TW200810157A - Composite for light conversion, light emitting device using the same, and method for controlling color tone - Google Patents

Abstract

This invention provides a composite for light conversion, which can obtain necessary fluorescence in a smaller thickness, is low in cost, and can suppress a light loss within the composite. The composite for light conversion comprises a plurality of oxide phases including at least one oxide crystalline phase which emits fluorescence. The composite for light conversion is characterized in that the surface roughness of at least one of a light incident surface of the composite for light conversion and a light emitting surface located on the opposite side of the light incident surface is not less than 0.05 μm in the arithmetic average roughness (Ra). Preferably, the composite for light conversion has a texture in which at least two or more oxide phases are continuously and three-dimensionally entangled with each other, and at least one of the oxide phase is formed of a solidification product which is a crystalline phase which emits fluorescence.

Description

200810157 IX. Invention description: C 日月月户^>#员3^] Description of the relevant application This application is filed on June 22, 2006 with the Japanese Patent Grant No. 2006-172163, and The application for priority is based on the Japanese Patent Application No. 2006-209435, the entire disclosure of which is hereby incorporated by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-emitting device that emits a light-emitting member such as a display, an illumination, a backlight, or the like, and more particularly to a light-converting member that obtains fluorescence by irradiation or light. A composite and a light-emitting device and a color tone control method using the composite for light conversion. [Prior Art] Background of the Invention 15 In recent years, a white light-emitting device using a color-sensing light-emitting element as a light-emitting source has been actively carried out. Because of the light weight, the use of mercury, and the long life, the special light-emitting diodes are expected to expand rapidly in the future. The blue light of the blue light-emitting element is turned into the most commonly used method of white light, and the blue color and the complementary color relationship are used to obtain the pseudo-white color. For example, it is described in Japanese Patent Laid-Open Publication No. 2000-2, No. 5, which is provided with a yellow light in front of a light-emitting diode that emits blue light, and contains a part of the 饯 八 * 八 八 八 八 色 色The coating of the light body is provided at its front end with a mold layer that mixes the blue light of the light source with the yellow light from the light-emitting body to form a white light-emitting diode. Luguang 200810157 The body is a YAG (Y3AI5O12) powder which is activated by hydrazine. However, in the structure of the white light-emitting diode which is generally used in the Japanese Patent Publication No. 2000-208815, since the phosphor powder is mixed with a resin such as epoxy, it has been pointed out that it is difficult to secure the firefly. The uniformity of the mixed state of the photo powder 5 and the resin, the stability of the thickness of the coating film, and the like are also difficult to control, and the chromatic aberration and unevenness of the white light-emitting diode are likely to occur. Further, since the resin which is necessary for the use of the phosphor powder is inferior to the metal or the ceramic, it is subjected to heat from the light-emitting element to cause denaturation, which tends to cause a decrease in transmittance, and the white light-emitting diode which is currently pursued. The high output of 10 is a bottleneck. In Japanese Patent Laid-Open Publication No. 2005-191197, the use of such a phosphor powder for the light-emitting efficiency and wavelength conversion efficiency of the light-converting white light-emitting diode is reduced, and the light transmittance is reduced. The light-emitting member is formed by coating the light-emitting element formed on the substrate, and further forming a light-transmitting member by forming a phosphor layer formed of a resin containing a phosphor powder in a state of covering the light-transmitting member 15 On the upper surface of the phosphor layer, a rough surface having an arithmetic mean roughness of 0.1 to 〇·8 μηι is formed. However, even the illuminating device cannot achieve sufficient fluorescence intensity and output. The present inventors have proposed to use a composite for light conversion formed by a solidified body containing a plurality of oxide phases of a (γ, 2〇Ce) 3Α150 phase and a Α12〇3 phase which are fluorescing and which are continuously and three-dimensionally intertwined with each other. A white light-emitting device comprising a body and a blue light-emitting element (International Publication WO 2004/065324). Since the phosphor composite has a uniform distribution of the phosphor phase, uniform yellow fluorescence can be stabilized, and since it is ceramic, heat resistance is excellent. In addition, since it is a bulk, it is not required to have a resin in the configuration of the white light-emitting device. Therefore, the white light-emitting device has a small color difference and unevenness, and is extremely suitable for high output. Further, in the white light-emitting device configured by using the blue light-emitting element and the light-converting 5 composite, the ratio of the blue light to the yellow fluorescent light can be controlled by changing the thickness of the composite for light conversion. Therefore, by making the thickness unevenness, the _ unevenness of the hue of the white light-emitting device can be easily suppressed to be small, and the manufacturing process is large compared with the conventional phosphor powder. advantage. 10 However, since the composite for light conversion utilizes the eutectic reaction between the oxide phases of the constituent phases in the manufacturing process, the ratio of each phase is limited to a certain extent, and the amount of the phosphor phase is greatly changed. Have difficulty. Therefore, in the adjustment of the color tone of the light-emitting device, when a large amount of light of a yellow component is required, the thickness of the composite for light conversion is increased, and the material cost of the composite for the partial light conversion 15 is increased. Further, although the light loss inside the composite melamine for light conversion is small, the thickness is increased as the thickness is increased, so that the surface for improving the luminous efficiency of the light-emitting device is not good. The purpose of the present invention is to provide a light-reducing composite which can obtain a necessary calendering with a relatively thin thickness, is low in cost, and is suppressed in light loss in the composite body. Further, the present invention provides a light-emitting device which is excellent in efficiency, color adjustment, and non-uniform in shape, and which is suitable for high-output. [Claim of the Invention] Summary of Invention 7 200810157 The present invention relates to a composite for light conversion, characterized in that it is a composite for light conversion formed by a plurality of oxide phases containing at least one crystal phase of a fluorescent oxide. The surface roughness of at least one of the light incident surface of the light conversion composite and the light emitting surface of the opposite side is arithmetically equal to 5 roughness (Ra) 〇. The composite for light conversion of the present invention is a bulk (block) of an oxide composite, and is different from a conventional light-converting body in which a particulate matter is dispersed in a resin. In addition, a suitable aspect of the present invention relates to a structure in which at least two or more oxide phases are continuously and three-dimensionally intertwined with each other, and at least 1 in the oxide phase. The type is a composite for light conversion formed by a solidified body that emits a crystal phase of fluorescence. Further, in a preferred aspect of the present invention, each of the oxide phases of the light-emitting surface of the composite for light conversion has a highly uneven surface. Further, a suitable aspect of the present invention relates to a composite for light conversion comprising at least a Y element, an A1 element and a Ce element in a composition. Further, the invention relates to a light-emitting device comprising the above-described composite for light conversion and a light-emitting element. In a suitable ship of the present invention, the hybrid composite body emits a fluorescent light having a peak at a wavelength of 530 to 58 〇 nm + and the light-emitting element emits light having a peak in a wavelength of 400 to 500 mn. Further, the present invention relates to a color turning method for adjusting the color tone of the light-emitting device by changing the surface roughness of the composite light-emitting conversion composite. By using the composite for light conversion of the present invention, it is possible to obtain more intense fluorescence than the conventional incident light 8 200810157. According to this, since the necessary fluorescence intensity can be obtained by using the thin composite for light conversion, it is possible to provide a composite for light conversion which is low in cost and which suppresses light loss in the composite body. In addition, since the fluorescence intensity can be controlled to 5 degrees without changing the thickness of the composite for light conversion, it is easy to adjust the color, and the gradual rate formed by the light-emitting element and the present light conversion composite is Ideal for high-output white light-emitting devices. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a mode 10 of an embodiment of the light-emitting device of the present invention. Fig. 2 is a photomicrograph of Example 1 of an example of the structure of the composite for light conversion of the present invention. 3 is a fluorescence spectrum diagram of Example 1 which is an example of the fluorescence characteristics of the composite for light conversion of the present invention. Fig. 4 is a luminescence spectrum of Example 8 of an example of a light-emitting device of the present invention. Fig. 5 is a chromaticity diagram of Embodiments 9, 1 and 11 of an example of the color tone adjusting method of the light-emitting device of the present invention. Fig. 6 is a 2 〇 cross-sectional micrograph of the surface of the composite for light conversion produced in Example 13. Fig. 7 is a cross-sectional micrograph of the surface of the composite for light conversion produced in Example 19. Fig. 8 is a photograph of a laser microscope of the surface of the composite for light conversion produced in Example 20. 9 200810157 Fig. 9 is a luminescence spectrum diagram of Example 21 of an example of a light-emitting device of the present invention. [Embodiment] Best Mode for Carrying Out the Invention 5 Hereinafter, the present invention will be described in detail. The composite for light conversion according to the present invention is characterized in that it is a composite for light conversion formed of a plurality of oxide phases containing at least one crystal phase which emits a fluorescent oxide, and the light for the composite for light conversion The surface roughness of at least one of the incident surface and the light radiating surface on the opposite side is an arithmetic mean of 10 roughness (Ra) of 0·05 μm or more. Generally, the composite for light conversion has a plate shape, and has an incident surface on which light rays before conversion are incident, and a converted light beam is emitted to the outside. It is characterized in that the surface roughness (Ra) of the incident surface or the radiating surface is 〇. 5 μm or more. The composite for light conversion according to the present invention is formed of a plurality of oxide phases containing at least one oxide crystal phase emitting the fluorescent light 15, and the constituent oxide phase other than the crystal phase of the emitted fluorescent oxide may be glass. Alternatively, it may be a molten solidified body, and is not particularly limited. A suitable aspect of the composite for light conversion may, for example, be a solidified body having at least two or more kinds of oxide phases continuously and three-dimensionally intertwined with each other, and at least one of the oxide phases is emitted. A composite for light conversion of a crystal phase of fluorescence. Fluorescence can be emitted by injecting excitation light onto the composite for light conversion. On the other hand, the surface of at least one of the composites for light conversion is processed to have a surface roughness of 0.05 μm or more in terms of arithmetic mean roughness (hereinafter referred to as Ra) described in JIS B 060.05-1994. 10 200810157

10 15

20 Because the surface of the composite for the light conversion is a rough surface of the surface of the 〇 (5), compared with the surface of the Ra<〇.〇5nm which is close to the mirror surface, it can be obtained from the composite of the light conversion of the same thickness. Stronger fluorescence, so the surface = degree Ra is limited to the above range. As the surface roughness Ra becomes larger, the obtained fluorescence intensity is enhanced, and the surface roughness Ra-〇^m is better. The composite for light conversion having a surface roughness Ra-Ο.ΐμηι is comparable to the same material and thickness of the surface-transparent surface roughness Ra < 0.05 pm near the mirror surface, It is more than 5% fluorescent. The surface roughness Ε^^0·25μιη is even better. Because it is possible to obtain more than 1% by weight of fluorescence. Therefore, by making the surface roughness of the surface of the composite for light conversion larger, it is possible to obtain the necessary fluorescence intensity with a thin thickness. According to this, the thickness of the composite for light conversion in the case of producing a light-emitting element can be made thin, and the amount of use of the composite for light conversion can be reduced, so that the cost of the material can be reduced. Further, since it is thinner than the conventional one, it is possible to suppress light loss inside the composite for light conversion. The upper limit of the surface roughness Ra is not particularly limited, but the surface roughness of the composite is relatively large with respect to the thickness of the composite for light conversion, and the shape retention is difficult, and the handleability is also deteriorated. Practically, the surface roughness Ra is preferably controlled to 1/2 or less of the thickness of the composite for light conversion. Further, from the viewpoint of easiness of forming surface roughness, etc., it is preferably 5 μm or less, and more preferably 30 μm or less. Further, in the composite for light conversion of the present invention, if the light transmission surface is a rough surface having a surface roughness Ra of 0.05 pm, the light is scattered on the light exit surface, but is finally transmitted through the entire light conversion composite. The radiation beam, its relative amount relative to the total incident beam, does not necessarily decrease, but may increase. Special 11 200810157 As described later, if a rough surface is formed on each oxide and a rough surface of Ra^ 〇·〇5μΐη is formed, the light extraction efficiency is significantly improved, and the fluorescence intensity is further improved. For improvement. In addition, if the rough surface of the surface roughness Ra-0.05 μπι * 5 in the composite for light conversion is located at the position of the path of the incident light, the incident light* will be scattered there, and the phase is efficiently It is preferred that the crystal phase which emits fluorescence is absorbed to obtain stronger fluorescence. In the case where the light conversion composite body is in the shape of a slab and the light is traveling in the thickness direction thereof, any one of the surface on which the light is incident (incident surface) and the surface on which the light on the opposite side is emitted (radiation surface) is 10 疋. The rough surface can get stronger fluorescence from the above effects. Further, if both the incident surface and the radiating surface are rough, it is preferable because the scattering effect is increased and stronger fluorescence can be obtained. The oxide phase varies depending on the composition of the component and the production conditions of the solidified body. Although there is no limitation of 4 inches, in the case where the composition contains at least a γ element, an A1 element, and 15 Ce quinone, for example, Al2〇3 ( The sapphire phase is equal to φ(Y, Ce)3Al5〇12 and contains at least two phases of such an oxide phase. At least two of the oxide phases form a structure in which they are continuous and three-dimensionally entangled with each other. There is also a case where a part of the oxide phase exists in a granular form in the other intertwined structure formed by the oxide phase. No matter in the 20 cases, there is no boundary layer of amorphous state in the realm of each phase, and the oxide phases are directly connected to each other. Therefore, the light loss in the composite for light conversion is small, and the light transmittance is also increased. The crystal phase in which the fluorescence is emitted is also changed depending on the production conditions of the component and the solidified body, and is not particularly limited, but in the case where the composition component contains at least a γ element, 12 200810157 A1 element, and a Ce element, for example, (γ, Ce) 3 eight 15012 are equal and contain at least one phase of this fluorescing crystalline phase. The oxide phase containing these crystal phases which emit fluorescence forms a structure which is continuous and three-dimensionally intertwined. 'Because the oxide phases are uniformly distributed in the light-transforming 5 composite body as a whole, part of the obtained is not obtained. Skewed homogeneous fluorescent light.

The combination of 2〇3 phase and (Y, CeLAlsO) 2 phase can easily obtain a structure in which both are continuous and three-dimensionally intertwined. In addition, (γ, CeLAl^2 phase is purple at 400~500nm) The blue excitation light is suitable as a 1 〇 light conversion member for a white light-emitting device because it emits fluorescence having a peak wavelength of 530 to 560 nm. Therefore, it is preferable that the composition contains at least a Y element, an A1 element, and a Ce element. Plus the Gd element, it will generate (γ, Gd,

The Ce3Al5〇12 phase serves as a crystal phase that emits fluorescence, and emits fluorescence of 540 to 580 nm having a peak wavelength on the longer wavelength side. The solidified body constituting the light-converting composite of the present invention is produced by melting the raw material oxide and then solidifying it. For example, a solidified body can be obtained by a simple method of controlling the cooling temperature while cooling and coagulating the material (4) placed at a predetermined temperature, but it is most suitable if it is produced by the early solidification method. The crystal phase contained is continuously grown in a single crystal state by performing :: solidification, thereby reducing the attenuation of light in the member. ~ The solidified body of the light conversion composite of the invention is at least 碛 the previous 2 is the crystal crystallization of the fluorescing, and can be the same as the applicant's door = (4) Ping 7·14959, the Ping TM3 bulletin, special 8 - US Pat. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. The same material as the ceramic composite disclosed in the fifth, ninth, and second, and the like, and can be manufactured by the manufacturing method 5 disclosed in the application (patent). The disclosures of these applications or patents are also hereby incorporated by reference. The composite for light conversion of the present invention can be obtained by processing a solidified body obtained by the above method into a predetermined shape and adjusting the surface to a predetermined surface roughness. The method for adjusting the surface roughness is not particularly limited. However, the physical method of grinding and polishing using grindstones and abrasive grains is easy to apply. The surface roughness of the composite for light conversion of the present invention can be adjusted so that the surface oxide phase can be formed into various predetermined heights, and irregularities having different heights can be formed on each oxide. The surface treatment method is not particularly limited. (4) A method of chemical treatment (wet residual) of an acid solution towel, heat treatment (dry etching) under various gas mist atmospheres, and the like is suitable. The so-called selective etching method is an etching method that makes different etching selectivity depending on the type of oxide. The residual agent can be appropriately selected depending on the type of the composite oxide. For example, a sulfuric acid or acid mixed solution may be used, and a gas containing an element having an action of an oxide such as a C or the like may be used. According to this method, since the desired surface roughness can be achieved without damaging the surface texture of the composite for light conversion when the surface roughness of the composite is adjusted, it is excellent and high fluorescence intensity can be achieved. It is also suitable to form a large surface roughness Ra. 14 200810157 In addition, the surface roughness of the composite for light conversion of the present invention is adjusted by the above-mentioned physical method using grinding stones, abrasive grains, grinding, and chemical treatment in an acid solution. A heat treatment under various gas mists may also be a combination of these methods. At this time, while each of the oxygen-containing compounds has irregularities of different south degrees, the uneven surface having the step is further roughened. ^Invented light conversion composite body due to surface (10) degree reduction, Jingguang intensity is thus increased, if the formation of each oxide height difference of the uneven surface 'is compared with the mirror surface, even with the rough surface formed by grinding Ratio, 10 Perhaps because the ratio of total reflection at the light exit surface is reduced, more light can be taken out from the composite for light conversion, and thus it is possible to have a greater contribution to the improvement of the glory intensity. It is preferable to form an uneven surface having a different height of each oxide, and the surface roughness is preferably Ο.ίμηι or more. As described above, the composite for light conversion of the present invention can obtain homogeneous fluorescence while converting light by converting each oxide phase containing a crystal phase which emits 15 fluorescences continuously and three times. The surface of the composite is treated to have a surface roughness of Ra-〇.〇5pm, and the crystal phase that emits fluorescence can absorb incident light with better efficiency than the composite of light conversion of the same thickness, so that more can be obtained. Strong fluorescent light. In addition, the obtained fluorescence intensity can be controlled by changing the surface roughness Ra, 20. Through such a treatment, the necessary fluorescence intensity can be obtained with a thin thickness, and the volume of the light conversion composite is reduced, so that it is possible to provide light conversion with low cost and suppressed light loss in the composite body. Use a composite. The light-emitting device of the present invention is characterized in that the light-emitting device is a device comprising the light-converting composite of the invention of the above-mentioned No. 15 200810157 and a light-emitting element, and the light from the light-emitting element is irradiated onto the light-converting composite body, and the transmitted light is used. The light of the conversion composite and the fluorescent light converted from the light-emitting element by the light-converting composite. Fig. 1 is a schematic cross-sectional view showing a state of a light-emitting device of the present invention. In the figure, 2 is a composite for light conversion, i is a light-emitting element (light-emitting diode element), 3 is a wire, and 4 is a lead electrode (5) is a fixing member and is used to hold light. The component of the conversion complex 2 •. The side surface of the composite body 2 for light conversion is covered by the member 5, and has a surface 2a for allowing light from the light-emitting element 1 to enter, and a light for transmitting the light-converting complex 10 (a part of the light is converted, and transmitted). The light is mixed together) the surface 2b of the radiation. An embodiment of the light-emitting device of the present invention is a white light-emitting device which emits a peak wavelength of 15~ from a violet-to-blue light-emitting element emitting light having a peak at a wavelength of 400 nm to 500 nm and using light emitted from the light-emitting element. The above-described light conversion composite of yellow fluorescent light of 580 nm is used. The violet-blue light emitted from the violet φ to the color illuminating element is incident on the light-converting composite which has been subjected to the adjustment of the wavelength of the luminescence peak to integrate the wavelengths to obtain white color. Thereby, the yellow fluorescent light from the crystal phase that emits the excited fluorescent light and the purple to blue light that transmits the crystal phase that does not emit fluorescence are homogenized by the structure in which the oxide phase is continuously entangled with each other and the second element is entangled. The ground is mixed, so that white with a small color difference can be obtained. The composite system for light conversion used in the light-emitting device of the present invention is formed into a suitable shape such as a plate shape by the method described in the above. In addition to changing the thickness of the light-converting body, the color tone of the light-emitting device can be easily controlled by changing the surface roughness of the surface of the composite body. By optimizing the thickness and surface roughness of the composite for light conversion, it is possible to obtain a highly efficient light-emitting device in which light loss inside the composite for light conversion is suppressed. In addition, in the case of the unevenness of the color tone of the light-emitting device, it is possible to easily suppress the thickness of the composite for light conversion by the precision of the thickness of the composite for light conversion, and it is also possible to use the surface roughness afterwards. Fine adjustment of the degree. Further suppression is even more. Since the light conversion iridium complex can be used as a member directly, it does not need to be enclosed in a resin, and is not deteriorated by heat and light, so it can be combined with a high-output purple-blue light-emitting element to be used. The device can be outputted high. The light-emitting element used in the light-emitting device of the present invention may, for example, be a light-emitting diode element or a device that emits laser light, but the light-emitting diode element is preferably small in size and can be obtained at low cost. According to the present invention, it is possible to provide an adjustment of the color tone by the thickness of the surface 15 of the composite for light conversion, and to suppress the light loss inside the composite for light conversion by optimizing the thickness and the surface roughness Φ. High efficiency lighting device. Further, the present illuminating device is not deteriorated by heat and light, and is extremely suitable for high output. EXAMPLE 20 Hereinafter, the present invention will be described in more detail by way of specific examples. - (Example 1) The amount of α-Α12〇3 powder (purity: 99.9%) was weighed to 0.82 in terms of Α103/2, and the powder of Υ3〇 (purity: 99.9%) was converted to 0.175 mol in Υ03/2. Ce02 powder (purity 99.9%) 〇·〇5 mol. These powders were wet-mixed in ethanol for 16 hours on a ball mill 17 200810157 basis, and then ethanol was removed by an evaporator to obtain a raw material powder. The raw material powder is preliminarily melted in a vacuum furnace to form a unidirectionally solidified raw material. Next, the raw material is placed directly into the molybdenum crucible, set to a unidirectional solidification apparatus #5, and the raw material is melted under the pressure of L33xl (r3pa(Kr5T〇n:). Then, the same mist is used in the mist. The speed of 5 mm/hour is decreased, and a solidified body formed by three oxide phases of _A12〇3 (Gemstone) phase (Y' Ce)3Al50124g 'ceAlu〇18;{:3 is obtained. ^ Vertical of solidified body The cross-sectional structure in the solidification direction is shown in Fig. 2. The black part of A is the Al2〇3 phase, and the white part of B is (γ, (^) 3 八15〇12 phase, only a little C gray The part is the CeAluOu phase. Each oxide phase has a structure that is successively intertwined and entangled with each other. It can be seen that the main phosphor phase 'is (Y, CehAlsO) 2 phases are uniformly distributed. Therefore, homogenization can be obtained. Fluorescence. 15 A disk-shaped sample of Φ 16 mm x 〇. 2 mm was cut out from the obtained solidified body, and the fluorescence characteristic was evaluated by the solid-state quantum efficiency measuring device of the spectroscopy. The true spectrum was obtained by the pair. The standard light source is used. The fluorescence spectrum is shown in Fig. 3. Using the excitation light with a wavelength of 460 nm, it can be obtained at 54. 7 nm has a broad fluorescence spectrum with a peak wavelength. 20 A plate of 2 mm x 2 mm x 〇.15 mm is made from the solidified body produced, and on the surface of 2 mm x 2 mm, the surface roughness is Ra = 〇. 〇 7 pm, below It is a composite sample for light conversion with Ra = 0.04 pm. The upper surface is ground with a grindstone using #3000 (JIS R6001), and the following is a surface roughness required for polishing using a polishing paste. 18 200810157 The side surface of the composite material for light conversion obtained is covered, and the excitation light having a wavelength of 463 nm is incident from the lower surface side of the composite material for light conversion. The fluorescence emitted from the upper side is concentrated by the integrating sphere. The intensity of the fluorescence at a wavelength of 547 nm was measured by a spectroscope. The maximum fluorescence intensity of Comparative Example 1 having the same thickness and 5 Å and 下面 μ μ μ μ 为 为 μ μ μ μ μ μ μ 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 The relative fluorescence intensity was 104 ′, and it was found that strong fluorescence was obtained only by the early surface treatment of the surface of the composite disk for the light conversion, 咸·μπι : (Comparative Example 1) 10 Example 1 made into a solidification system made 2mmx2 The plate shape of mm×0·15 mm was adjusted to a surface of 2 mm×2 mm in the same manner as in Example 1, and the surface of the surface roughness was Ra=〇〇4llim for the light conversion composite sample, and the excitation light was incident from the lower side. In the same manner as in the example, the measurement of the intensity of the fluorescence emitted from the upper side is performed. At the same time, the light emitted from the upper side is concentrated by the integrating sphere 15 to obtain the integrated value of the total light emitted (the total radiation beam). . The maximum fluorescence intensity obtained and the total radiation beam were taken as 1 〇〇, and the fluorescence intensity and the total radiation beam of the subsequent examples were expressed as relative values. (Examples 2 to 7) 20 2 mm x 2 mm x was made from the solidification system prepared in Example 1.

In the plate-like shape of 0.15 mm and the surface roughness of the surface of 2 mm x 2 mm, the light-converting composite sample shown in Table 入射, the excitation light was incident from the lower side, and the fluorescence intensity emitted on the upper surface side was performed in the same manner as in Example 1. Determination. The adjustment of the surface roughness is performed by using the abrasive grain size of the grindstone applied to the grinding (JIS 19 200810157, the surface to the surface. The relative fluorescence intensity of each example is shown in Table 1. From Table 1, it is known that In Examples 2, 3, and 4, the relative fluorescence intensity increases as the surface roughness Ra increases, and the relative fluorescence intensity of 105 or more can be obtained by any of the above, and the surface roughness Ra^〇1μιη can be obtained. The strength is 5/. The above glory, step by step, can obtain a fluorescence of 10°/❾ or more. In Examples 4 and 5, it can be seen that the surface roughness Ra is above 0·05μπι. The following incident surface, or the upper surface of the radiation surface, can also obtain strong relative fluorescence intensity. In addition, in Examples 4, 6, and 7, it can be known that the surface roughness Ra of both the upper and lower surfaces is increased. The relative fluorescence intensity is further increased. Further, in the examples 2, 4, 6, and 7, the fluorescence intensity is measured, and the integrated light is concentrated on the upper side to obtain the integrated value of the emitted total light ( Full radiation beam). If the comparison example is 100, then In the embodiment, the total radiation beam is more than 100, and it is known that the total radiation beam is also increased. Table 1 15 Surface roughness [above] Ra (μπι) Surface roughness [below] Ra (μπι) Thickness (mm) Relative firefly Light intensity is relatively full. Ten beams are used. Example 1 0.07 0·04 0.15 104 Example 2 0.14 0.04 0.15 106 101 Example 3 0.43 0.04 0.15 113 Example 4 0.67 0.04 0.15 118 103 Example 5 0.04 0.67 0.15 118 Example 6 0.67 0.67 0.15 124 105 Example 7 1.6 1.6 0.15 128 106 Comparative Example 1 0.04 . 0.4 0.15 100 100 20 200810157 (Comparative Example 2) A plate shape of 2 mm x 2 mm x 0.15 mm was prepared from the solidification system prepared in Example 1, and 2 mm x 2 mm. The surface roughness of the surface was adjusted in the same manner as in the case of Example 5, and the light conversion composite having Ra==0.04 pm was combined with the blue (463 nm) light-emitting diode element. The result of the white light-emitting device, which is not shown in Fig. 1, is shown in Fig. 4. The results are shown in Fig. 4. Blue (463 nm) and yellow (about 540 nm) from the composite for light conversion. The light component of the crest is mixed The CIE color 10 degree coordinate is χ=〇·27, y=0.29. (Example 8) A plate shape of 2 mm x 2 mm x 0.07 mm was produced from the solidification system prepared in Example 1, and the surface of the surface of 2 mm x 2 mm was rough. The degree of use of the grinding wheel of #200 (JIS R6001) is adjusted by the grinding of the grindstone into a composite for light conversion of the upper and lower surfaces of 15^^.64111, and a light-emitting diode element emitting blue (463 nm). The white light-emitting device similar to that of Comparative Example 2 was combined and subjected to measurement of an emission spectrum. The results are shown in FIG. 4 in combination with Comparative Example 2. The CIE chromaticity coordinates x = 0.27 and y = 0.29 were obtained, and even if the thickness was about 50% thinner than that of Comparative Example 2, the same chromaticity was exhibited. It is understood that as the surface roughness Ra of the surface of the composite for light conversion 20 becomes larger than this, it is possible to constitute a light-emitting device of the same chromaticity with a thinner thickness. Further, when the integrated value of the total light in the spectrum (total radiation beam) is compared, the comparative example is 1, and in the eighth embodiment, U is obtained, and in the eighth embodiment, a large amount of light (radiation beam) can be obtained. From this, it can be seen that by increasing the surface roughness Ra of the surface of the composite, it is possible to constitute an efficient light-emitting device in which the loss of light 21 200810157 and 5 is suppressed. (Examples 9 to 11) A plate shape of 2 mm x 2 mm x 0.15 mm was prepared from the solidification system prepared in Example 1, and the surface roughness of the surface of 2 mm x 2 mm was adjusted to the above in the same manner as in Examples 2 to 7. Ra=〇·14μηι (Example 9), i 0·43μπι (Example 1〇), 〇·67μπι (Example 11), all of which are light conversion of Ra=0.04 pm, 3⁄4 composite sample, etc. The cie color when the white light-emitting device is combined with the blue-emitting (463 nm) light-emitting diode element and the comparative example 2 are shown in Fig. 5 in combination. When the thickness 10 of the composite for light conversion is 0.15 mm, the surface roughness Ra of the surface increases, and the CIE chromaticity coordinates X and y change in the direction in which the surface is enlarged (the direction in which the yellow color is enhanced). Thereby, the surface roughness Ra of the surface of the light conversion composite can be utilized to control the color tone of the light-emitting device. (Example 12) 15 A glass powder containing a softening point of 750 t of A1203, SiO 2 , B 2 Cb, Na 20 and K 20 components and a fluorescent powder (Y 〇 95, 〇 € 0. (5) were weighed at a volume ratio of 99:1. ) 3 8 15 〇 12 crystalline powder. These powders were subjected to wet mixing in a ball mill for 16 hours in ethanol, and then ethanol was removed by an evaporator to obtain a raw material powder. To the raw material powder, 1 wt% of PVA was added as a binder, and it was filled in a mold 20, and pressurized at a surface pressure of 100 kgf/cm2 to obtain a molded body of $10 mm x 5 mm. The obtained molded body was subjected to a debonding treatment, and then fired at 800 ° C to obtain a sintered body containing a crystal phase which emits fluorescence. The obtained sintered body is formed into a plate shape of 2 mm x 2 mm x 0.5 mm, and the surface rough greenness of the surface of 2 mm x 2 mm is made into the upper and lower surfaces by grinding 22 200810157

The composite sample for light conversion of Ra = 0.04 pm and the composite sample for light conversion of the upper and lower Ra = 1 · 6 μm were ground by a grinding method, and the fluorescence intensity was measured in the same manner as in Example 1. As a result, the surface roughness is above

The Ra=1.6 pm light conversion composite sample can obtain approximately 15% stronger fluorescence. (Example 13) A sample of a mirror surface having a surface roughness of Ra = 0.04 pm in a plate shape of 2 mm x 2 mm x 0.15 mm and a surface roughness of Ra = 0.04 pm in a solidified body prepared by A. In a mixed acid of 1 (volume ratio), 10 rows of heat treatment at 200 ° C for 2 hours was carried out to obtain a ceramic composite for light conversion of a concave-convex surface having a (γ, Ce) 3Al5012 lower than the Al2〇3 phase by about 7 μm. A cross section of the surface of the obtained ceramic composite for light conversion is shown in Fig. 6. The black portion of a is an Al 2 〇 3 (sapphire) phase, and the white portion of B is (Y, 〇 6) 3 八 15012 phase, forming a concave-convex surface of (Y, CeLAlsO 〗 2 is about 7 μηη lower than the 丨 2 〇 3 phase. The surface roughness of the uneven surface 15 is Ra = 3.2 pm. The side surface of the obtained composite material for light conversion is covered and held, and excitation light of a wavelength of 46311111 is incident from the lower surface side of the composite material for light conversion. The ball is concentrated on the fluorescent light emitted from the upper side, and the intensity of the fluorescent light having a wavelength of 547 nm is measured by a spectroscope. If the maximum fluorescence intensity of Comparative Example 1 having the same thickness and the upper 20 is regarded as 1 〇〇, then The relative fluorescence intensity of the conventional example was 131, and it was found that strong fluorescence was obtained by forming the uneven surface having different heights of each oxide phase and making the surface roughness Ra^〇〇5iLim. At the same time as the light intensity, the light emitted from the upper side 23 200810157 is concentrated by the integrating sphere, and the integrated value of the emitted total light (total radiation beam) is obtained. If the comparative example 1 is 100, the relative total radiation beam is obtained. At 109, it is known that the total radiation beam is significant (Examples 14 to 18) 5 From the solidified body produced in Example 1, a plate shape of 2 mm x 2 mm x 0.15 mm was formed in the same manner as in Example 13, and the surface roughness of the surface of 2 mm x 2 mm was Ra = G. The specular sample of G4pm was subjected to heat treatment at 150 to 200 ° C for 1 to 4 hours in a mixed acid of sulfuric acid: taramic acid = 1: i (volume ratio) to obtain (Y, CehAUOu compared to Al2〇3 phase). The ceramic composite for light conversion of the uneven surface having the step height and the average roughness of 10 Ra as shown in Table 2. The ceramic composite for light conversion of each Example was subjected to fluorescence intensity in the same manner as in Example 13. The obtained fluorescence intensity is shown in Table 2. From the results, it can be seen that when the uneven surface having different heights of each oxide phase is formed, the surface roughness Ra increases with the height difference and the accompanying increase. When the light intensity is increased, by making the surface roughness of the surface of the table 15 1^-0·~1», it is possible to obtain more than 5% of the fluorescent light, and further Ra-0.25 pm, and more than 1% by weight of the fluorescent light can be obtained. It is also known that the total radiation beam is also increased at the same time. (Example 19) 2 mm was obtained from the solidification system prepared in Example 1. X2mmx 2〇〇. 15mm plate-shaped and 2mmx2mm surface roughness Ra=〇〇4 array of mirror sample, under the pressure of 1.33xl〇-3Pa(l〇-5T〇rr), in carbon capacity The heat treatment of the ruthenium was carried out to obtain a ceramic composite for light conversion in which the surface of each of the oxides having different degrees of phase return was formed. The cross section of the surface of the obtained light-converting composite was shown in Fig. 7. The black part of A is 24 200810157

In the Al2〇3 (sapphire) phase, the white portion of B is (Υ, Ce)3Al5〇i:^, and in contrast to Examples 13 to 18, the uneven surface of Al2〇3 is formed to be approximately 20 μm lower than that of (γ, Ce)3Al5012. . When the fluorescence intensity and the total radiation beam were measured in the same manner as in Example 13, as shown in Table 2, the same values as in Example 18 of the same step height were obtained, and it was found that the same effect was obtained in this case. Table 2 Surface roughness Ra (μπι) Height step difference Ra (μπι) Thickness (mm) Relative fluorescence intensity Relative to full body beam Example 13 3.2 7 0.15 131 109 Example 14 0.09 0.2 0.15 106 102 Example 15 0.35 1 0.15 118 105 Example 16 1.3 4 0.15 128 107 Example 17 5.8 12 0.15 133 110 Example 18 9.6 20 0.15 134 112 Example 19 9.5 20 0.15 134 111 Comparative Example 1 0.04 — 0.15 100 100

(Example 20) A plate-shaped composite material for light conversion of 2 mm x 2 mm x 10 0.15 mm was prepared from the solidification system prepared in Example 1, and the surface roughness of the surface of 2 mm x 2 mm was adjusted to Ra = 1.6 pm. Sulfuric acid: sulphuric acid = 1: 1 (volume ratio) of the mixed acid was subjected to heat treatment at 200t: x2h, and as shown in Fig. 8, (Y, Ce) 3Al5〇12 was lower than the a1203 phase by about 5_1 〇μηι surface. Although the surface of the Al2〇3 phase is still the same as the rough surface, (γ, 〇6)3,8,15,12,12,15 will become a surface with reduced roughness due to the treatment. The surface of the entire uneven surface was rough: degree Ra = 7.2 pm. 25 200810157 The side surface of the obtained composite material for light conversion is covered, and the excitation light having a wavelength of 463 nm is incident from the lower surface side of the composite material for light conversion, and the fluorescence emitted from the upper side is concentrated by the integrating sphere. The intensity of fluorescence at a wavelength of 547 nm was measured. If the maximum fluorescence intensity of the comparative example having the same thickness and the upper and lower 5 is Ra=0.04 pm is 1 〇〇, the relative fluorescence intensity of the present embodiment may reach 135, and it is known that each oxide is formed by The uneven surface of the phase height is different, and the uneven surface is further made rough; the surface roughness Ra is increased, and the fluorescence intensity is further increased. Table 3 Surface roughness sugar Ra (μηι) Height step difference Ra (μχη) Thickness (mm) Relative fluorescence intensity relative to full release έ Beam Example 20 7.2 5-!0 0.15 135 112 Comparative Example 1 0.04 — 0.15 100 100 In addition While measuring the intensity of the glory, the integrated light is concentrated on the upper side and the integrated value of the emitted total light (total radiation beam) is obtained. When the comparative example 1 is 100, the total radiation beam is 112, and the total radiation beam is remarkably increased by the uneven surface of each oxide phase having a different height and the rough surface of the uneven surface. (Example 21) From the solidification system prepared in Example 1, a plate-shaped light conversion composite material reduction of 2πιπι>2πιπιχ 0.07 mm was used to adjust the surface roughness of the surface of 2mnix2nini to Ra=L6pm The heat treatment at 200 ° C for 20 min was carried out in a mixed acid of sulfuric acid: phosphoric acid = 1: 丨 (capacity ratio) to obtain the same as in Example 20 (Y, CeLAlsO! 2 is about 5 - i lower than Al 2 〇 3 phase)凹 pm concave 26 200810157 convex ' and convex surface is a rough surface. The present light conversion composite sample and the blue (463 nm) light emitting diode element are combined to form the same white light emitting device as in Comparative Example 2. The results of the luminescence spectrum measurement were shown in Fig. 9 and Comparative Example 2 - and the CIE chromaticity coordinates x = 〇.27, 5 corpses 0·29 were obtained, and the thickness was about 50% thinner than that of Comparative Example 2. It is almost the same chromaticity. In addition, if the integrated value of the total light in the spectrum (total radiation beam) is compared with 1 in Comparative Example 2, Example 21 is 1·13, and feeding 22 can be obtained. More light (radiation beam). According to this, the height of each oxide phase is different. The uneven surface and the surface roughness Ra of the surface of the ruthenium complex are further increased by treating the uneven surface to a rough surface, and it is possible to constitute a light-emitting device which is excellent in suppressing light loss. [Illustration! Simple Cui ^言明] Fig. 1 is a schematic cross-sectional view showing an embodiment of the light-emitting device of the present invention. Fig. 2 is a micrograph of Example 1 of the woven structure of the composite for light conversion of the present invention. Fig. 3 is a fluorescence spectrum diagram of Example 1 which is an example of the fluorescence characteristics of the composite for light conversion of the present invention. Fig. 4 is a view showing the spectrum of the luminescent light of Example 8 of an example of the light-emitting device of the present invention. Fig. 5 is a chromaticity diagram of Examples 9, 10, and 11 of an example of the color tone adjustment method of the light-emitting device of the present invention. Fig. 6 is a cross-sectional microscope of the surface of the composite for light conversion produced in Example 13. Photograph 27 200810157 Fig. 7 is a cross-sectional micrograph of the surface of the composite for light conversion produced in Example 19. Fig. 8 is a laser micrograph of the surface of the composite for light conversion produced in Example 20. 5 Figure 9 is a light-emitting device of the present invention An example of the luminescence of the embodiment 21 is a spectrogram. r 士亚々〆生炫妹约日曰"1 1...light-emitting element® 2...light conversion composite 2a...light incident surface 2b... Surface of light emission • 3... wire, 4... wrong electrode 5... fixing member 28

Claims (1)

200810157 X. Patent application scope: L-Symbolization complex, characterized in that it is a light conversion composite formed by a plurality of oxide phases containing at least a kind of oxide crystal phase which emits fluorescence. (4) The surface roughness of the surface of the combined light human face and the opposite side 5 & light radiating surface is above the arithmetic mean roughness (Ra) of 0.05 pm. 2. The light-converting two-composite according to claim 1, wherein the light-converting composite has at least two or more oxide phases which are continuously and three-dimensionally intertwined with each other, and at least one of the oxide phases The latter is formed by a solidified body of 10 crystalline phases that emit fluorescence. 3. The composite for light conversion according to the first or second aspect of the invention, wherein the surface roughness of both the light incident surface and the light radiating surface on the opposite side is an arithmetic mean roughness (Ra) (h05 pm or more). 4. The surface roughness of the surface of any of the light incident surface and the light radiating surface of the opposite side of the light-converting composite 15 body as described in the first or second aspect of the patent application is arithmetic mean roughness ( Ra) 〇 μ μ μ μ 5 5 5 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光The composite for light conversion according to the second aspect of the invention is characterized in that the light-emitting surface of the composite for light conversion is a concave-convex surface having a different height of each oxide phase. 7· Patent Application No. 2 or 6 The light-converting composite described in the item is characterized in that the light-incident surface of the composite for light conversion is a concave-convex surface having a different height for each oxide phase. 29 200810157 8. The light conversion composite according to claim 6 Light emitting surface The average roughness (Ra) is Ιμιη or more. 9. The composite for light conversion according to the first or second aspect of the invention, wherein the composition for the light conversion composite contains at least a quinone, Α1 The light-emitting device according to any one of claims 1 to 9 and the light-emitting element. 11. The invention is as described in claim 10 In the light-emitting device, the light-converting composite emits fluorescent light having a peak at a wavelength of 530 to 580 nm, and the light-emitting element emits light having a peak at a wavelength of 400 nm to 500 nm. 12. A method of adjusting the color tone by changing the foregoing The color roughness of the light-emitting device described in claim 10 or 11 is adjusted by the surface roughness of the composite for light conversion.