubbles is 4.4 ⁇ 10 5 to 8.8 ⁇ 10 5 .
- FIG. 41 compares the relationship between the number of bubbles per 1 mm 2 and the light extraction efficiency when the bubble diameter is 2 ⁇ m and the measurement result this time. Comparing the measurement result of FIG. 41 with the simulation result of FIG. 14, it was found that the evaluation element can obtain the same result as the simulation result. Specifically, when the thickness of the scattering layer is 15 ⁇ m, the number of bubbles is insufficient and the light extraction efficiency is insufficient. When the thickness of the scattering layer is 60 ⁇ m, the light extraction efficiency is also in the saturation region.
- FIG. 42 shows the refractive indices of the scattering layer glass, ITO film, and Alq 3 film of the example.
- the refractive index of the ITO film data of the same film formed at room temperature was used. Since the emission wavelength of the Alq 3 film is about 430 nm to 670 nm, the relationship in refractive index over the entire wavelength range is scattering layer glass> ITO film> Alq 3 film. From this, it is considered that there is no loss of light that propagates inside the Alq 3 film or the ITO film. As a cause of the loss of light extraction efficiency, the reflectance of the Ag film, the Alq 3 film, the ITO film, the scattering layer glass, and the absorption of the substrate glass are considered.
- the light extraction efficiency at this time is about 60% when there is no other loss from the graph with scattering materials in FIG.
- the total light transmittance in the case of the scattering layer thickness of 60 ⁇ m produced this time is as low as 83%. Therefore, it is estimated that the loss in the scattering layer is not negligible.
- the optical path length in the scattering layer is unknown, if it is about 1 mm, the loss at the absorption of 17% can be estimated to be about 12% from the simulation result described above.
- an antireflection film is formed on the outermost surface of the glass substrate.
- Example 2 (Demonstration of smoothness of the main surface of the scattering layer)
- the main surface of the scattering layer has waviness and is smooth (surface roughness Ra (: arithmetic average roughness) is 30 nm or less).
- surface roughness Ra (: arithmetic average roughness) is 30 nm or less).
- the scattering layer was produced as follows. First, powder raw materials were prepared so that the glass composition was as shown in Table 6, melted in an electric furnace at 1100 ° C., and cast into a roll to obtain glass flakes.
- This glass has a glass transition temperature of 499 ° C., a yield point of 545 ° C., and a thermal expansion coefficient of 74 ⁇ 10 ⁇ 7 (1 / ° C.) (an average value of 100 to 300 ° C.).
- the refractive index nF of this glass at F line (486.13 nm) is 2.0448, the refractive index nd at d line (587.56 nm) is 2.0065, and the refractive index nC at C line (656.27 nm) is 1.9918.
- the method of measuring the refractive index and the glass transition point / sag point is the same as in the above example.
- the prepared flakes were pulverized with a zirconia planetary mill for 2 hours, and then sieved to prepare a powder.
- the particle size distribution at this time was as follows: D 50 was 0.905 ⁇ m, D 10 was 0.398 ⁇ m, and D 90 was 3.024 ⁇ m.
- 20 g of the obtained glass powder was kneaded with 7.6 g of an organic vehicle to produce a glass paste. This glass paste was printed uniformly on the above glass substrate so that the film thickness was 10 mm and the film thickness after firing was 15 ⁇ m, dried at 150 ° C. for 30 minutes, and then returned to room temperature.
- the glass substrate with a scattering layer thus prepared had a total light transmittance of 77.8 and a haze value of 85.2.
- the measuring device was a haze computer (trade name: HZ-2) manufactured by Suga Test Instruments Co., Ltd., and a glass substrate [PD200] base plate was used as a reference.
- a glass substrate with a scattering layer prepared as described above and a glass substrate without a scattering layer [PD200] were prepared to prepare an organic LED element.
- ITO was formed into a film having a thickness of 150 nm by DC magnetron sputtering as a translucent electrode. The refractive indexes of the scattering layer glass and ITO are shown in FIG. Subsequently, ultrasonic cleaning using pure water was performed, and then the surface was cleaned by irradiating ultraviolet rays with an excimer UV generator.
- ⁇ -NPD N, N′-diphenyl-N, N′-bis (l-naphthyl) -l, l′ biphenyl-4,4 ′′ diaminine
- Alq 3 using a vacuum deposition apparatus.
- Tris8-hydroxyquinoline aluminum was deposited at 60 nm, LiF at 0.5 nm, and Al at 80 nm.
- ⁇ -NPD and Alq 3 form a circular pattern having a diameter of 12 mm using a mask, and LiF and Al form a pattern using a mask having a 2 mm square region on the ITO pattern through the organic film.
- the device was completed.
- a concave portion was formed by sandblasting on [PD200] as a counter substrate, and a photosensitive epoxy resin was applied to the bank around the concave portion for peripheral sealing.
- a photosensitive epoxy resin was applied to the bank around the concave portion for peripheral sealing.
- put the element substrate and the counter substrate in the glove box paste the water catching material containing CaO in the counter substrate recess, then bond the element substrate and the counter substrate together, irradiate with ultraviolet rays, and seal the periphery
- the resin was cured. Table 7 shows the state of occurrence of a short circuit between the electrodes in each element.
- self-repair refers to causing an overcurrent of 10 mA to flow through the element and causing the short-circuited portion to self-repair with its Joule heat.
- FIG. 45 and 46 show how the element emits light.
- FIG. 45 shows an element having a scattering layer
- FIG. 46 shows an element without a scattering layer.
- the element without the scattering layer light emission is confirmed only from the approximately 2 mm square region formed by the crossing of the ITO pattern and the Al pattern.
- the element fabricated on the scattering layer not only the above approximately 2 mm square region. It can be seen that light is also extracted from the surrounding scattering layer forming portion into the atmosphere.
- FIG. 47 shows current-voltage characteristics of an element with and without a scattering layer. Thus, almost the same characteristics are obtained, and it can be seen that a large leak current does not exist even in the element formed on the scattering layer.
- FIG. 48 shows current luminance characteristics. Thus, regardless of the presence or absence of the scattering layer, the amount of light flux is proportional to the current, and when the scattering layer is present, the amount of light flux is increased by 15% compared to the case where there is no scattering layer. As shown in FIG.
- the refractive index of the scattering layer is higher than the refractive index of ITO which is a translucent electrode at the emission wavelength of Alq3 (450 nm to 700 nm)
- the EL emission light of Alq3 is scattered with ITO. Suppressing total reflection at the interface of the layers, indicating that light is efficiently extracted into the atmosphere.
- FIGS. FIG. 50 shows the measurement results of the organic LED element having no scattering layer
- FIG. 51 is a graph obtained by standardizing the luminance at the wavelength showing the maximum luminance at each measurement angle as 1.
- FIG. 51 It can be seen from FIG. 51 that the spectrum is shifted depending on the measurement angle.
- FIG. 52 shows the measurement results of the element having the scattering layer
- FIG. 53 is a graph obtained by standardizing the luminance at the wavelength showing the maximum luminance at each measurement angle as 1.
- FIG. 53 it can be seen that even if the measurement angle changes, there is almost no spectral shift.
- Table 8 the result of converting the spectrum into chromaticity coordinates is shown in Table 8 and FIG.
- the cross-sections of those fired at 570 ° C. and 580 ° C. were polished and SEM photographs were taken at a magnification of 10,000 times. From the photograph, the number of bubbles and the bubbles from the surface of the glass scattering layer were taken. The relationship of distance was investigated. The length in the transverse direction of the SEM photograph was 12.5 ⁇ m. A line was drawn from the surface layer of the scattering layer to the SEM photograph in increments of 0.25 ⁇ m, and the number of bubbles that could be confirmed in this 0.25 ⁇ m ⁇ 12.5 ⁇ m frame was counted. Here, bubbles present across a plurality of frames were counted as being in the lower frame. The results are shown in FIG.
- the X-axis indicates the distance from the surface of the glass scattering layer.
- a point of 0.5 ⁇ m is the number of bubbles confirmed in a frame of 0.25 ⁇ m to 0.5 ⁇ m measured from the surface of the glass scattering layer.
- the firing temperature is 570 ° C.
- the curve a in the case of 0.5 ⁇ m to 580 ° C. from the surface, as shown by the curve b
- the bubbles become closer to the surface from 1.25 ⁇ m to the surface. It can be confirmed that the number is decreasing. In addition, no dent was observed on the surface in any case.
- FIG. 55 shows the case where the firing temperatures are 570 ° C. and 580 ° C., but similar results could be obtained even if the firing temperature was slightly changed.
- the cause cannot be determined. There are the following two possibilities. (1) In the case of the 580 ° C. fired product, the bubbles are expanded by the higher temperature, making it easier to count. (2) The decomposition of the organic residue adhered to the glass powder was more advanced at 580 ° C., and the number of bubbles increased.
- bubbles and crystals are generated by different mechanisms, it is possible to generate only bubbles or crystals only by controlling the glass material, powder particle size, surface condition, firing conditions (atmosphere, pressure), etc. is there. For example, by increasing the number of glass network formers or increasing the number of alkali oxide components that suppress crystal precipitation, crystal precipitation is suppressed, and if fired under reduced pressure, bubble generation is suppressed.
- Example 3 (About swell) Next, Embodiment 3 of the present invention will be described.
- a scattering layer was formed on a [PD200] substrate, and an Al thin film having a thickness of about 80 nm was further formed thereon by vapor deposition. Seven types shown in Table 10 were used as the scattering layer. Glass compositions A, B, C, and D are shown in Table 11, Table 12, and Table 13, respectively.
- spectroscopic measurement of total reflection is performed in a state where the other openings are blocked, and the reflectance is calculated using the data.
- the reflectance is calculated by multiplying the measured spectral data by the spectral distribution of the light source and the color matching function y ( ⁇ ).
- the light source data was D65 standard light source, and the color matching function was 2 ° field of view data.
- spectroscopic measurement is performed with the opening of the integrating sphere at the position where the light regularly reflected on the sample is emitted, and the reflectance at that time is calculated.
- the reflectance at this time is referred to as diffuse reflectance.
- the diffuse reflectance ratio was calculated by dividing the diffuse reflectance by the total reflectance.
- the metal electrode surface is not visually recognized like a mirror surface, but if the scattering property is lowered, it is visually recognized as a mirror surface, which may be undesirable in appearance.
- the appearance of the metal electrode can be evaluated without being affected by the scattering layer. From the measurement results, it was found that the diffuse reflection ratio was increased by the undulation. In either case, the specularity in appearance is suppressed.
- the diffuse reflection ratio when Al was directly deposited on the glass substrate was 40%, which was a large value compared with 38% of material C, but the appearance was clearly scattered by material C. The mirror visibility was suppressed when the layer was formed.
- the material A is more preferably fired at 580 ° C.
- Example 4 Total transmittance of scattering layer (Haze value)
- Table 1 Total transmittance of scattering layer
- organic LED elements were prepared and evaluated in the same manner as described above, and the ratio of light extraction efficiency with respect to the case without the scattering layer was evaluated.
- the sample is set inside the integrating sphere 300 as shown in FIG. The measurement was performed without loss.
- FIG. 57 shows the relationship between the thickness of the scattering layer 102 and the total light transmittance
- FIG. 58 shows the relationship between the thickness of the scattering layer 102 and the haze value.
- FIG. 59 shows the total light transmittance and the light extraction efficiency ratio (light extraction magnification) compared to the case without the scattering layer 102, and the light extraction efficiency ratio (the light extraction efficiency ratio compared to the case without the scattering layer).
- FIG. 60 shows the light extraction magnification.
- the translucent substrate preferably has a Haze value of 80 to 87.
- the organic LED element has been described.
- the organic LED element is effective for both the top emission structure and the bottom emission structure, and the inorganic LED element is not limited to the above structure.
- a layer laminated on a translucent electrode such as a solar cell
- a layer having various photoelectric conversion functions can be laminated, and there are a light emitting layer, a light detecting layer, a power generating layer, etc.
- an optical device such as a light emitting device, a light detection device, and a power generation device.
- application to an electronic device such as a DRAM or a composite device of these and an optical device is also effective.
- the substrate for an electronic device of the present invention can suppress the visibility of the reflective electrode by having undulations, has good light scattering properties, and is stable and reliable scattering. Since the layer is provided, the light extraction efficiency or the light extraction efficiency can be increased, and the present invention can be applied to a general electronic device including a light emitting device and a light receiving device.
- Translucent substrate with electrodes DESCRIPTION OF SYMBOLS 101 Glass substrate 102 Scattering layer 103 Translucent electrode 104 Scattering substance 110 Organic layer 120 Reflective electrode
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Abstract
Description
有機層の屈折率は波長430nmで1.8~2.1程度である。一方、例えば透光性電極層としてITO(酸化インジウム錫:Indium Tin Oxide)を用いる場合の屈折率は、ITO成膜条件や組成(Sn-In比率)で異なるが、1.9~2.1程度が一般的である。このように有機層と透光性電極層の屈折率は近く、発光光は有機層と透光性電極層間で全反射することなく、透光性電極層と透光性基板の界面に到達する。透光性基板には通常ガラスや樹脂基板が用いられるが、これらの屈折率は1.5~1.6程度であり、有機層或いは透光性電極層よりも低屈折率である。スネルの法則から考えると、ガラス基板に浅い角度で進入しようとした光は全反射で有機層方向に反射され、反射性電極で再度反射され再び、ガラス基板の界面に到達する。この時、ガラス基板への入射角度は変わらないため、有機層、透光性電極層内で反射を繰り返し、ガラス基板から外に取り出すことができない。概算では、発光光の60%程度がこのモード(有機層・透光性電極層伝播モード)で取り出せないことが分かる。同様なことが基板、大気界面でも起き、これにより発光光の20%程度がガラス内部を伝播して、光が取り出せない(基板伝播モード)。従って、有機LED素子の外部に取り出せる光の量は、発光光の20%足らずになっているのが現状である。
このように光散乱部を設けることで、反射性電極面は鏡面のように視認されず、外観が向上する。
一方、散乱性を落とした場合、あるいは光散乱部のない場合は、反射性電極は鏡面として視認され、外観上好ましくない可能性がある。
そこで、うねりを持つ表面に電極を形成するようにした有機LED素子が提案されている(特許文献2)。
この構成によれば、表面のうねりにより、鏡面視認性を抑制可能である。また、うねりの波長と粗さを上記範囲に規定することで、表面に形成される電子デバイスの電極間短絡を抑制し、長寿命で、実効面積の高い電子デバイスを提供することが可能となる。
この構成によれば、散乱層をガラスで構成することにより、安定性と高強度性を実現することができ、本来のガラスからなる透光性基板に比べて厚みを増大することなく、散乱性に優れた透光性基板を提供することが可能となる。
有機LED素子は、電極間に挟まれた有機層に電圧を印加して発光させるデバイスであるため、電極間距離の局所的な変化は、電界の集中により有機層の劣化を招くことになり易いが、上記構成によれば、電極間距離の局所的変化を抑制することができる。
この構成によれば、非発光時に、基板の第2の主面側から見た時に反射した像がゆがんで見えるのを防止することができる。前記基板の第1の主面が湾曲面で構成されたうねりを構成する表面であり、前記第2の主面が前記第1の主面よりも平坦な面となるようにすることで、素子の実装工程において、素子の形成された基板を基台上に載置し、外周にシール材を塗布しその上に封止用基板を重ね合わせて硬化させる場合にも、基台上のシール材が接着する面は平坦であり、十分な接着性を確保することが出来る。
また、表面粗さRaとは、微視(ミクロ)的にみた表面粗さをいい、長波長カットオフ値を10μmとしてJIS B0601(1994年)に準じて算出した値を指す。
また、本発明によれば、表面に形成される電子デバイスの電極間短絡を抑制し、長寿命で、実効面積の大きい電子デバイスを提供することが可能となる。
さらにまた、散乱層をガラスで構成することにより、安定性と高強度性を実現することができ、本来のガラスからなる透光性基板に比べて厚みを増大することなく、散乱性に優れた透光性基板を提供することが可能となる。
以下、図面を用いて、本発明の実施の形態1の電子デバイス用基板(電極付き透光性基板)および有機LED素子について説明する。図1(a)は、本発明の実施の形態の電子デバイス用基板であり、図1(b)はこの電子デバイス用基板を備えた有機LED素子の構造を示す断面図である。
本発明の有機LED素子を形成するための電子デバイス用基板は、図1(a)に示すように、ガラス基板101と、前記ガラス基板101の第1の主面側の面101aに形成されたガラス層からなる散乱層102とを具備し、前記散乱層102は前記第1の主面側の面101aと接する第2の面102bと、前記第2の面102bに対向する第1の面102aを具備し、前記第1の面102aが湾曲面で構成されたうねりを構成して第1の主面を構成することを特徴とする。そしてこの第1の面102aに透光性電極103が形成されるが、図1(a)では電極形成前の状態を示す。また、この表面は、うねりの波長Rλaが50μmより大きく、うねりを構成する表面の表面粗さRaの、表面のうねりの波長Rλaに対する比Ra/Rλaが1.0×10-4以上3.0×10-2以下であるのが望ましい。符号101bは第2の主面である。
本発明の有機LED素子は、うねりを有する電極付き透光性基板100と、有機層110と、反射性電極120とにより構成される。電極付き透光性基板100は、透光性のガラス基板からなる基板101と、散乱層102と、透光性電極103とにより構成される。
また、ガラスからなる前記散乱層102の半分の厚さ(δ/2)における散乱物質の密度ρ1と、前記透光性電極と対向する側の前記散乱層の表面(すなわち基板側の表面)から距離x(δ/2<x≦δ)における散乱物質の密度ρ2とは、ρ1≧ρ2を満たす。
ガラス粉末を焼成する場合、ガラス粉末を好適な方法で、塗布した状態の模式図を図2に示す。ここでは本発明の透光性基板を構成する散乱層であるガラス層の最上部の断面を示している。この状態は、例えば、溶剤或いは樹脂と溶剤を混合したものにガラス粒子Gを分散させ所望の厚さに塗布することで得られる。例えば、ガラス粒子Gの大きさは最大長さで0.1から10μm程度のものを用いる。樹脂と溶剤を混合した場合には、ガラス粒子Gが分散した樹脂膜を加熱し、樹脂を分解することで、図2の状態が得られる。図2は簡略して記載しているが、ガラス粒の間には、隙間が空いている。
例えば、このような透光性基板上に有機LED素子を形成する場合、例えば透光性電極は薄く形成する必要があるが、この透光性電極が下地の影響を受ける事無く形成できるのは表面粗さが30nm以下、望ましくは10nm以下である。表面粗さが30nmを越えると、その上に形成される有機層の被覆性が悪くなる場合があり、ガラス散乱層上に形成される透光性電極ともう一方の電極との間で短絡が発生する場合がある。電極間短絡により、素子は不灯となるが、過電流を印加することにより、修復することが可能な場合がある。修復を可能とするうえで、ガラス散乱層の粗さは望ましくは10nm以下であり、さらに望ましくは、3nm以下である。
なお、ある材料系では焼成温度を570℃以上としたときに表面粗さ10nm以下とすることができることがわかっている(表1参照)。材料系によって最適な焼成条件は異なるが、散乱物質の種類や大きさをコントロールすることで散乱物質が最表面に存在するのを抑制し、表面平滑性に優れた散乱層を得ることができる。
その結果を表1に示す。
上記のようなガラスを用いて、ガラス粉末に加工し、さらに樹脂と混合してペーストを作製してガラス基板上に印刷した後、それぞれ表1に示す温度にて焼成を行った。このように焼成条件を調整することで、うねりの粗さRaやうねりの波長Rλaの異なる7種類の散乱層付きガラス基板を作製した。そしてさらに比較用として散乱層のない平らなガラス基板も準備した。
評価結果は、シャープペンシルの芯がゆがんで見える場合を○、芯がまっすぐにゆがまずに見える場合を×、判断が難しい場合を△とした。
また、この比(Ra/Rλa)が3.0×10-2を越えるほどうねりの粗さRaが大きいときは、電極、あるいは有機層を均一に成膜できないため、デバイスの形成が困難となる。
したがって上記のように、Rλa>50μm 且つ Ra/Rλa=1.0×10-4~3.0×10-2以下とするのが望ましい。また、Rλa>10μm 且つ Ra/Rλa =1.0×10-5~1.0×10--1であっても、おおむね映りこみすなわち鏡面反射性を低減させることができる。
これは実験結果から1vol%以上散乱物質が含有されているとき、十分な光散乱性を得ることができることがわかる。
また、ガラスからなる前記散乱層の半分の厚さ (δ/2)における散乱物質の密度ρ1と、散乱層最表面からの距離xが0≦x≦δ/2を満足する、xにおける散乱物質の密度ρ2が、ρ1≧ρ2を満たすδが存在するような透光性基板を用いることで、十分な散乱特性を有しかつ平滑な表面を持つ透光性基板を得ることが可能となる。
散乱物質が気泡である場合には、焼成温度などの焼成条件を調整することで、気泡の大きさや気泡分布や密度を調整可能である。
前記散乱物質が前記ベース層を構成するガラスの析出結晶である場合には、焼成温度などの焼成条件を調整することで、気泡の大きさや気泡分布や密度を調整可能である。
(基板)
透光性基板の形成に用いられる透光性の基板101としては、主としてガラス基板など、可視光に対する透過率が高い材料が用いられる。透過率の高い材料は、具体的には、ガラス基板のほかにはプラスチック基板が用いられる。ガラス基板の材料としては、アルカリガラス、無アルカリガラスまたは石英ガラスなどの無機ガラスがある。また、プラスチック基板の材料としては、ポリエステル、ポリカーボネート、ポリエーテル、ポリスルホン、ポリエーテルスルホン、ポリビニルアルコールならびにポリフッ化ビニリデンおよびポリフッ化ビニルなどのフッ素含有ポリマーがある。なお、基板を水分が透過するのを防止するために、プラスチック基板にバリア性をもたせる構成としてもよい。透光性の基板101の厚さは、ガラスの場合0.1mm~2.0mmが好ましい。但し、あまり薄いと強度が低下するので、0.5mm~1.0mmであることが特に好ましい。
散乱層表面のうねりについてはすでに説明したとおりである。また続いて、散乱層の構成、作製方法、特性および屈折率の測定方法について、詳細に説明する。なお、詳細は後述するが、有機LEDの主眼である光取り出し効率の向上を実現するためには、散乱層の屈折率は、透光性電極材料の屈折率よりも同等若しくは高くするのが望ましいが、0.2程度であれば小さくてもよい場合もある。
本発明者らは、後述する散乱層の特性を得るために、光学シミュレーションを行い、それぞれのパラメータについて、その取り出し効率に与える影響を調べた。用いた計算ソフトはOPTIS社製、ソフトSPEOSである。本ソフトは光線追跡ソフトであると同時に、散乱層はMie散乱の理論式を適用することが可能である。実際に電荷注入・輸送層、発光層などの発光機能を有する層として用いられる有機層の厚さは、実際は合計0.1μmから0.3μm程度であるが、光線追跡では光線の角度は厚さを変えても変わらないことから、ソフトで許される最小厚さ1μmとした。ガラス基板および散乱層の合計厚さも同様の理由から100μmとした。また簡単の為、有機層および透光性電極を電子注入層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。計算ではこれらの屈折率を同じとしているが、有機層と透光性電極の屈折率は同程度の値であり、計算結果を大きく変えるものではない。また有機層が薄いことから、厳密に考えると干渉による導波路モードが立つが、幾何光学的に扱っても、大きく結果を変えることはないので、今回の発明の効果を計算で見積もるには十分である。有機層では、合計6面から指向性を持たずに発光光が出射するものとする。全光束量を1000lmとし、光線本数を10万本或いは100万本として計算した。透光性基板から出射した光は、透光性基板の上部10μmに設置した受光面で捕らえ、その照度から取り出し効率を算出した。
本実施の形態では、散乱層102は、前述したように、塗布などの方法でガラス基板上にガラス粉末を形成し、所望の温度で焼成することで形成され、第1の屈折率を有するベース材105と、前記ベース材105中に分散された、前記ベース材105と異なる第2の屈折率を有する複数の散乱物質104とを具備し、前記散乱層内部から最表面にむかって、前記散乱層中の前記散乱物質の層内分布が、小さくなっており、ガラス層を用いることで前述したように、優れた散乱特性を有しつつも表面の平滑性を維持することができ、発光デバイスなどの光出射面側に用いることで極めて高効率の光取り出しを実現することができる。
散乱層の作製方法は、塗布および焼成により行うが、特に、10~100μmの厚膜を大面積にうねりを形成するように、均一かつ迅速に形成するという観点から、ガラスをフリットペースト化して作製する方法が好ましい。フリットペースト法を活用するために、基板ガラスの熱変形を抑制するために、散乱層のガラスの軟化点(Ts)が基板ガラスの歪点(SP)よりも低く、かつ熱膨張係数αの差が小さいことが望ましい。軟化点と歪点の差は30℃以上であることが好ましく、50℃以上であることがより好ましい。また、散乱層と基板ガラスの膨張率差は、±10×10-7(1/K)以下であることが好ましく、±5×10-7(1/K)以下であることがより好ましい。ここで、フリットペーストとは、ガラス粉末が樹脂、溶剤、フィラーなどに分散したものを指す。フリットペーストをスクリーン印刷などのパターン形成技術を用いてパターニング、焼成することで、ガラス層被覆が可能となる。以下技術概要を示す。
1.ガラス粉末
ガラス粉末粒径は1μm~10μmである。焼成された膜の熱膨張を制御するため、フィラーを入れることがある。フィラーは、具体的には、ジルコン、シリカ、アルミナなどが用いられ、粒径は0.1μm~20μmである。
本発明では、例えば、前記散乱層が、P2O5が20~30mol%、B2O3が、3~14mol%、Li2OとNa2OとK2Oの総量が10~20mol%、Bi2O3が10~20mol%、TiO2が3~15mol%、Nb2O5が10~20mol%、WO3が5~15mol%を含み、以上成分の合量が、90mol%以上であるものを用いる。
P2O5は、このガラス系の骨格を形成しガラス化させる必須成分であるが、含有量が小さすぎる場合、ガラスの失透性が大きくなりガラスを得ることができなくなるため、15%以上が好ましく、18%以上がより好ましい。一方、含有量が大きすぎると屈折率が低下するため、発明の目的を達成することができなくなる。従って、含有量は30%以下が好ましく、28%以下がより好ましい。
MgO、CaO、SrOは、溶融性を向上させる任意成分であるが、同時に屈折率を低下させる成分であるため、いずれも10%以下であることが好ましく、8%以下であることがより好ましい。
B2O3は、ネットワーク形成酸化物であり、このガラス系における必須成分である。含有量が少なすぎる場合、ガラス形成しなくなるか、ガラスの耐失透性の低下をもたらすため、20%以上含有することが好ましく、25%以上であることがより好ましい。一方、含有量が多すぎると、屈折率が低下し、さらに耐熱性の低下を招くため、含有量は60%以下に制限され、より好ましくは55%以下である。
Li2Oは、ガラス転移温度を低下させる成分である。しかしながら、導入量が大きすぎる場合、ガラスの耐失透性が低下してしまう。そのため、含有量は20%以下が好ましく、18%以下がより好ましい。
ZnOは、ガラスの屈折率を向上させるとともに、ガラス転移温度を低下させる必須成分である。そのため、導入量は5%以上が好ましく、7%以上がより好ましい。一方、添加量が大きすぎる場合、耐失透性が低下してしまい均質なガラスが得られなくなってしまうため、50%以下であることが好ましく、45%以下であることがより好ましい。
Y2O3およびYb2O3は高屈折率を達成し、かつB2O3系ガラスに導入すると耐侯性を向上させ、La2O3と共存させることにより、ガラスの安定性を向上させる成分であるが、導入量が大きすぎる場合、ガラスの安定性が低下してしまうため、含有量はそれぞれ20%以下であることが好ましく、18%以下であることが好ましい。
本発明の目的に合致させるためには、以上に記載の成分の合量は90%以上であることが望ましく、95%以上であることがさらに好ましい。以上に記載の成分以外であっても、清澄、溶解性向上などの目的で本発明の効果を損なわない範囲で添加しても良い。このような成分として、例えば、Sb2O3、SnO2、MgO、CaO、SrO、GeO2、Ga2O3、In2O3、フッ素が挙げられる。
高屈折率のガラスを得るためには、Nb2O5+TiO2+Bi2O3+ZrO2が5%以上であることが好ましく、8%以上であることがより好ましい。一方、この合量が大きすぎると、ガラスの耐失透性が低下したり、着色を生じたりするため、40%以下が好ましく、38%以下がより好ましい。
Bi2O3は、高屈折率を達成し、かつ多量に導入しても安定にガラスを形成する必須成分である。そのため、その含有量は、10%以上が好ましく、15%以上がより好ましい。一方、過剰に添加すると、ガラスに着色が生じ、本来透過すべき光を吸収してしまい、取り出し効率が低下してしまうことに加え、失透性が高くなり、均質なガラスを得ることができなくなってしまう。そのため、含有量は50%以下が好ましく、45%以下がより好ましい。
B2O3は、Bi2O3を多量に含むガラスにおいて、ネットワークフォーマとして働き、ガラス形成を助ける必須成分であり、その含有量は、1%以上が好ましく、3%以上がより好ましい。しかしながら、添加量が大きすぎる場合、ガラスの屈折率が低下してしまうため、40%以下が好ましく、38%以下がより好ましい。
樹脂は、スクリーン印刷後、塗膜中のガラス粉末、フィラーを支持する。具体例としては、エチルセルロース、ニトロセルロース、アクリル樹脂、酢酸ビニル、ブチラール樹脂、メラミン樹脂、アルキッド樹脂、ロジン樹脂などが用いられる。主剤として用いられるのは、エチルセルロースとニトロセルロースがある。なお、ブチラール樹脂、メラミン樹脂、アルキッド樹脂、ロジン樹脂は塗膜強度向上の為の添加として用いられる。焼成時の脱バインダ温度は、エチルセルロースで350℃から400℃、ニトロセルロースで200℃から300℃である。
樹脂を溶解しかつ印刷に必要な粘度を調整する。また印刷中には乾燥せず、乾燥工程では、すばやく乾燥する。沸点200℃から230℃のものが望ましい。粘度、固形分比、乾燥速度調整のためブレンドして用いる。具体例としては、スクリーン印刷時のペーストの乾燥適合性からエーテル系溶剤(ブチルカルビトール(BC)、ブチルカルビトールアセテート(BCA)、ジエチレングリコールジ-n-ブチルエーテル、ジプロピレングリコールブチルエーテル、トリプロピレングリコールブチルエーテル、酢酸ブチルセロソルブ)、アルコール系溶剤(α-テルピネオール、パインオイル、ダワノール)、エステル系溶剤(2,2,4-トリメチル-1,3-ペンタンジオールモノイソブチレート)、フタル酸エステル系溶剤(DBP(ジブチルフタレート)、DMP(ジメチルフタレート)、DOP(ジオクチルフタレート))がある。主に用いられているのは、α-テルピネオールや2,2,4-トリメチル-1,3-ペンタンジオールモノイソブチレート)である。なお、DBP(ジブチルフタレート)、DMP(ジメチルフタレート)、DOP(ジオクチルフタレート)は、可塑剤としても機能する。
粘度調整、フリット分散促進の為、界面活性剤を使用しても良い。フリット表面改質の為、シランカップリング剤を使用しても良い。
(1)フリットペースト
ガラス粉末とビヒクルを準備する。ここで、ビヒクルとは、樹脂、溶剤、界面活性剤を混合したものをいう。具体的には、50℃~80℃に加熱した溶剤中に樹脂、界面活性剤などを投入し、その後4時間から12時間程度静置したのち、ろ過し、得られる。
次に、ガラス粉末とビヒクルとを、プラネタリーミキサーで混合した後、3本ロールで均一分散させる。その後粘度調整のため、混練機で混練する。通常ガラス材料70~80wt%に対してビヒクル20~30wt%とする。
(1)で作製したフリットペーストをスクリーン印刷機を用いて印刷する。スクリーン版のメッッシュ荒さ、乳剤の厚み、印刷時の押し圧、スキージ押し込み量などで形成される、フリットペースト膜の膜厚を制御できる。印刷後焼成炉で乾燥させる。
焼成炉で印刷、乾燥した基板を焼成する。焼成は、フリットペースト中の樹脂を分解・消失させる脱バインダ処理とガラス粉末を焼結、軟化させる焼成処理からなる。脱バインダ温度は、エチルセルロースで350℃~400℃、ニトロセルロースで200℃~300℃であり、30分から1時間大気雰囲気で加熱する。その後温度を上げて、ガラスを焼結、軟化させる。焼成温度は軟化温度から軟化温度+20℃であり、処理温度により内部に残存する気泡の形状、大きさが異なる。その後、冷却して基板上にガラス層が形成される。得られる膜の厚さは、5μm~30μmであるが、印刷時に積層することでさらに厚いガラス層が形成可能である。
図11は、光取り出し効率(%)と散乱物質の含有率(vol%)との関係を示すグラフである。以下、簡略化のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(厚さ:30μm、ベース材の屈折率:1.9、散乱物質の屈折率:1.0)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。グラフで示されるように、散乱層中における散乱物質の含有率は、1vol%以上が好ましい。散乱物質の大きさで挙動が異なるが、散乱層中における散乱物質の含有率が1vol%あれば、光取り出し効率を40%以上にすることができる。また、散乱層中における散乱物質の含有率が5vol%以上であれば、光取り出し効率を65%以上にすることができるので、より好ましい。また、散乱層中における散乱物質の含有率が10vol%以上であれば、光取り出し効率を70%以上に向上することができるので、さらに好ましい。また、散乱層中における散乱物質の含有率が15vol%近傍であれば、光取り出し効率を80%以上に向上することができるので、特に好ましい。なお、散乱層の量産を考えると、製造ばらつきの影響を受けにくい10vol%~15vol%が好ましい。ここで散乱物質の散乱層内での面内分布は均一となっているのが望ましい。
図12は、光取り出し効率(%)と散乱物質の屈折率との関係を示すグラフである。以下、簡略のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(厚さ:30μm、ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の数:約3600万個、散乱物質の含有量:15vol%)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。グラフで示されるように、ベース材の屈折率(2.0)と散乱物質の屈折率との差が0.2以上(散乱物質の屈折率が1.8以下)であれば、光取り出し効率を80%以上にすることができるので、特に好ましい。なお、ベース材の屈折率と散乱物質の屈折率との差が0.1であっても(散乱物質の屈折率が1.9)、光取り出し効率を65%以上にすることができる。
図13は、光取り出し効率(%)と散乱物質の含有率(vol%)との関係を示すグラフである。以下、簡略のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の屈折率:1.0)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。グラフで示されるように、散乱層中における散乱物質の含有率が1vol%以上であれば、散乱層の厚さが15μm以下であっても、光取り出し効率を55%以上にすることができるので、好ましい。また、散乱層中における散乱物質の含有率が20vol%以上であれば、散乱層の厚さが60μm以上であっても、光取り出し効率を70%以上にすることができるので、好ましい。また、散乱層中における散乱物質の含有率が5vol%~15vol%あれば、散乱層の厚さが15μm以下や60μm以上であっても、光取り出し効率を80%以上にすることができるので、特に好ましい。
図14は、光取り出し効率(%)と散乱物質(粒子)の個数(個/mm2)との関係を示すグラフである。以下、簡略のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の屈折率:1.0)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。グラフで示されるように、散乱層の厚さにかかわらず、散乱物質の数で光取り出し効率が変わることがわかる。グラフで示されるように、散乱層1mm2当たりの散乱物質の数が1×104個以上あれば、光取り出し効率を55%以上にすることができるので、好ましい。また、散乱層1mm2当たりの散乱物質の数が2.5×105個以上あれば、光取り出し効率を75%以上にするできるので、より好ましい。
また、散乱層1mm2当たりの散乱物質の数が5×105~2×106個あれば、光取り出し効率を80%以上にすることができるので、特に好ましい。ここで、散乱物質の径が60μm以上であっても、3×106個あっても、光取り出し効率を70%以上にすることができる。
図15は、光取り出し効率(%)と散乱層のベース材の1mmt%における透過率との関係を示すグラフである。以下、簡略のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(厚さ:30μm、ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の屈折率:1.0、散乱物質の数:約3600万個、散乱物質の含有量:15vol%)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した。グラフで示されるように、散乱層のベース材の透過率が50%であっても、光取り出し効率は55%以上にすることができる。また、散乱層のベース材の透過率が90%であれば、光取り出し効率は80%以上にすることができる。ベース材をガラスとした場合、その透過率は98%ぐらいであるため、光取り出し効率は80%を超えることができる。
図16は、光取り出し効率(%)と陰極の反射率(%)との関係を示すグラフである。以下、簡略のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(厚さ:30μm、ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の屈折率:1.0、散乱物質の数:約3600万個、散乱物質の含有量:15vol%)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。グラフで示されるように、陰極の反射率が低下すると、光取り出し効率も低下する。ここで、青色LEDの陰極反射率は80%~90%であるため、光取り出し効率が40%~50%を得られることがわかる。ここで、特許文献1の有機LED素子は反射率100%を想定し、その光取り出し効率が約50%である。一方、本発明の有機LED素子の反射率を100%として特許文献1の有機LED素子の反射率と同じ条件とした場合、グラフからわかるように、その光取り出し効率は80%を超える。つまり、本発明の有機LED素子の光取り出し効率は、特許文献1の有機LED素子の光取り出し効率に比べ、1.6倍向上していることがわかる。よって、本発明の有機LEDは、蛍光灯に代わる照明用光源として用いられることができる。
図17は、散乱層に出射する光の割合と散乱層のベース材の屈折率との関係を示すグラフである。以下、簡略化のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(厚さ:30μm、散乱物質の径:2μm、散乱物質の屈折率:1.0、散乱物質の数:約3600万個、散乱物質の含有量:15vol%)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。グラフで示されるように、陽極の屈折率が散乱層の屈折率よりも大きい場合、散乱層の表面で全反射が発生し、散乱層に進入する光の量が減る。よって、光の取り出し効率が低下することがわかる。従って、本発明の散乱層の屈折率は、陽極の屈折率と同等若しくはそれ以上であることが好ましい。ただし、陽極の屈折率が散乱層の屈折率よりも大きい場合、40%の光を取り出すことができる。特に、陽極と散乱層の屈折率差が0.2以下であれば50%の光を取り出すことができる。従って、本発明の散乱層の屈折率は、陽極の屈折率と同等若しくはそれ以下でない場合も有効である場合がある。
図18は、波長と散乱層のベース材の屈折率との関係を示すグラフである。図19は、波長と受光面照度との関係を示す結果である。なお、図19(a)は図18のCase1に、図19(b)は図18のCase2に、図19(c)は図18のCase3に、図19(d)は図18のCase4に対応するスペクトル図である。以下、簡略のため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、上記グラフは、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、散乱層(厚さ:30μm、ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の屈折率:1.0、散乱物質の数:約3600万個、散乱物質の含有量:15vol%)、透光性基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した。なお、透光性電極の屈折率を1.9とした。図19に示されるように、散乱層のベース材の屈折率が有機層および透光性電極の屈折率よりも低い場合、その波長での取り出し効率が低下し、色味が変化してしまうことがわかる。具体的に説明すると、図19(c)からわかるように、波長が550nm以上の場合、屈折率が1.9以下になると、発光効率が低下することがわかる。つまり、有機LED素子の赤味において特性が劣化する。この場合は、素子の構成として、赤味を強くした素子を形成することが必要となる。
散乱層の屈折率を測定するには、下記の2つの方法がある。
一つは、散乱層の組成を分析し、その後、同一組成のガラスを作製し、プリズム法にて屈折率を評価する。他の一つは、散乱層を1~2μmまで薄く研磨し、泡のない10μmΦ程度の領域で、エリプソ測定し、屈折率を評価する。なお、本発明では、プリズム法にて屈折率を評価することを前提としている。
散乱層は、透光性電極が設けられる主表面を有している。上述したように、本発明の散乱層は、散乱物質を含有している。上述したように、散乱物質の径としては、大きければ大きいほど含有量が少なくても光取り出し効率の向上が図れる。しかし、発明者の実験によれば、径が大きければ大きいほど、散乱層の主表面から突出した場合に散乱層の主表面の表面粗さすなわち算術平均粗さRaが大きくなる傾向にある。上述したように、散乱層の主表面には透光性電極が設けられる。そのため、散乱層の主表面の算術平均粗さRaが大きいほど、透光性電極と散乱層間で短絡し、有機LED素子が発光しないという問題がある。上述した特許文献1は、段落0010において、基板に形成された凹凸が数μm程度であっても問題であること開示しているが、発明者らの実験によると、μmの単位では有機LED素子の発光が得られにくにくいことがわかった。
透光性電極(陽極)103は、有機層110で発生した光を外部に取り出すために、80%以上の透光性が要求される。また、多くの正孔を注入するため、仕事関数が高いものが要求される。具体的には、ITO、SnO2、ZnO、IZO(Indium Zinc Oxide)、AZO(ZnO-Al2O3:アルミニウムがドーピングされた亜鉛酸化物)、GZO(ZnO-Ga2O3:ガリウムがドーピングされた亜鉛酸化物)、NbドープTiO2、TaドープTiO2などの材料が用いられる。陽極103の厚さは、100nm以上が好ましい。なお、陽極103の屈折率は、1.9~2.2程度である。ここで、キャリア濃度を増加させると、ITOの屈折率を低下させることができる。市販されているITOは、SnO2が10wt%が標準となっているが、これより、Sn濃度を増やすことで、ITOの屈折率を下げることができる。但し、Sn濃度増加により、キャリア濃度は増加するが、移動度および透過率の低下がある為、これらのバランスをとって、Sn量を決める必要がある。
ここで、ITOの屈折率は、散乱層102を構成するベース材105の屈折率や反射電極120の屈折率を考慮して決定することが好ましい。ITOの屈折率は、散乱層102を構成するベース材105の屈折率よりも小さいか同等であるのが望ましいが、若干は大きくてもよい。導波路計算や反射性電極120の反射率等を考慮すると、ITOの屈折率とベース材105の屈折率との差は0.2以下であることが好ましい。
なお、透光性電極を陰極としても良いことは言うまでもない。
有機層110は、発光機能を有する層であり、正孔注入層111と、正孔輸送層112と、発光層113と、電子輸送層114と、電子注入層115とにより構成される。有機層110の屈折率は、1.7~1.8程度である。
正孔注入層111は、陽極103からの正孔注入障壁を低くするために、イオン化ポテンシャルの差が小さいものが要求される。正孔注入層111における電極界面からの電荷の注入効率の向上は、素子の駆動電圧を下げるとともに、電荷の注入効率を高める。高分子では、ポリスチレンスルフォン酸(PSS)がドープされたポリエチレンジオキシチオフェン(PEDOT:PSS)、低分子ではフタロシアニン系の銅フタロシアニン(CuPc)が広く用いられる。
正孔輸送層112は、正孔注入層111から注入された正孔を発光層133に輸送する役割をする。適切なイオン化ポテンシャルと正孔移動度を有することが必要である。正孔輸送層112は、具体的には、トリフェニルアミン誘導体、N,N’-ビス(1-ナフチル)-N,N’-ジフェニル-1,1’-ビフェニル-4,4’-ジアミン(NPD)、N,N’-ジフェニル-N,N’-ビス[N-フェニル-N-(2-ナフチル)-4’-アミノビフェニル-4-イル]-1,1’-ビフェニル-4,4’-ジアミン(NPTE)、1,1-ビス[(ジ-4-トリルアミノ)フェニル]シクロヘキサン(HTM2)およびN,N’-ジフェニル-N,N’-ビス(3-メチルフェニル)-1,1’-ジフェニル-4,4’-ジアミン(TPD)などが用いられる。正孔輸送層112の厚さは、10nm~150nmが好ましい。厚さは薄ければ薄いほど低電圧化できるが、電極間短絡の問題から10nm~150nmであることが特に好ましい。
発光層113は、注入された電子と正孔が再結合する場を提供し、かつ、発光効率の高い材料を用いる。詳細に説明すると、発光層113に用いられる発光ホスト材料および発光色素のドーピング材料は、陽極および陰極から注入された正孔および電子の再結合中心として機能する、また、発光層におけるホスト材料への発光色素のドーピングは、高い発光効率を得ると共に、発光波長を変換させる。これらは電荷注入のための適切なエネルギーレベルを有すること、化学的安定性や耐熱性に優れ、均質はアモルファス薄膜を形成することなどが求められる。また、発光色の種類や色純度が優れていることや発光効率の高いことが求められる。有機材料である発光材料には、低分子系と高分子系の材料がある。さらに、発光機構によって、蛍光材料、りん光材料に分類される。発光層113は、具体的には、トリス(8-キノリノラート)アルミニウム錯体(Alq3)、ビス(8-ヒドロキシ)キナルジンアルミニウムフェノキサイド(Alq′2OPh)、ビス(8-ヒドロキシ)キナルジンアルミニウム-2,5-ジメチルフェノキサイド(BAlq)、モノ(2,2,6,6-テトラメチル-3,5-ヘプタンジオナート)リチウム錯体(Liq)、モノ(8-キノリノラート)ナトリウム錯体(Naq)、モノ(2,2,6,6-テトラメチル-3,5-ヘプタンジオナート)リチウム錯体、モノ(2,2,6,6-テトラメチル-3,5-ヘプタンジオナート)ナトリウム錯体およびビス(8-キノリノラート)カルシウム錯体(Caq2)などのキノリン誘導体の金属錯体、テトラフェニルブタジエン、フェニルキナクドリン(QD)、アントラセン、ペリレン並びにコロネンなどの蛍光性物質が挙げられる。ホスト材料としては、キノリノラート錯体が好ましく、特に、8-キノリノールおよびその誘導体を配位子としたアルミニウム錯体が好ましい。
電子輸送層114は、電極から注入された電子を輸送するという役割をする。電子輸送層114は、具体的には、キノリノールアルミニウム錯体(Alq3)、オキサジアゾール誘導体(例えば、2,5-ビス(1-ナフチル)-1,3,4-オキサジアゾール(BND)および2-(4-t-ブチルフェニル)-5-(4-ビフェニル)-1,3,4-オキサジアゾール(PBD)など)、トリアゾール誘導体、バソフェナントロリン誘導体、シロール誘導体などが用いられる。
電子注入層115は、電子の注入効率を高めるものが要求される。電子注入層115は、具体的には、陰極界面にリチウム(Li)、セシウム(Cs)等のアルカリ金属をドープした層を設ける。
反射性電極(陰極)120は、仕事関数の小さな金属またはその合金が用いられる。陰極120は、具体的には、アルカリ金属、アルカリ土類金属および周期表第3属の金属などが挙げられる。このうち、安価で化学的安定性の良い材料であることから、アルミニウム(Al)、マグネシウム(Mg)またはこれらの合金などが好ましく用いられる。また、Al、MgAgの共蒸着膜、LiFまたはLi20の薄膜蒸着膜の上にAlを蒸着した積層電極等が用いられる。また、高分子系では、カルシウム(Ca)またはバリウム(Ba)とアルミニウム(Al)の積層等が用いられる。
なお、反射性電極を陽極としてもよいことは言うまでもない。
以下に、図面を用いて、本発明の電子デバイス用基板の製造方法を説明する。図20は、本発明の電子デバイス用基板の製造方法を示すフローチャートである。本発明の電子デバイス用基板の製造方法は、透光性基板を準備する工程(ステップ1100)と、透光性基板上に、有機LED素子の発光光の波長において第1の屈折率を有するベース材と、ベース材内部に設けられベース材と異なる屈折率を有する複数の散乱物質とを備えた散乱層を形成する工程(ステップ1110)と、散乱層上に、透光性電極を形成する工程(ステップ1120)とを有する。
次に、有機LED素子の発光光の波長において第1の屈折率を有するベース材と、ベース材内部に設けられベース材と異なる屈折率を有する複数の散乱物質とを備えた散乱層形成材料を準備する。そして、準備した散乱層形成材料を塗布し、焼成することで、散乱物質が面内に均一に分布された散乱層を透光性基板上に形成する(ステップ1110)。
以下に、図面を用いて、本発明の有機LED素子の製造方法を説明する。図21は、本発明の有機LED素子の製造方法を示すフローチャートである。本発明の有機LED素子の製造方法は、透光性基板を準備する工程(ステップ1100)と、透光性基板上に、有機LED素子の発光光の波長において第1の屈折率を有するベース材と、ベース材内部に設けられベース材と異なる屈折率を有する複数の散乱物質とを備えた散乱層を形成する工程(ステップ1110)と、散乱層上に、透光性電極を形成する工程(ステップ1120)と、透光性電極上に有機層を形成する工程(ステップ1200)と、有機層上に反射性電極を形成する工程(ステップ1210)とを有する。
そしてさらに、反射電極の映りこみを防止するためのうねりの大きさについても種々の実験と考察を重ね最適の範囲を規定しているため、信頼性の高い有機LED素子を得ることが可能となっている。
ここで、表面に凹凸があると、この上層に形成される第1の電極表面に凹凸が形成され易く、この上層に蒸着法などによって発光機能を有する層などを形成すると、これらの有機層の凸凹に対する被覆性が悪くなり、有機層の膜厚にばらつきが生じたり、また、その結果、上記第1の電極と有機層上に形成される第2の電極表面との間の電極間距離にばらつきが生じることになる。その結果、電極間距離の小さい領域においては、有機層に局所的に大電流が流れることになり、電極間短絡を生じ不灯の原因となることがわかった。また高解像度ディスプレイのように、微細画素で構成する表示装置を形成する場合には、微細な画素パターンを形成する必要があり、表面の凹凸は、画素の位置やサイズにばらつきが生じる原因となるだけでなく、この凸凹で、表面に形成される電子デバイスの電極間が短絡してしまう場合がある。
(有機LED素子の他の構成例)
次に、図面を用いて、本発明の実施の形態2の電子デバイス用基板および有機LED素子の構成について説明する。なお、図1と同じ構成については、同じ番号を付与し、説明を省略する。図23は、本発明の有機LED素子用の透光性基板およびこれを用いて形成した有機LED素子の他の構造を示す断面図である。本発明の他の有機LED素子は、透光性電極つき透光性基板1400と、有機層1410と、反射性電極120とにより構成される。透光性電極付き透光性基板1400は、透光性の基板101と、散乱層1401と、透光性電極103とにより構成される。有機層1410は、正孔注入・輸送層1411と、発光層1412と、電子注入・輸送層1413とにより構成される。
また本発明の電子デバイス用基板は、有機LED素子に限定されることなく、無機EL素子、液晶など、種々の発光デバイス、あるいは光量センサ、太陽電池などの受光デバイスなど光デバイスの高効率化に有効である。
(散乱層の効果の実証)
以下、光取り出し効率の向上のために、散乱層が効果的であることの実証を説明する。試料1は本発明のうねりをもつ散乱層を備えた実施例であり、試料2が内部に散乱物質が設けられていない散乱層を備えた比較例である。計算方法は、上述の散乱層の計算方法と同じである。以下、各条件および結果(前面取り出し効率)を表2に示す。
各散乱層付き基板の全光透過率とヘイズ値を測定した。測定装置として、スガ試験機ヘーズメータHGM-2を用いた。リファレンスとして、上述したガラス基板[PD200]の素板を測定した。測定した結果を表4に示す。
散乱層1620および散乱層1620が形成されていないガラス基板1610上にITO膜1630を膜厚が150nmとなるように、スパッタにより成膜した。スパッタは室温で実施し、Ar 99.5SCCM、O2 0.5SCCM、圧力 0.47Pa、投入電力 2.35W/cm2であった。その後、蒸着装置を用いて、ITO膜1630上にAlq3膜1640を、Alq3膜1640上にAg膜1650をそれぞれ膜厚が200nmおよび70nmとなるように成膜した。今回の評価では、Ag膜1650の上方側から紫外線を照射し、Alq3膜1640を励起した。Ag膜1650の膜厚が厚い場合には、紫外線が透過せず、薄すぎるとAlq3膜1640からの蛍光光が反射されずに透過してしまう。Ag膜1650の膜厚を70nmとすることで、320nmの紫外光の場合、25%程度が透過することができ、一方で蛍光光のうちAg膜1650を透過してしまう割合を1%以下に抑えることが可能となった。Alq3膜1640はAg膜1650側から入射してきた紫外線により励起されるが、Alq3膜1640のAg膜1650に近い側では、ガラス基板1610側に発光した光とAg膜1650側に発光してAgで反射してガラス基板側に進行する光の干渉で弱め合う。なぜなら光路差は少ない一方で、Agでの反射により位相がπ程度ずれるからである。この問題については、Alq3膜1640の膜厚を200nmと厚めにすることで解決でき、測定される発光輝度を上げることができた。
(散乱層の主表面の平滑性の実証)
以下、光取り出し効率の向上のために、散乱層の主表面がうねりをもつのに加え、平滑(表面粗さRa(:算術平均粗さ)が30nm以下)であることが効果的であることの実証を説明する。
まず、ガラス基板としては、上述の旭硝子株式会社製ガラス基板[PD200]を用いた。散乱層は以下のように作製した。まずガラス組成が表6になるように粉末原料を調合し、1100℃の電気炉にて溶解し、ロールにキャストしてガラスのフレークを得た。このガラスのガラス転移温度は499℃、屈服点は545℃、熱膨張係数は74×10-7(1/℃)(100~300℃の平均値)である。このガラスのF線(486.13nm)での屈折率nFは2.0448、d線(587.56nm)での屈折率ndは2.0065、C線(656.27nm)での屈折率nCは1.9918である。屈折率およびガラス転移点・屈服点の測定方法は、上述の例と同様である。
(1)580℃焼成品の方が、温度が高い分だけ泡が膨張しており、カウントし易くなっている、
(2)ガラス粉末に付着した有機系の残渣物の分解が580℃でより進んでいて、泡数が多くなった。
(うねりについて)
次に、本発明の実施例3について説明する。
まず、測定用サンプルとして、[PD200]基板上に散乱層を成膜し、さらにその上に厚さ約80nmのAl薄膜を蒸着法で成膜したものを用意した。散乱層としては表10に示した7種類を用いた。ガラス組成A,B,C、Dをそれぞれ表11、表12、表13に示す。
(散乱層の全透過率(Haze値))
次に散乱層の全透過率について測定した結果を説明する。
ガラス基板上に表1に示したガラス組成で厚さの異なる散乱層を作製した。それぞれの厚さは9μm、15μm、30μmである。これらの散乱層の上に、前述と同様に有機LED素子を作製し、評価して、散乱層がない場合との光取り出し効率の比率を評価した。前述のヘーズメータを用いて、全光透過率、Haze値を測定する場合、図56に示すようにサンプルは積分球300内部にセットして、基板101を導波して、横方向に伝播する光をロスとしないようにして測定した。散乱層102の膜厚と全光透過率の関係を図57に、散乱層102の膜厚とhaze値の関係を図58に示す。
101 ガラス基板
102 散乱層
103 透光性電極
104 散乱物質
110 有機層
120 反射性電極
Claims (16)
- 相対向する第1および第2の主面を具備した基板と、
前記基板の前記第1の主面に形成された電極パターンとを備えた電子デバイス用基板であって、
前記基板の前記第1の主面が湾曲面で構成されたうねりを構成する表面であり、
前記表面のうねりの波長Rλaが50μmより大きく、
前記うねりを構成する表面のうねりの粗さRaの、うねりの波長Rλaに対する比Ra/Rλaが1.0×10-4以上3.0×10-2以下である電子デバイス用基板。 - 請求項1に記載の電子デバイス用基板であって、
前記基板は、
ガラス基板と、
前記ガラス基板の第1の主面に形成されたガラス層とを具備し、
前記ガラス層は前記ガラス基板の第1の主面側に当接する第2の面と、前記第2の面に対向する第1の面を具備し、前記第1の面が湾曲面で構成されたうねりを構成する表面である電子デバイス用基板。 - 請求項1または2に記載の電子デバイス用基板であって、
前記第1の主面に有機LED素子が形成される電子デバイス用基板。 - 請求項1乃至3のいずれかに記載の電子デバイス用基板であって、
前記第2の主面が前記第1の主面よりも平坦な面である電子デバイス用基板。 - 請求項1乃至4のいずれかに記載の電子デバイス用基板であって、
前記うねりを構成する表面の表面粗さRaが30nm以下である電子デバイス用基板。 - 相対向する第1および第2の主面のうち、少なくとも第1の主面が湾曲面で構成されたうねりを構成する表面である基板と、
前記基板の前記表面に形成された第1の電極と、
前記第1の電極の上層に形成された機能層と、
前記機能層の上層に形成された第2の電極とを具備し、
前記うねりを構成する表面のうねりの粗さRaの、うねりの波長Rλaに対する比Ra/Rλaが1.0×10-4以上3.0×10-2以下である電子デバイス。 - 請求項6に記載の電子デバイスであって、
前記基板は、ガラス基板と、
前記ガラス基板の第1の主面側に当接する第2の面と、前記第2の面に対向する第1の面を具備し、前記第1の面が湾曲面で構成されたうねりを構成する表面である電子デバイス。 - 請求項6または7に記載の電子デバイスであって、
前記うねりを構成する表面の表面粗さRaが30nm以下である電子デバイス。 - 請求項7または8に記載の電子デバイスであって、
前記ガラス基板は透光性のガラス基板であり、
ガラス基板上に形成され、透過する光の少なくとも1波長に対して第1の屈折率を有するベース材と、前記ベース材中に分散された、前記ベース材と異なる第2の屈折率を有する複数の散乱物質とを具備したガラスからなる散乱層を具備し、
前記散乱物質の前記散乱層内分布が、前記散乱層内部から前記第1の電極としての透光性電極にむかって、小さくなっている電子デバイス。 - 請求項9に記載の電子デバイスであって、
前記第1の電極は、前記散乱層上に形成され、前記第1の屈折率と同じ若しくはより低い第3の屈折率を有する透光性電極である電子デバイス。 - 請求項9または10に記載の電子デバイスであって、
前記散乱層の透光性電極側の表面からの距離x(x≦0.2μm)における散乱物質の密度ρ3が、距離x=2μmにおける前記散乱物質の密度ρ4に対し、ρ4>ρ3を満たす電子デバイス。 - 請求項9乃至11のいずれかに記載の電子デバイスであって、
前記散乱層が、mol%表記で、P2O5 15~30%、SiO2 0~15%、B2O3 0~18%、Nb2O5 5~40%、TiO2 0~15%、WO3 0~50%、Bi2O3 0~30%、ただし、Nb2O5+TiO2+WO3+Bi2O3 20~60%、Li2O 0~20%、Na2O 0~20%、K2O 0~20%、ただしLi2O+Na2O+K2O 5~40%、MgO 0~10%、CaO 0~10%、SrO 0~10%、BaO 0~20%、ZnO 0~20%、Ta2O5 0~10%を含む電子デバイス。 - 請求項9乃至12のいずれかに記載の電子デバイスであって、
前記散乱層は、前記透光性基板上に形成され、LED素子の発光光の波長のうち少なくとも一つの波長において第1の屈折率を有するベース材と、前記ベース材内部に位置し前記ベース材と異なる第2の屈折率を有する複数の散乱物質と、を備え、
前記散乱層上に形成され、前記第1の屈折率と同じ若しくはより低い前記波長における第3の屈折率を有する第1の電極としての透光性電極と、
前記透光性電極上に形成される光電変換機能を有する層と、
前記光電変換機能を有する層上に形成される第2の電極としての反射性電極とを備えた電子デバイス。 - 請求項13に記載の電子デバイスであって、
前記光電変換機能を有する層は、発光機能を有する層である電子デバイス。 - 請求項13に記載の電子デバイスであって、
前記光電変換機能を有する層は、光検出機能を有する層である電子デバイス。 - 請求項13に記載の電子デバイスであって、
前記光電変換機能を有する層は、発電機能を有する層である電子デバイス。
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| WO2012133832A1 (ja) * | 2011-03-31 | 2012-10-04 | 旭硝子株式会社 | 有機led素子、透光性基板、および透光性基板の製造方法 |
| JPWO2012133832A1 (ja) * | 2011-03-31 | 2014-07-28 | 旭硝子株式会社 | 有機led素子、透光性基板、および透光性基板の製造方法 |
| CN103199200A (zh) * | 2012-01-09 | 2013-07-10 | 三星显示有限公司 | 供体膜、用其制造有机发光二极管显示器的方法及用该方法制造的有机发光二极管显示器 |
| DE102012206955B4 (de) * | 2012-04-26 | 2016-09-22 | Osram Oled Gmbh | Verfahren zum Herstellen einer Streuschicht für elektromagnetische Strahlung |
| DE102012206955A1 (de) | 2012-04-26 | 2013-10-31 | Osram Opto Semiconductors Gmbh | Verfahren zum Herstellen einer Streuschicht für elektromagnetische Strahlung und Streuschicht zum Streuen elektromagnetischer Strahlung |
| US9945989B2 (en) | 2012-04-26 | 2018-04-17 | Osram Oled Gmbh | Process for producing a scattering layer for electromagnetic radiation and scattering layer for scattering electromagnetic radiation |
| JP2013246932A (ja) * | 2012-05-24 | 2013-12-09 | Konica Minolta Inc | 面発光素子およびその面発光素子を用いた照明装置 |
| JP2015222707A (ja) * | 2014-05-01 | 2015-12-10 | 東洋製罐グループホールディングス株式会社 | ガラス基板、有機el照明装置、ガラス基板の製造方法 |
| JP2018504747A (ja) * | 2014-12-24 | 2018-02-15 | コーニング精密素材株式会社Corning Precision Materials Co., Ltd. | 有機発光素子 |
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| JPWO2016159366A1 (ja) * | 2015-04-02 | 2018-02-01 | 凸版印刷株式会社 | 量子ドット保護フィルム並びにこれを用いて得られる波長変換シート及びバックライトユニット |
| US10557970B2 (en) | 2015-04-02 | 2020-02-11 | Toppan Printing Co., Ltd. | Quantum dot protective film, and wavelength conversion sheet and backlight unit obtained by using the same |
| CN106784081A (zh) * | 2016-11-22 | 2017-05-31 | 上海空间电源研究所 | 一种柔性薄膜太阳电池微量点胶组件及其工艺方法 |
| JP2019019011A (ja) * | 2017-07-12 | 2019-02-07 | 日本電気硝子株式会社 | 波長変換材料に用いられるガラス、波長変換材料、波長変換部材及び発光デバイス |
| JP7121329B2 (ja) | 2017-07-12 | 2022-08-18 | 日本電気硝子株式会社 | 波長変換材料に用いられるガラス、波長変換材料、波長変換部材及び発光デバイス |
| WO2023238831A1 (ja) * | 2022-06-09 | 2023-12-14 | Agc株式会社 | 舗装用光起電力モジュール、太陽光発電舗装ブロック、舗装用光起電力モジュールの製造方法、ガラス板、及びガラス床用合わせガラス |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2010084923A1 (ja) | 2012-07-19 |
| CN102293054B (zh) | 2016-08-03 |
| US20120025245A1 (en) | 2012-02-02 |
| KR20110116142A (ko) | 2011-10-25 |
| CN102293054A (zh) | 2011-12-21 |
| EP2384086A1 (en) | 2011-11-02 |
| EP2384086A4 (en) | 2014-01-08 |
| JP5824807B2 (ja) | 2015-12-02 |
| US8729593B2 (en) | 2014-05-20 |
| EP2384086B1 (en) | 2018-04-11 |
| TW201041205A (en) | 2010-11-16 |
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